WO2018159812A1 - 積層フィルム、画像表示装置用積層体及び画像表示装置 - Google Patents

積層フィルム、画像表示装置用積層体及び画像表示装置 Download PDF

Info

Publication number
WO2018159812A1
WO2018159812A1 PCT/JP2018/008012 JP2018008012W WO2018159812A1 WO 2018159812 A1 WO2018159812 A1 WO 2018159812A1 JP 2018008012 W JP2018008012 W JP 2018008012W WO 2018159812 A1 WO2018159812 A1 WO 2018159812A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
film
resin
laminated film
porosity
Prior art date
Application number
PCT/JP2018/008012
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
昌幸 瀬尾
俊介 小井土
裕人 山田
隆敏 牟田
根本　友幸
Original Assignee
三菱ケミカル株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三菱ケミカル株式会社 filed Critical 三菱ケミカル株式会社
Priority to KR1020197025436A priority Critical patent/KR20190120228A/ko
Priority to CN201880015327.2A priority patent/CN110382647A/zh
Publication of WO2018159812A1 publication Critical patent/WO2018159812A1/ja

Links

Images

Classifications

    • 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
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • 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
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
    • 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
    • C09J7/26—Porous or cellular plastics
    • 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
    • C09J7/29—Laminated material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general
    • F16L59/02—Shape or form of insulating materials, with or without coverings integral with the insulating materials
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present application relates to a laminated film, a laminate for an image display device, and an image display device.
  • Thermal insulation materials are widely applied to various products such as precision instruments, home appliances, interiors of various vehicles, residential walls, ceilings, etc., which are greatly affected by temperature changes.
  • mobile electronic devices such as smartphones and tablet terminals
  • the influence on users and internal components due to heat generation has become a problem, and a heat insulating material having a high heat insulating effect in a limited installation space has become a problem.
  • a heat insulating material a urethane foam obtained by foaming urethane resin with Freon gas, or a heat insulating material using hydrocarbons as a foaming gas instead of Freon gas, is used, while these heat insulating materials have high heat insulating properties, Since it is difficult to reduce the thickness of the film, its use is limited to applications that can secure a sufficient installation space.
  • Glass mats using glass fibers Patent Document 1
  • heat insulating materials in which xerogel and / or airgel particles are dispersed in the fibers Patent Documents 2 and 3
  • propylene-based resins There is a heat insulating material (Patent Document 4) made porous by stretching.
  • Such a heat insulating material can be easily made into a thin film and can easily follow a complicated shape. Therefore, it is easy to use even in a limited space such as the interior of various vehicles and mobile electronic devices.
  • Patent Document 5 discloses a laminated heat insulating sheet composed of a non-porous layer and a porous layer made of a propylene-based resin and an elastomer. Since the front and back layers of this sheet are non-porous layers, it is considered that the risk of the adhesive or pressure-sensitive adhesive soaking in is reduced.
  • a thin and high-performance heat insulating material is required when used in a limited space such as a mobile electronic device, but a laminated heat insulating sheet obtained by the manufacturing method disclosed in Patent Document 5 is required. It has been found by the inventors that high heat insulation properties cannot be obtained.
  • the present invention has been made in view of the above problems, and is a laminated film excellent in heat insulation and processability even in a thin film, a laminate for an image display device provided with the laminated film, and the It is an object to provide an image display device provided with a laminate for an image display device.
  • a laminated film having an air permeability of 1000 seconds / dL or more and a porosity of 50% or more [2] The laminated film according to [1], wherein the resin film having the porous layer (I) and the layer (II) has a thermal conductivity of less than 0.025 W / mK.
  • a laminate for an image display device comprising at least one selected from the group consisting of a touch panel, an image display panel, a surface protection panel, a retardation film, a polarizing film, a color filter, and a flexible substrate.
  • An image display device provided with the laminate for an image display device according to [6].
  • the laminated film of this invention is excellent in sufficient heat insulation, and excellent in workability.
  • the laminated film of the present invention has a porous layer (I) and reduces pore heat transfer.
  • the air permeability is 1000 seconds / dL or more and the porosity of the film is 50% or more, material heat transfer is reduced and excellent heat insulation is provided.
  • the laminated film of the present invention has the layer (II), when the adhesive layer or the adhesive layer is provided on the layer (II), the adhesive or adhesive material is dyed when the adhesive or adhesive is applied. The pores derived from the internal porous structure are maintained, and the heat insulating property does not deteriorate.
  • the laminated film of the present invention forms a porous layer by making it porous upon stretching, it does not use a foaming agent such as gas and has high environmental compatibility.
  • a foaming agent such as gas
  • no foaming agent since no foaming agent is used, it is easy to make a thin film, and it can be used in limited installation spaces such as interiors of various vehicles and mobile electronic devices.
  • Laminated film A laminated film according to an embodiment of the present invention includes a porous layer (I) mainly composed of a propylene-based resin (A) and a porous layer (I ) At least on one side of the layer (II) mainly composed of the propylene-based resin (B), and an adhesive layer or an adhesive layer on the layer (II), and the air permeability is 1000 seconds / dL or more. And a laminated film having a porosity of 50% or more.
  • the “adhesive layer or adhesive layer” may be referred to as “layer (III)”.
  • Air permeability The air permeability of this film is 1000 seconds / dL or more, preferably 5000 seconds / dL or more, and more preferably 10,000 seconds / dL or more.
  • the air permeability represents the difficulty in passing through the air in the thickness direction of the laminated film, and is specifically expressed in the number of seconds required for 100 ml of air to pass through the laminated film. Therefore, it means that the smaller the numerical value is, the easier it is to pass through, and the higher numerical value is, the more difficult it is to pass. That is, the smaller the value means that the communication in the thickness direction of the laminated film is better, and the larger the value means that the communication in the thickness direction of the laminated film is worse.
  • Communication is the degree of connection of holes in the thickness direction of the laminated film.
  • the air permeability of the laminated film By setting the air permeability of the laminated film to 1000 seconds / dL or more, air communication in the thickness direction of the film is lowered, so that the laminated film is excellent in heat insulation.
  • a layer (II) described later it becomes easy to obtain a film having an air permeability in the above range.
  • the adhesive film or adhesive is applied to form the adhesive layer or the adhesive layer on the layer (II) because the laminated film has the layer (II), adhesion to the porous layer (I) portion Intrusion of the adhesive or the pressure-sensitive adhesive can be prevented, and a decrease in heat insulation can be suppressed.
  • the air permeability (seconds / 100 ml) can be measured according to JIS P8117, and specifically can be measured by the method described in the examples.
  • the porosity of the film is an important factor for defining the porous structure, and is a numerical value indicating the ratio of the space portion of the porous layer in the film. In general, it is known that the higher the porosity, the better the heat insulating properties.
