WO2018159812A1

WO2018159812A1 - Laminated film, laminate for image display device, and image display device

Info

Publication number: WO2018159812A1
Application number: PCT/JP2018/008012
Authority: WO
Inventors: 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: 2017-03-02
Filing date: 2018-03-02
Publication date: 2018-09-07
Also published as: JP2018144490A; JP2018144489A; TW201842109A; CN110382647A; JP7283032B2; JP7283033B2; KR20190120228A

Abstract

The present invention relates to: a laminated film which includes a porous layer (I) having a propylene-based resin (A) as a main component, a layer (II) formed on at least one surface of the porous layer (I) and having a propylene-based resin (B) as a main component, and a bonding layer or an adhesive layer on the layer (II), and which has an air permeability of 1000 sec/dL or greater and a porosity of 50% or greater; a laminate which is for an image display device and is provided with the laminated film; and an image display device provided with the laminate for an image display device. Although the laminated film is thin, the laminated film has excellent heat insulation and processability.

Description

LAMINATED FILM, LAMINATE FOR IMAGE DISPLAY DEVICE, AND IMAGE DISPLAY DEVICE

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. In recent years, in 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. There is a strong demand.
Conventionally, as 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.

However, when using the above heat-insulating material in combination with other electronic material members, if an adhesive or pressure-sensitive adhesive made of a solvent is applied during the heat-insulating sheet processing, the adhesive or pressure-sensitive adhesive penetrates into the porous structure. In addition, there is a concern about uniform adhesiveness, as well as filling pores in the porous structure, which may reduce the heat insulation.

On the other hand, 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. However, 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.

JP 2005-009566 A JP 2014-237910 A International Publication No. 2016/121372 JP 2007-56253 A JP 2016-117249 A

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.

[1] A porous layer (I) mainly composed of a propylene-based resin (A);
A layer (II) mainly composed of a propylene-based resin (B) on at least one surface of the porous layer (I);
Having an adhesive layer or an adhesive layer on the layer (II);
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.
[3] The laminated film according to [1] or [2], wherein the thickness is 1 μm or more and 300 μm or less.
[4] The laminated film according to any one of [1] to [3], which satisfies formula (1).
Formula (1): N _A ≦ 1
_{[N A} represents the abundance ratio of the porous layer (I) of at open area 3 [mu] m ² or more in a cross section hole (pieces / 100 [mu] m ^2). ]
[5] The porosity P1 (%) of the resin film having the porous layer (I) and the layer (II) and the porosity P2 (%) of the resin film in the laminated film are expressed by the following formula (2). The laminated film according to any one of [1] to [4], which is satisfied.
Formula (2): P1-P2 <3
[6] On at least one side of the laminated film according to any one of [1] to [5],
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.
[7] An image display device provided with the laminate for an image display device according to [6].

Even if it is a thin film, the laminated | multilayer film of this invention is excellent in sufficient heat insulation, and excellent in workability.
Specifically, the laminated film of the present invention has a porous layer (I) and reduces pore heat transfer. Furthermore, since 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.
Moreover, since 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.
Furthermore, since 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. In addition, 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.

It is the cross-sectional image which image | photographed the cross section of the TD direction of the resin film of Example 1 with the scanning electron microscope.

Hereinafter, the present invention will be described in detail. However, the contents of the present invention are not limited to the embodiments described below.

1. Laminated film A laminated film according to an embodiment of the present invention (hereinafter sometimes referred to as “the present film”) 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.
Hereinafter, the “adhesive layer or adhesive layer” may be referred to as “layer (III)”.

(1) 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.
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. By having a layer (II) described later, it becomes easy to obtain a film having an air permeability in the above range. When 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.

(2) Porosity 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. In this film, 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 substantial amount W1 of the measurement sample is measured, the mass W0 when the porosity is 0% is calculated based on the density of the resin composition, and the porosity is calculated based on the following formula from these values.
Porosity (%) = {(W0−W1) / W0} × 100

Here, 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.

In the present film, it is preferable that 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.
In this film, 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.

Further, regarding the porosity before and after the formation of the adhesive layer or the adhesive layer, 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).
Formula (2): P1-P2 <3
If the porosity change is less than 3%, the penetration of the adhesive or the pressure-sensitive adhesive into the resin film is suppressed, and a decrease in heat insulation can be reduced.
In addition, 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. For example, when the adhesive layer or the pressure-sensitive adhesive layer is formed on one side of the resin film by applying an adhesive or the pressure-sensitive adhesive, 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, and the porosity of the resin film after applying the adhesive or pressure-sensitive adhesive is the porosity P2.