  • the porosity of the film is 50% or more, preferably 55% or more, more preferably 60%. That's it. If the porosity is 50% or more, a laminated film having excellent heat insulation can be obtained. The upper limit is not particularly defined but is usually 75% or less.
  • the method for measuring the porosity is as follows.
  • the density of the resin composition is calculated by heating the laminated film to the melting point or higher to melt the film and eliminating the voids, and then producing a press sample and measuring the volume and mass of the press sample. To do.
  • the porosity of the resin film portion having the porous layer (I) and the layer (II) excluding the adhesive layer or the adhesive layer is 50% or more. Preferably it is 55% or more, more preferably 60% or more. If the porosity is 50% or more, a laminated film having excellent heat insulation can be obtained.
  • the “resin film” refers to a film having a porous layer (I) and a layer (II) and not having an adhesive layer and an adhesive layer, and is a stretched film or an unstretched film. It doesn't matter if it exists.
  • the porosity P1 (%) of the resin film having the porous layer (I) and the layer (II), and the porosity of the resin film in the laminated film It is preferable that the rate P2 (%) satisfies the following formula (2).
  • the porosity P1 is a porosity of the resin film which has a porous layer (I) and a layer (II) and does not have an adhesive layer and an adhesive layer on the layer (II).
  • the porosity P2 has a porous layer (I) and a layer (II), and a film having an adhesive layer or an adhesive layer on the layer (II), that is, a resin film portion of a laminated film. It is porosity.
  • the resin film has a hole before the adhesive or the pressure-sensitive adhesive is applied on one side of the resin film.
  • the rate is the porosity P1
  • the porosity of the resin film after applying the adhesive or pressure-sensitive adhesive is the porosity P2.
  • a resin film having the layer (II) on at least one surface of the porous layer (I) is produced, and the porosity P1 is calculated for this film.
  • an adhesive or pressure-sensitive adhesive is applied to the resin film using a coating device such as a bar coater and dried, and then a PET film is pasted to obtain a measurement sample.
  • an adhesive or a pressure-sensitive adhesive is applied on a PET film by the same method as in the measurement sample preparation and dried to obtain a comparative sample.
  • the substantial amount W2 of the resin film part is calculated by calculating the difference in mass between the comparative sample and the measurement sample.
  • the mass W0 when the porosity is 0% is calculated based on the density of the resin composition constituting the resin film, and the porosity P2 is calculated based on the following formula from these values.
  • Porosity (%) ⁇ (W0 ⁇ W2) / W0 ⁇ ⁇ 100
  • the porosity P2 can be calculated by the method using the PET film described above for the laminated film obtained by calculating and applying an adhesive or a pressure-sensitive adhesive to the resin film.
  • the change in porosity can be measured by any measurement method.
  • Pore abundance ratio of porous layer (I) The porosity of this film is 50% or more, and this film has a number of pore structures. Most of the pore structure is present in the porous layer. Porous layer of the present film (I) is preferably present ratio of the porous layer (I) hole is pore area 3 [mu] m 2 or more in the cross section of the (N A, pieces / 100 [mu] m 2) satisfies the formula (1) .
  • abundance ratio of the porous layer (I) of at open area 3 [mu] m 2 or more in the cross section hole is one / 100 [mu] m 2 or less, to suppress the generation of coarse pore size leading to deterioration of holes heat transfer, the film It can have excellent heat insulation.
  • the abundance ratio of pores having a pore area of 3 ⁇ m 2 or more in the cross section of the porous layer (I) is measured by the following method. Using a scanning electron microscope (SEM) (“S-4500 manufactured by Hitachi High-Technologies Corporation”), it was visually confirmed that the porous layer (I) and the layer (II) were formed from the cross-sectional image of the porous film. The porous layer (I) is confirmed, and image processing is performed using image analysis software “SPIP (version 6.6.4)” manufactured by Image Metrology.
  • SPIP version 6.6.4
  • the detection method is set as a threshold, the detection is set as a hole, the threshold type is set as a fixed level, the hole threshold level is set as 80 Arbitrary, and the area is selected in the output without defining the hole range by a filter. After measuring the area of each hole, the ratio of holes having a hole area of 3 ⁇ m 2 or more in the cross section of the porous layer (I) is calculated.
  • the thickness of the film is not particularly limited, but is preferably 1.1 ⁇ m or more, more preferably 10 ⁇ m or more, and further preferably 20 ⁇ m or more.
  • the upper limit is preferably 400 ⁇ m or less, more preferably 300 ⁇ m or less, and particularly preferably 200 ⁇ m or less. If thickness is 1.1 micrometers or more, Preferably it is 10 micrometers or more, it has a sufficient air layer in a porous layer, and can ensure heat insulation. Moreover, if thickness is 400 micrometers or less, use is easy also for the use used for the limited space where an installation place is narrow.
  • the thermal conductivity is an important factor for defining the heat insulating material, and is one of the indexes of the heat insulating performance in this film.
  • the thermal conductivity is preferably less than 0.025 (W / mK), more preferably less than 0.023 (W / mK), still more preferably less than 0.021 (W / mK). is there.
  • the thermal conductivity is less than 0.025 (W / mK)
  • a laminated film having excellent heat insulation is obtained. If the film satisfies the above “abundance ratio of pores in the porous layer” and the “porosity”, it is easy to obtain a film having a thermal conductivity in the above range.
  • the measurement method of thermal conductivity is as follows.
  • the film is cut into 10 mm squares, and the thickness is measured with a micrometer.
  • the thermal diffusivity is evaluated using a xenon flash method (manufactured by NETZSCH, model: LFA447 nanoflash).
  • the thermal conductivity is obtained from the product of the bulk density calculated from this value and the mass and the specific heat measured by a differential scanning calorimeter (DSC Pyris 1 manufactured by Perkin Elmer).
  • the laminated film of the present invention comprises a porous layer (I) containing propylene resin (A) as a main component and a layer (II) containing propylene resin (B) as a main component on at least one surface of the porous layer (I). And a layered structure having the layer (III) (adhesive layer or adhesive layer) on the layer (II).
  • the layer (II) is provided on at least one surface of the porous layer (I)
  • the adhesive layer or the pressure-sensitive adhesive layer is applied to the surface of the layer (II) to form the adhesive layer or the pressure-sensitive adhesive layer. Since the pore structure is not blocked, the heat insulation can be prevented from lowering, so that the laminated film has excellent workability. So to speak, the layer (II) functions as a protective layer for protecting the pores of the porous layer (I) from being blocked.
  • the layer structure of the laminated film of the present invention is not particularly limited, and the porous layer (I) mainly composed of the propylene resin (A) and the layer (II) mainly composed of the propylene resin (B).
  • the porous layer (I) mainly composed of the propylene resin (A) and the layer (II) mainly composed of the propylene resin (B).
  • a multilayer structure of four layers, five layers, or more may be used.
  • it has a layer (II) on at least one side of the porous layer (I), and has an adhesive layer or an adhesive layer on the layer (II)
  • it has excellent heat insulation, It becomes a laminated film excellent in workability.
  • the porous layer (I) is arranged in the intermediate layer, and the layer (II) is arranged in the front and back layers of the porous layer (I).
  • the laminated film of the present invention is a laminated heat insulating film.
  • the adhesive layer or the pressure-sensitive adhesive layer formed on the layer (II) is a resin after stretching a resin film including the porous layer (I) and the layer (II). It is preferable to form an adhesive layer or an adhesive layer by applying an adhesive or an adhesive to the surface of the layer (II) of the film.
  • the ratio of the thickness of each layer (laminate ratio) of the laminated film of the present invention is not particularly limited.
  • the thickness ratio between the porous layer (I) and the layer (II) in the laminated film of the present invention can be appropriately adjusted according to the application and purpose.
  • the layer thickness of the layer (III) adheresive layer or adhesive layer
  • the thickness ratio [(I) :( II)] between the porous layer (I) and the layer (II) is preferably 1: 1 to 1: 0.025, more preferably. Is from 1: 0.5 to 1: 0.05.
  • the thickness ratio between the porous layer (I) and the layer (II) is in the above range, the balance between the heat insulating properties and the mechanical properties is good, and it is particularly suitable for use as a heat insulating film.
  • the “thickness of the porous layer (I)” refers to the total thickness of the plurality of porous layers (I). The same applies to layer (II). Adjustment of the thickness and thickness ratio of the porous layer (I) and the layer (II) in the laminated film can be controlled by adjusting the thickness of the nonporous film-like material before stretching, stretching conditions, and the like.
  • the lamination ratio of the porous layer (I) with respect to the total thickness is preferably 50% or more and 97% or less, more preferably 55% or more and 96% or less, and further preferably 60% or more and 95% or less.
  • the thickness of the porous layer (I) layer in the laminated film is preferably 5 to 290 ⁇ m, more preferably 10 ⁇ m to 280 ⁇ m. If the thickness ratio of the porous layer (I) and the thickness in the film are within this range, the film can have excellent heat insulation properties.
  • the lamination ratio of the layer (II) with respect to the total thickness is preferably 3% or more and 50% or less, more preferably 4% or more and 45% or less, and further preferably 5% or more and 40% or less.
  • the thickness of the layer (II) in the laminated film is preferably 1 to 100 ⁇ m, and more preferably 2 to 95 ⁇ m. If the thickness ratio of the layer (II) and the thickness in the film are within this range, when the adhesive or adhesive is applied onto the layer (II), the penetration of the adhesive or adhesive is suppressed. The pores derived from the internal porous structure are maintained, and the heat insulating property does not deteriorate.
  • the total thickness of each layer is used for calculation.
  • the film only needs to have the above-described configuration, and may further include other layers.
  • Resin film A resin film constituting a laminated film according to an example of the embodiment of the present invention includes a porous layer (I) containing a propylene-based resin (A) as a main component and at least one surface of the porous layer (I) with a propylene-based resin. It is a resin film which has layer (II) which has resin (B) as a main component.
  • Air permeability of the resin film is 1000 seconds / dL or more, preferably 5000 seconds / dL or more, and more preferably 10,000 seconds / dL or more.
  • the air permeability of the resin film is 1000 seconds / dL or more, preferably 5000 seconds / dL or more, and more preferably 10,000 seconds / dL or more.
  • the air permeability (seconds / 100 ml) can be measured according to JIS P8117, and specifically can be measured by the method described in the examples.
  • the porosity of the resin film is an important factor for defining the porous structure, and is a numerical value indicating the ratio of the space portion of the porous layer in the film. In general, it is known that the higher the porosity, the better the heat insulating property.
  • the porosity of the resin film is 50% or more, preferably 55% or more, more preferably 60%. That's it. If the porosity is 50% or more, a resin film having excellent heat insulation can be obtained.
  • the upper limit is not particularly defined but is usually 75% or less.
  • the method for measuring the porosity of the resin film is as follows.
  • the adhesive or adhesive layer on the surface of the laminated film is wiped off with an organic solvent, etc., and the laminated film is immersed in an organic solvent, etc.
  • the porosity can be calculated by calculating the porosity of the resin film obtained by completely removing the adhesive layer and then drying.
  • Pore abundance ratio of porous layer (I) The porosity of the resin film is 50% or more, and the resin film has a large number of pore structures. Most of the pore structure is present in the porous layer. Porous layer constituting the resin film Film (I), the porous layer (I) abundance ratio of the open area 3 [mu] m 2 or more at a hole in the cross section of the (N A, pieces / 100 [mu] m 2) is able to satisfy the equation (1) preferable.
  • the presence ratio of pores having a pore area of 3 ⁇ m 2 or more in the cross section of the porous layer (I) is 1 piece / 100 ⁇ m 2 or less, thereby suppressing generation of a coarse pore diameter that causes deterioration of pore heat transfer, It can have excellent heat insulation.
  • the abundance ratio of pores having a pore area of 3 ⁇ m 2 or more in the cross section of the porous layer (I) is measured by the following method. Using a scanning electron microscope (SEM) (“S-4500 manufactured by Hitachi High-Technologies Corporation”), it was visually confirmed that the porous layer (I) and the layer (II) were formed from the cross-sectional image of the porous film. The porous layer (I) is confirmed, and image processing is performed using image analysis software “SPIP (version 6.6.4)” manufactured by Image Metrology.
  • SPIP version 6.6.4
  • the detection method is set as a threshold, the detection is set as a hole, the threshold type is set as a fixed level, the hole threshold level is set as 80 Arbitrary, and the area is selected in the output without defining the hole range by a filter. After measuring the area of each hole, the ratio of holes having a hole area of 3 ⁇ m 2 or more in the cross section of the porous layer (I) is calculated.
  • the thickness of the resin film is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, and further preferably 20 ⁇ m or more.
  • the upper limit is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, and particularly preferably 150 ⁇ m or less. If thickness is 1 micrometer or more, Preferably it is 10 micrometers or more, it has a sufficient air layer in a porous layer, and can ensure heat insulation. Further, if the thickness is 300 ⁇ m or less, it can be used easily for applications that are used in a limited space where the installation place is narrow.
  • Thermal conductivity is an important factor for defining a heat insulating material, and is one of the indexes of heat insulating performance in a resin film.
  • the thermal conductivity is preferably less than 0.025 (W / mK), more preferably less than 0.023 (W / mK), still more preferably less than 0.021 (W / mK). is there.
  • the thermal conductivity is less than 0.025 (W / mK)
  • the resin film has excellent heat insulation. If the film satisfies the above “abundance ratio of pores in the porous layer” and the “porosity”, it is easy to obtain a film having a thermal conductivity in the above range.
  • the measurement method of thermal conductivity is as follows.
  • the film is cut into 10 mm squares, and the thickness is measured with a micrometer.
  • the thermal diffusivity is evaluated using a xenon flash method (manufactured by NETZSCH, model: LFA447 nanoflash).
  • the thermal conductivity is obtained from the product of the bulk density calculated from this value and the mass and the specific heat measured by a differential scanning calorimeter (DSC Pyris 1 manufactured by Perkin Elmer).
  • the adhesive or adhesive layer on the surface of the laminated film is wiped off with an organic solvent or the like, and the laminated film is immersed in the organic solvent, etc.
  • the porosity can be calculated by calculating the thermal conductivity of the resin film for the resin film obtained by completely removing the adhesive layer and then drying.
  • the resin film of the present invention includes a porous layer (I) mainly composed of a propylene-based resin (A), and a layer (II) mainly composed of a propylene-based resin (B) on at least one surface of the porous layer (I). Is a laminated structure.
  • the layer (II) is provided on at least one surface of the porous layer (I)
  • the adhesive layer or the pressure-sensitive adhesive layer is applied to the surface of the layer (II) to form the adhesive layer or the pressure-sensitive adhesive layer. Since it does not block the pore structure, a decrease in heat insulation can be suppressed, so that the resin film has excellent processability. So to speak, the layer (II) functions as a protective layer for protecting the pores of the porous layer (I) from being blocked.
  • the layer structure of the resin film of the present invention is not particularly limited, and the porous layer (I) mainly composed of the propylene-based resin (A) and the layer (II) mainly composed of the propylene-based resin (B).
  • the porous layer (I) mainly composed of the propylene-based resin (A) and the layer (II) mainly composed of the propylene-based resin (B).
  • a multi-layer structure of three layers, four layers, five layers, or more may be used.
  • the resin film is excellent in heat insulation and processability.
  • the porous layer (I) is arranged in the intermediate layer, and the layer (II) is arranged in the front and back layers of the porous layer (I).
  • the ratio of the thickness of each layer (lamination ratio) of the resin film of the present invention is not particularly limited.
  • the thickness ratio between the porous layer (I) and the layer (II) in the resin film of the present invention can be appropriately adjusted according to the application and purpose. From the viewpoint of obtaining the effect of the present invention, the thickness ratio [(I) :( II)] between the porous layer (I) and the layer (II) is preferably 1: 1 to 1: 0.025, more preferably. Is from 1: 0.5 to 1: 0.05.
  • the thickness ratio between the porous layer (I) and the layer (II) is in the above range, the balance between the heat insulating properties and the mechanical properties is good, and it is particularly suitable for use as a heat insulating film.
  • the “thickness of the porous layer (I)” refers to the total thickness of the plurality of porous layers (I).
  • layer (II) Adjustment of the thickness and thickness ratio of the porous layer (I) and the layer (II) in the resin film can be controlled by adjusting the thickness of the nonporous film-like material before stretching, stretching conditions, and the like.
  • the lamination ratio of the porous layer (I) with respect to the total thickness is preferably 50% or more and 97% or less, more preferably 55% or more and 96% or less, and further preferably 60% or more and 95% or less.
  • the thickness of the porous layer (I) layer in the resin film is preferably 5 to 290 ⁇ m, more preferably 10 ⁇ m to 280 ⁇ m. When the thickness ratio of the porous layer (I) and the thickness in the film are within this range, the resin film can have excellent heat insulation properties. Further, the lamination ratio of the layer (II) with respect to the total thickness is preferably 3% or more and 50% or less, more preferably 4% or more and 45% or less, and further preferably 5% or more and 40% or less. The thickness of the layer (II) in the resin film is preferably 1 to 100 ⁇ m, and more preferably 2 to 95 ⁇ m.
  • the thickness ratio of the layer (II) and the thickness in the film are within this range, when the adhesive or adhesive is applied onto the layer (II), the penetration of the adhesive or adhesive is suppressed. The pores derived from the internal porous structure are maintained, and the heat insulating property does not deteriorate.
  • the total thickness of each layer is used for calculation.
  • porous layer (I), layer (II) (protective layer) and layer (III) (adhesive layer or adhesive layer) constituting the laminated film of the present invention will be described. Then, the formation method of this film as a manufacturing method is demonstrated.
  • Porous layer (I) The porous layer (I) constituting the laminated film of the present invention contains a propylene-based resin (A).
  • A propylene-based resin
  • Propylene resin (A) As the propylene-based resin (A) in the present invention, homopolypropylene (propylene homopolymer), or propylene and ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene or Examples thereof include a random copolymer or a block copolymer with an ⁇ -olefin such as 1-decene. Among these, homopolypropylene is more preferably used from the viewpoint of mechanical strength.
  • the propylene resin (A) preferably has a stereotactic regular isotactic pentad fraction of 80 to 99%, more preferably 83 to 98%, and still more preferably 85 to 97%. . If the isotactic pentad fraction is 80% or more, the mechanical strength is good. On the other hand, the upper limit of the isotactic pentad fraction is defined by the upper limit that can be obtained industrially at the present time, but this is not the case when a more regular resin is developed at the industrial level in the future. is not.
  • the isotactic pentad fraction is a three-dimensional structure in which all five methyl groups as side chains are located in the same direction with respect to the main chain of carbon-carbon bonds composed of arbitrary five propylene units. Or the ratio is meant.
  • Signal assignment of the methyl group region is as follows. Zambelli et al. (Macromol. 8, 687 (1975)).
  • the propylene-based resin (A) preferably has a Mw / Mn, which is a parameter indicating a molecular weight distribution, of 1.5 to 10.0. More preferably, it is 2.0 to 8.0, and still more preferably 2.0 to 6.0. This means that the smaller the Mw / Mn, the narrower the molecular weight distribution.
  • Mw / Mn is measured by a GPC (gel per emission chromatography) method.
  • the melt flow rate (MFR) of the propylene-based resin (A) is not particularly limited, but usually the MFR is preferably 0.5 to 15 g / 10 minutes, and preferably 1.0 to 10 g / 10. More preferably, it is minutes.
  • the MFR is preferably 0.5 to 15 g / 10 minutes, and preferably 1.0 to 10 g / 10. More preferably, it is minutes.
  • the MFR is measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg according to JIS K7210-1 (2014).
  • the manufacturing method of propylene-type resin (A) is not specifically limited,
  • the well-known polymerization method using the well-known polymerization catalyst for example, the multisite catalyst represented by the Ziegler-Natta type
  • propylene-based resin (A) examples include, for example, trade names “Novatech PP” “WINTEC” (manufactured by Nippon Polypro), “Versify” “Notio” “Toughmer XR” (manufactured by Mitsui Chemicals), “Zeras”, “Thermo Run”.
  • the porous layer (I) can be obtained, for example, by stretching a nonporous film-like material made of a resin composition containing as a main component a propylene-based resin (A) containing a large amount of ⁇ crystals, which is one of crystal forms.
  • a porous structure using ⁇ crystals since the ⁇ crystals in the propylene-based resin are converted into ⁇ crystals during the stretching process, the porous structure is dense and the conventionally known inorganic filler, non- Compared to pore formation by adding a compatible organic substance or the like, it is advantageous for the preparation of a porous structure because it does not depend on the particle diameter and dispersion diameter.
  • the ⁇ crystal activity of the porous layer (I) can be regarded as an index indicating that the propylene-based resin was generating ⁇ crystals in the non-porous film-like material before stretching. If the propylene-based resin in the non-porous film-like material before stretching produces ⁇ -crystals, many fine and uniform pores are formed by subsequent stretching, so it has excellent mechanical properties and is fine and uniform. Excellent heat insulation can be obtained by forming the holes.
  • the presence or absence of ⁇ crystal activity in the porous layer (I) is determined by performing differential thermal analysis of the porous layer (I) using a differential scanning calorimeter and detecting the crystal melting peak temperature derived from the ⁇ crystal of the propylene resin. It is judged by whether or not it is done. Specifically, the laminated film is heated from 25 ° C. to 240 ° C. at a heating rate of 10 ° C./min for 1 minute, and then cooled from 240 ° C. to 25 ° C. at a cooling rate of 10 ° C./min. When the temperature is lowered for 1 minute and then heated again from 25 ° C. to 240 ° C. at a heating rate of 10 ° C./min, the crystal melting peak temperature (Tm ⁇ ) derived from the ⁇ crystal of the propylene resin at the time of reheating is If detected, it is determined to have ⁇ crystal activity.
  • Tm ⁇ crystal melting peak temperature
  • Patent No. A method of adding a propylene-based resin that has been treated to generate peroxide radicals as described in Japanese Patent No. 3739481, and a ⁇ -crystal nucleating agent is added to the resin composition constituting the porous layer (I)
  • the method etc. are mentioned.
  • a ⁇ crystal nucleating agent By adding a ⁇ crystal nucleating agent, the production of ⁇ crystals of a propylene resin can be promoted more uniformly and efficiently, and a laminated film having a porous layer (I) having ⁇ crystal activity can be obtained. it can.
  • the porous layer (I) contains the propylene resin (A) as a main component, and the content thereof is 50% by mass or more, preferably 70 to 99.9999% by mass, more preferably 80 to 99.999% by mass, and still more preferably. 90 to 99.99% by mass.
  • the porous layer (I) preferably has the ⁇ -crystal activity in order to obtain a fine porous structure, and among them, it preferably includes a ⁇ -crystal nucleating agent.
  • the ⁇ crystal nucleating agent used in the present invention include the following, but are not particularly limited as long as they increase the generation and growth of ⁇ crystals of the propylene resin, and two or more types are mixed and used. May be.
  • ⁇ crystal nucleating agent examples include amide compounds; tetraoxaspiro compounds; quinacridones; iron oxides having a nanoscale size; potassium 1,2-hydroxystearate, magnesium benzoate or magnesium succinate, magnesium phthalate, etc.
  • Alkali metal salts or alkaline earth metal salts of carboxylic acids represented by: aromatic sulfonic acid compounds represented by sodium benzenesulfonate or sodium naphthalenesulfonate; di- or triesters of dibasic or tribasic carboxylic acids; Phthalocyanine pigments typified by phthalocyanine blue, etc .; two-component compounds consisting of component A, which is an organic dibasic acid, and component B, which is an oxide, hydroxide or salt of a Group 2 metal in the periodic table; cyclic phosphorus compounds And magnesium compound Such as the formation thereof.
  • one or more selected from the group consisting of amide compounds, tetraoxaspiro compounds, and quinacridones are preferable.
  • ⁇ crystal nucleating agents include the ⁇ crystal nucleating agent “NJESTER NU-100” manufactured by Shin Nippon Rika Co., Ltd., and specific examples of propylene resins to which ⁇ crystal nucleating agents are added include Aristech. Examples thereof include polypropylene “Bepol B-022SP”, polypropylene manufactured by Borealis “Beta ( ⁇ ) -PP BE60-7032,” polypropylene manufactured by Mayzo “BNX BETAP-LN”, and the like.
  • the content of the ⁇ -crystal nucleating agent in the porous layer (I) can be appropriately adjusted depending on the type of the ⁇ -crystal nucleating agent or the composition of the propylene-based resin, but 100 mass of the propylene-based resin in the porous layer (I). 0.0001 to 5.0 parts by mass with respect to parts, preferably 0.001 to 3.0 parts by mass, and more preferably 0.01 to 1.0 parts by mass. If it is 0.0001 part by mass or more, ⁇ -crystals of propylene resin can be generated and grown sufficiently at the time of production, sufficient ⁇ -crystal activity can be secured, and sufficient ⁇ -crystal activity can be secured even when a laminated film is formed. The desired heat insulating properties can be obtained. On the other hand, addition of 5.0 parts by mass or less is preferable because it is economically advantageous and there is no bleeding of the ⁇ crystal nucleating agent on the film surface.
  • the layer (II) (protective layer) in the laminated film of the present invention is a layer that does not soak when a solvent is dropped on its surface.
  • the protective layer (II) is observed with a scanning electron microscope (SEM) (“S-4500, manufactured by Hitachi High-Technologies Corporation), and image analysis software“ SPIP (version 6.6. 4) ”as the image processing method, the detection method is set as a threshold, the detection is set as a hole, the threshold type is set as a fixed level, the hole threshold level is set as 80 Arbitrary, and the output is performed without defining the hole range by a filter.
  • the layer (II) has no pores of 1 ⁇ m 2 or more.
  • Propylene resin (B) The propylene-based resin (B) in the present invention is preferably a propylene-based resin described in the above-mentioned propylene-based resin (A), and is particularly preferably a random propylene-based resin from the viewpoint of hardly generating a porous structure.
  • a random propylene-based resin for the layer (II) it is possible to make it difficult to form voids (holes) during stretching that occur when a homopropylene-based resin, a block propylene-based resin, or the like is selected.
  • coating an adhesive the penetration
  • the layer (II) is mainly composed of the propylene-based resin (B), and the content thereof is 50% by mass or more, preferably 70 to 99.9999% by mass, more preferably 80 to 99.999% by mass, and still more preferably 90%. To 99.99 mass%.
  • Layer (III) adheresive layer or adhesive layer
  • the laminated film of the present invention can easily impart heat insulation to various members bonded through the layer (III).
  • it is used as an interior member of various vehicles, a member of a mobile electronic device or the like.
  • the layer thickness of the layer (III) varies depending on the mass of the adherend, the material, etc., but is preferably 0.1 to 100 ⁇ m from the viewpoint of the adhesive strength to the adherend.
  • Examples of the base polymer (or base elastomer) used in the composition containing at least one of an adhesive and a pressure-sensitive adhesive applied to one side of the layer (II) include natural rubber, synthetic isoprene, styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene / butylene-styrene triblock copolymer (SEBS) hydrogenated with SBS, styrene-ethylene / propylene block copolymer hydrogenated with SI Rubber adhesives mainly composed of styrene-ethylene / propylene-styrene block copolymer (SEPS) hydrogenated with SIS (hydrogenated SIS), acrylic acid ester such as 2-ethylhexyl acrylate or butyl acrylate, or methacrylic acid Mainly ester It is appropriately selected from an
  • the pressure-sensitive adhesive is alicyclic petroleum resin, aliphatic petroleum resin, terpene resin, ester resin, coumarone-indene resin, rosin resin, An epoxy resin, a phenol resin, an acrylic resin, a butyral resin, an olefin resin, a chlorinated olefin resin, a vinyl acetate resin, and a tackifier mainly composed of these modified resins or hydrogenated resins, liquid isoprene, liquid butadiene, Liquid butadiene / isoprene, liquid styrene / butadiene, liquid styrene / isoprene, polybutene, polyisobutylene, liquid terpene, liquid rosin, paraffin oil, plasticizers, isocyanate crosslinkers, epoxy crosslinkers, amine crosslinks Agent, melamine crosslinking agent, aziridine crosslinking agent, hydrazi A crosslinking
  • Solvents used for preparing the adhesive include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; n-pentane, n -Aliphatic hydrocarbon solvents such as hexane and n-heptane; and alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane. These solvents can be used alone or in combination of two or more.
  • Each layer constituting this film has additives that do not impair its properties, such as heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, crystal nucleating agents, colorants, antistatic agents, and hydrolysis inhibitors.
  • additives such as an agent, a lubricant, a flame retardant, and an elastomer may be appropriately included.
  • other resin compositions may be contained to such an extent that the property is not impaired.
  • Manufacturing method of laminated film The manufacturing method of the laminated film of the present invention will be described. The following description is an example of a method of manufacturing the laminated film of the present invention, and the laminated film of the present invention is manufactured by such a manufacturing method. It is not limited to a laminated film.
  • a method for producing a laminated film according to an example of an embodiment of the present invention includes a layer containing a propylene resin (A) as a main component and a ⁇ crystal nucleating agent (C).
  • A propylene resin
  • C ⁇ crystal nucleating agent
  • the film production method may include the above-described steps, and may further include other steps, treatments, and the like.
  • resins include polystyrene resins, polyvinyl chloride resins, polyvinylidene chloride resins, chlorinated polyethylene resins, polyester resins, polycarbonate resins, polyamide resins, polyacetal resins, acrylic resins, ethylene acetate Vinyl copolymer, polymethylpentene resin, polyvinyl alcohol resin, cyclic olefin resin, polylactic acid resin, polybutylene succinate resin, polyacrylonitrile resin, polyethylene oxide resin, cellulose resin, polyimide resin , Polyurethane resin, polyphenylene sulfide resin, polyphenylene ether resin, polyvinyl acetal resin, polybutadiene resin, polybutene resin, polyamideimide resin, polyamide bismaleimide resin, Arylate resins, polyether imide resins, polyether ether ketone resin, polyether ketone resin, polyether sulfone resin, polyketone resin, polysulfone resin, aramid-based resin, flu
  • additives that are generally blended can be added as appropriate within a range that does not significantly impair the effects of the present invention.
  • the additive include recycled resin generated from trimming loss of ears and the like, silica, talc, kaolin, carbonic acid, which are added for the purpose of improving or adjusting molding processability, productivity and various physical properties of the porous film.
  • Inorganic particles such as calcium, pigments such as titanium oxide and carbon black, flame retardants, weathering stabilizers, heat stabilizers, antistatic agents, melt viscosity improvers, crosslinking agents, lubricants, nucleating agents, plasticizers, anti-aging agents , Antioxidants, light stabilizers, ultraviolet absorbers, neutralizers, antifogging agents, antiblocking agents, slip agents, colorants and the like.
  • the machine to be used is not particularly limited.
  • a known extruder such as a single screw extruder, a twin screw extruder, or a multi-screw extruder can be used.
  • a pressure reducer may be connected to the vent port to remove moisture and low molecular weight substances.
  • Film-forming process examples of a method for heating and melting the material resin include a T-die method and an inflation method. Among these, the T-die method is preferably employed. Practically, it is preferable that the material resin is melt-extruded from a T-die and cast by a cast roll.
  • a sheet-like molten resin extruded from the T-die is laminated and adhered onto a rotating cast roll (chill roll, cast drum).
  • a rotating cast roll chill roll, cast drum.
  • molding in a take-off sheet-like material can be mentioned.
  • a touch roll, an air knife, an electric contact device or the like may be attached to the cast roll in order to bring the film-like material into close contact with the cast roll.
  • the temperature of the cast roll is preferably 100 ° C. or higher. More preferably, it is 110 degreeC or more, More preferably, it is 120 degreeC or more.
  • the porosity of the cast roll can be increased by 100 ° C. or higher because the porosity can be increased by the opening of the crystalline portion and the amorphous portion of the propylene-based resin in the porous layer (I) by the stretching step.
  • the thickness of the effective portion excluding both ends is preferably 50 ⁇ m to 1000 ⁇ m, more preferably 80 ⁇ m or more and 800 ⁇ m or less, and particularly preferably 100 ⁇ m or more or 600 ⁇ m or less. If the unstretched film thickness is 50 ⁇ m or more, the film is too thin to prevent breakage during stretching. If the unstretched film thickness is 1000 ⁇ m or less, the film becomes too rigid. It is possible to prevent the stretching from becoming difficult.
  • the layer structure of the laminated film of the present invention in the original fabric may be not only the above layer structure but also a structure in which other layers are combined.
  • the ratio (T2 / T1) of the thickness (T2) of the layer (II) to the thickness (T1) of the porous layer (I) preferably satisfies the relationship of 0.05 to 1.0.
  • the thickness ratio is within this range, a film excellent in heat insulation even in the case of a thin film and excellent in workability that does not cause deterioration in heat insulation even when an adhesive or a pressure-sensitive adhesive is applied can be obtained. It is done.
  • the total thickness of each layer is used for calculation.
  • the unstretched film preferably has a layer (I) having a thickness of 50 to 600 ⁇ m.
  • the lower limit of this thickness is more preferably 55 ⁇ m, still more preferably 60 ⁇ m.
  • the upper limit is more preferably 580 ⁇ m, still more preferably 550 ⁇ m.
  • the laminated film which has favorable heat insulation is obtained because the thickness of layer (I) is 50 micrometers or more.
  • the thickness of the layer (I) is 600 ⁇ m or less, a stretched film having a thickness of 300 ⁇ m or less after stretching can be obtained.
  • the unstretched film preferably has a layer (II) of 5 to 300 ⁇ m.
  • the lower limit of this thickness is more preferably 10 ⁇ m and even more preferably 20 ⁇ m.
  • the upper limit is more preferably 250 ⁇ m, and still more preferably 200 ⁇ m.
  • Uniaxial stretching may be longitudinal uniaxial stretching or transverse uniaxial stretching.
  • Biaxial stretching may be simultaneous biaxial stretching or sequential biaxial stretching.
  • sequential biaxial stretching is more preferred because the stretching conditions can be selected in each stretching step and the porous structure can be easily controlled.
  • stretching to the flow direction (MD) of a film-like thing is called “longitudinal stretching”
  • vertical direction (TD) with respect to a flow direction is called "lateral stretching.”
  • the stretching temperature needs to be selected in a timely manner according to the composition of the resin composition to be used, the crystal melting peak temperature, the crystallinity, etc., but the control of the porous structure is relatively easy, the mechanical strength, It is easy to balance with other physical properties such as shrinkage.
  • the longitudinal stretching temperature is preferably 60 to 140 ° C, more preferably 80 to 120 ° C. It is preferable to set the longitudinal stretching temperature to 140 ° C. or lower because stretching can be performed without breaking below the melting point of the main component propylene resin. On the other hand, since it can suppress the fracture
  • the longitudinal stretching ratio can be arbitrarily selected, but the stretching ratio per uniaxial stretching is preferably 1.1 to 10 times, more preferably 1.5 to 8.0 times, and further preferably 1.5 to 6. 0 times.
  • the stretch ratio per uniaxial stretching is 1.1 times or more, whitening proceeds and sufficient porosity is achieved by stretching.
  • the transverse stretching temperature is preferably 100 to 160 ° C, more preferably 110 to 150 ° C.
  • the pores generated during the longitudinal stretching can be expanded to increase the porosity of the porous layer, and thus sufficient heat insulation can be achieved.
  • the transverse draw ratio can be arbitrarily selected, but is preferably 1.1 to 10 times, more preferably 1.5 to 9.0 times, and still more preferably 1.5 to 8.0 times.
  • an adhesive or a pressure-sensitive adhesive is applied to the surface of the layer (ii) of the resin film prepared by the stretching process to form the layer (iii).
  • the method of applying the adhesive or pressure-sensitive adhesive layer (ii) on the surface is not particularly limited, and is a spin coater, roll coater, slit coater, air knife coater, bar coater, spray coating, curtain coater, dip coater, die coater, gravure roll. A known method such as the above can be used.
  • the laminated film of the present invention can be subjected to surface treatment such as corona treatment, plasma treatment, printing, coating, vapor deposition, and further perforation as necessary within the range not impairing the present invention. Depending on the situation, it is possible to stack several laminated films of the present invention.
  • Laminated body for image display apparatus, image display apparatus has a touch panel, an image display panel, a surface protection panel, a retardation film, a polarizing film, a color filter on at least one side of the laminated film of the present invention. And any one or more selected from the group consisting of flexible substrates.
  • the image display device of the present invention is provided with the laminate for an image display device of the present invention.
  • An image display device including members for an image display device such as a touch panel, an image display panel, a surface protection panel, a retardation film, a polarizing film, a color filter, and a flexible substrate is generally easily heated and functions by heat generation. May decrease.
  • the laminated film of the present invention is excellent in heat insulation and processability even if it is a thin film. Therefore, it is easy to be bonded to a member for an image display device and an image display device, and the weight of the member for an image display device and the image display device. It is possible to perform heat insulation while suppressing the reduction of the function, and it is possible to suppress the functional deterioration of the image display device member and the image display device.
  • styrene-based elastomer styrene-ethylene / butylene-sty
  • Example 1 100 parts by mass of propylene resin (A-1), 0.2 part by mass of ⁇ -crystal nucleating agent (C-1) and 0.1 part by mass of antioxidant (D-1) were mixed and mixed in a twin screw extruder.
  • the mixture 1 was obtained by melt extrusion at 280 ° C.
  • the thickness of the surface layer [layer (II)] / intermediate layer [layer (I)] / back layer [layer (II)] of the laminated non-porous film (unstretched film) is “unstretched film” in Table 1.
  • the laminated non-porous film-like material was longitudinally stretched by using a longitudinal stretching machine between rolls set at 105 ° C. with a draw ratio of 65% multiplied by 3 stages (longitudinal stretching ratio: 4.5 times).
  • the film after longitudinal stretching was preheated at a preheating temperature of 150 ° C.
  • the adhesive (F-1) for application was applied to the measurement sample using a 50th bar coater, dried at 80 ° C. for 1 minute, and the adhesive layer (III) A laminated film provided with
  • Comparative Example 1 Molding was performed using the mixture 1 with a T die having a lip opening of 1 mm, and the film was guided to a cast roll to obtain a nonporous film-like material. Thereafter, longitudinal stretching and lateral stretching were performed in the same manner as in Example 1 to obtain a resin film. On one side of the obtained resin film, a coating adhesive (F-1) was applied to obtain a laminated film provided with an adhesive layer (III). The evaluation results of the obtained resin film are summarized in Table 1.
  • Comparative Example 2 Using a T-die with a lip opening of 1 mm, molding was performed using propylene-based resin (A-1) in an extruder to obtain a nonporous film. Then, the resin film was obtained by performing longitudinal stretch and lateral stretch by the method similar to Example 1. FIG. On one side of the obtained resin film, a coating adhesive (F-1) was applied to obtain a laminated film provided with an adhesive layer (III). The evaluation results of the obtained resin film are summarized in Table 1.
  • the film thickness, porosity, abundance of holes (N A), an air permeability, thermal conductivity, solvent penetration, the porosity after the adhesive coating It measured by the following method.
  • the porosity, the abundance ratio, the air permeability, the thermal conductivity, and the film thickness were measured on the resin film before forming the adhesive layer (III).
  • Example 1 the film provided with the adhesive layer (III) was also measured.
  • Porosity (i) Porosity P1 The substantial amount W1 of the resin film was measured, the mass W0 when the porosity was 0% was calculated based on the density of the resin composition, and the porosity was calculated based on the following formula from these values.
  • Porosity (%) ⁇ (W0 ⁇ W1) / W0 ⁇ ⁇ 100
  • Porosity of laminated film A substantial amount W1 of the laminated film is measured, and a mass W0 when the porosity is 0% is calculated based on the density of the resin composition. The porosity was calculated.
  • Porosity (%) ⁇ (W0 ⁇ W1) / W0 ⁇ ⁇ 100
  • the abundance ratio (N A ) of pores having a pore area of 3 ⁇ m 2 or more in the porous layer (I) was calculated.
  • Table 1 shows that the abundance ratio (N A ) satisfies the formula (1) (N A ⁇ 1) as Y, and that the abundance ratio does not satisfy N as N.
  • Air permeability at 25 ° C. In the air atmosphere at 25 ° C., the air permeability was measured according to JIS P8117. As a measuring instrument, a digital type Oken type air permeability dedicated machine (Asahi Seiko Co., Ltd.) was used.
  • Porosity of resin film after application of adhesive P2
  • the prepared pressure-sensitive adhesive was applied on a PET film and dried to obtain a comparative sample.
  • the substantial amount W2 of the resin film was calculated by subtracting the mass of the comparative sample from the mass of the measurement sample.
  • ⁇ crystal activity The presence or absence of ⁇ crystal activity in each of the resin films of Examples and Comparative Examples was analyzed using a differential scanning calorimeter. Specifically, a differential scanning calorimeter (DSC Pyris 1 manufactured by Perkin Elmer) was used as follows. The resin film was heated from 25 ° C. to 240 ° C. at a heating rate of 10 ° C./min, held for 1 minute, then cooled from 240 ° C. to 25 ° C. at a cooling rate of 10 ° C./min, and then held for 1 minute. ⁇ crystals were produced and grown.
  • DSC Pyris 1 manufactured by Perkin Elmer DSC Pyris 1 manufactured by Perkin Elmer
  • the crystal melting peak temperature (145 to 160 ° C) derived from the ⁇ crystal of the propylene-based resin is detected when the temperature is raised again.
  • Table 1 shows the resin film having ⁇ crystal activity as Y and the resin film not having ⁇ crystal activity as N.
  • Table 1 shows the evaluation results regarding the examples and comparative examples.
  • Y in the “Presence / absence of adhesive layer” column means that the laminated film of Examples or Comparative Examples has an adhesive layer.
  • Example 1 satisfies Formula (1), and there are few coarse pores in the porous layer (I), so that the thermal conductivity is reduced and the heat insulation is excellent. Furthermore, by having the layer (II), it is possible to suppress the change in porosity and to reduce the heat insulation property even when the adhesive is applied in combination with other members. On the other hand, in Comparative Example 1 having no layer (II) (protective layer), uniform application is difficult at the time of application of the pressure-sensitive adhesive, and there is a concern that the heat insulating property is lowered. In the film having no porous layer (I) and layer (II) (protective layer) of Comparative Example 2, no decrease in thermal conductivity is observed.
  • Example 1 the thickness, porosity, air permeability, and pore abundance ratio (N A ) in the state provided with the adhesive layer were 80 ⁇ m in thickness, 57% in porosity, air permeability abundance of 99999 sec / dL, the porous layer hole (N a) was 0/100 [mu] m 2.
  • the laminated film of the present invention can be widely used for various products such as precision equipment, home appliances, interiors of various vehicles, housing walls, ceilings, etc., which are greatly affected by temperature changes, and in particular, it can be thinned. Therefore, it can be expected to be used in the interior of various vehicles, where the installation space is limited, and in the field of mobile electronic devices.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Thermal Insulation (AREA)
PCT/JP2018/008012 2017-03-02 2018-03-02 積層フィルム、画像表示装置用積層体及び画像表示装置 WO2018159812A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020197025436A KR20190120228A (ko) 2017-03-02 2018-03-02 적층 필름, 화상 표시 장치용 적층체 및 화상 표시 장치
CN201880015327.2A CN110382647A (zh) 2017-03-02 2018-03-02 层叠膜、图像显示装置用层叠体及图像显示装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017039834 2017-03-02
JP2017-039834 2017-03-02

Publications (1)

Publication Number Publication Date
WO2018159812A1 true WO2018159812A1 (ja) 2018-09-07

Family

ID=63370086

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/008012 WO2018159812A1 (ja) 2017-03-02 2018-03-02 積層フィルム、画像表示装置用積層体及び画像表示装置

Country Status (5)

Country Link
JP (2) JP7283032B2 (zh)
KR (1) KR20190120228A (zh)
CN (1) CN110382647A (zh)
TW (1) TW201842109A (zh)
WO (1) WO2018159812A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7215034B2 (ja) * 2018-09-19 2023-01-31 三菱ケミカル株式会社 積層多孔フィルム
JP7428044B2 (ja) * 2020-03-26 2024-02-06 三菱ケミカル株式会社 圧電シート

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1060396A (ja) * 1996-08-26 1998-03-03 Nippon Foil Mfg Co Ltd スリーブ穴埋用粘着シート
JP2010510368A (ja) * 2006-11-24 2010-04-02 テーザ・ソシエタス・ヨーロピア 高い耐衝撃性を有する接合手段
WO2016047272A1 (ja) * 2014-09-25 2016-03-31 積水化学工業株式会社 発泡複合シート
JP2016117249A (ja) * 2014-12-22 2016-06-30 三菱樹脂株式会社 積層断熱シート

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004292800A (ja) * 2003-03-13 2004-10-21 Toray Ind Inc 白色ポリプロピレンフィルム
JP2005009566A (ja) 2003-06-18 2005-01-13 Yazawa Sangyo Kk 断熱材
JP2005321593A (ja) * 2004-05-10 2005-11-17 Nitto Denko Corp 液晶表示装置および断熱シート
JP4940808B2 (ja) 2005-07-28 2012-05-30 東レ株式会社 断熱パネル用多孔質ポリプロピレンフィルムおよびそれを用いた車輌用断熱パネル
JP5151017B2 (ja) * 2005-09-22 2013-02-27 東レ株式会社 積層ポリプロピレンフイルム
US20080000581A1 (en) * 2006-06-28 2008-01-03 Gilles Leon Nison Preparation of laminated composite substrates using coated oriented polymeric film
JP4924324B2 (ja) * 2006-09-27 2012-04-25 東レ株式会社 金属化多孔質フィルム
JP2009235232A (ja) * 2008-03-27 2009-10-15 Toray Ind Inc 多孔性ポリプロピレンフィルム
KR101741854B1 (ko) * 2009-06-20 2017-05-30 트레오판 저머니 게엠베하 앤 코. 카게 셧다운 기능을 갖는 전지용 미세다공성 포일
JP2014237910A (ja) 2013-06-10 2014-12-18 パナソニック株式会社 繊維シート
JPWO2015115289A1 (ja) * 2014-01-28 2017-03-23 東レ株式会社 多孔性フィルム、透湿防水シート、複合体および防護服
JP6188245B2 (ja) 2014-01-30 2017-08-30 オゾンセーブ株式会社 断熱材及び断熱材の製造方法
JP6672633B2 (ja) * 2015-08-12 2020-03-25 三菱ケミカル株式会社 反射シート及び反射板
JP6194938B2 (ja) * 2015-10-21 2017-09-13 三菱ケミカル株式会社 積層多孔性延伸フィルム、それを利用した電池用セパレータ及び電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1060396A (ja) * 1996-08-26 1998-03-03 Nippon Foil Mfg Co Ltd スリーブ穴埋用粘着シート
JP2010510368A (ja) * 2006-11-24 2010-04-02 テーザ・ソシエタス・ヨーロピア 高い耐衝撃性を有する接合手段
WO2016047272A1 (ja) * 2014-09-25 2016-03-31 積水化学工業株式会社 発泡複合シート
JP2016117249A (ja) * 2014-12-22 2016-06-30 三菱樹脂株式会社 積層断熱シート

Also Published As

Publication number Publication date
JP2018144490A (ja) 2018-09-20
TW201842109A (zh) 2018-12-01
KR20190120228A (ko) 2019-10-23
JP7283032B2 (ja) 2023-05-30
JP2018144489A (ja) 2018-09-20
JP7283033B2 (ja) 2023-05-30
CN110382647A (zh) 2019-10-25

Similar Documents

Publication Publication Date Title
US8680169B2 (en) Porous polypropylene film
WO2017170244A1 (ja) 二軸配向ポリプロピレンフィルム
TWI781149B (zh) 二軸配向聚丙烯膜
JP6047964B2 (ja) 離型フィルム用樹脂組成物及び離形フィルム
WO2018159812A1 (ja) 積層フィルム、画像表示装置用積層体及び画像表示装置
JP6500699B2 (ja) 延伸フィルム
JP2004142238A (ja) 積層フィルム
JP2020007443A (ja) 食品用包装フィルムおよび食品用包装体
JP7215034B2 (ja) 積層多孔フィルム
JP6561857B2 (ja) 延伸フィルム
JP2016030825A (ja) 二軸延伸ポリプロピレンフィルム
JP6617426B2 (ja) 気体透過性フィルム
JP2020158762A (ja) 圧電フィルム
KR101624334B1 (ko) 단열재 보호필름 및 그 제조방법
JP6672633B2 (ja) 反射シート及び反射板
JP7172498B2 (ja) 多孔フィルム
WO2021132521A1 (ja) 多孔性断熱フィルム及びその製造方法
JP7135709B2 (ja) 多孔フィルム
JP7480550B2 (ja) 多孔フィルム
JP2020131545A (ja) 積層圧電フィルム、圧電素子、および積層圧電フィルムの製造方法
JP2023151346A (ja) 樹脂シート及び樹脂シートの製造方法
JP2022157234A (ja) 樹脂シート及び樹脂シートの製造方法
WO2024005115A1 (ja) 多孔フィルム
JP2022133991A (ja) エレクトレットフィルムの製造方法及び製造装置
TW201510033A (zh) 含空洞聚丙烯膜

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18761144

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20197025436

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18761144

Country of ref document: EP

Kind code of ref document: A1