In order to obtain the porosity P1, P2 defined by the present invention, there are the following methods.
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. Thereafter, 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. On the other hand, 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
However, the porosity P1 of the resin film obtained by wiping off the adhesive layer or the adhesive layer on the surface using an organic solvent or the like and further removing the adhesive layer or the adhesive layer by immersing in an organic solvent and drying the laminated film. 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.
In the present invention, the change in porosity can be measured by any measurement method.

(3) 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) .
Formula (1): N _A ≦ 1
N _A is more preferably 0.5 pieces / 100 μm ² or less (N _A ≦ 0.5), further preferably 0.25 pieces / 100 μm ² or less (N _A ≦ 0.25), and 0 particularly preferably from pieces ^{_{/ 100μm 2 (N a = 0}} ).
By 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 μm 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. As an 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 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 μm ² or more in the cross section of the porous layer (I) is calculated.

(4) Thickness The thickness of the film is not particularly limited, but is preferably 1.1 μm or more, more preferably 10 μm or more, and further preferably 20 μm or more. On the other hand, the upper limit is preferably 400 μm or less, more preferably 300 μm or less, and particularly preferably 200 μm 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.

(5) Thermal conductivity 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. 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. When 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.
Here, 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. After blackening with a graphite spray, 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).
When 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). In addition to the three-layer structure having the layer (III) (adhesive layer or adhesive layer), a multilayer structure of four layers, five layers, or more may be used. In any layer configuration, if 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.
In particular, as shown in (II) / (I) / (II), 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). ) Can be formed as pseudo independent pores, so that liquid permeation into the porous layer (I) does not occur, gas convection is prevented, and excellent heat insulating properties are obtained. Therefore, it can be said that the laminated film of the present invention is a laminated heat insulating film.
Although the manufacturing method of the laminated film of the present invention will be described later, 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) (adhesive layer or adhesive layer) will be described later.
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. When 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. In addition, when there are two or more porous layers (I), 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 μm, more preferably 10 μm to 280 μm. 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.
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 laminated film is preferably 1 to 100 μm, and more preferably 2 to 95 μm. 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.
Here, when a plurality of porous layers (I) and (II) are arranged, 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.

Hereinafter, the resin film having the porous layer (I) and the layer (II) constituting the film will be described.

2. 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.

(1) Air permeability 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.
By setting the air permeability of the resin film to 1000 seconds / dL or more, air communication in the thickness direction of the film is reduced, and thus the resin film is excellent in heat insulation. By having the layer (II), it becomes easy to obtain a film having an air permeability in the above range. Even if an adhesive layer or an adhesive layer is formed on the layer (II) because the laminated film has the layer (II), the adhesive to the porous layer (I) is applied when the adhesive or adhesive is applied. 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.

(2) Porosity 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. In the resin film, 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 substantial amount W1 of the measurement sample is measured, the mass W0 when the porosity is 0% is calculated based on the density of the resin composition, and the porosity is calculated based on the following formula from these values.
Porosity (%) = {(W0−W1) / W0} × 100

In order to obtain the porosity of the resin film using the above laminated film, 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. Alternatively, the porosity can be calculated by calculating the porosity of the resin film obtained by completely removing the adhesive layer and then drying.

(3) 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.
Formula (1): N _A ≦ 1
N _A is more preferably 0.5 pieces / 100 μm ² or less (N _A ≦ 0.5), further preferably 0.25 pieces / 100 μm ² or less (N _A ≦ 0.25), and 0 particularly preferably from pieces ^{_{/ 100μm 2 (N a = 0}} ).
The presence ratio of pores having a pore area of 3 μm ² or more in the cross section of the porous layer (I) is 1 piece / 100 μm ² or less, thereby suppressing generation of a coarse pore diameter that causes deterioration of pore heat transfer, It can have excellent heat insulation.

(4) Thickness The thickness of the resin film is not particularly limited, but is preferably 1 μm or more, more preferably 10 μm or more, and further preferably 20 μm or more. On the other hand, the upper limit is preferably 300 μm or less, more preferably 200 μm or less, and particularly preferably 150 μm 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 μm or less, it can be used easily for applications that are used in a limited space where the installation place is narrow.

(5) Thermal conductivity
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. In the 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. When 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.
Here, 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. After blackening with a graphite spray, 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).

In order to obtain the thermal conductivity of the resin film using the above laminated film, 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. Alternatively, 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.
When 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). In addition to a two-layer structure having layers, a multi-layer structure of three layers, four layers, five layers, or more may be used. In any layer configuration, if the porous layer (I) has the layer (II) on at least one side, the resin film is excellent in heat insulation and processability.
In particular, as shown in (II) / (I) / (II), 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). ) Can be formed as pseudo independent pores, so that liquid permeation into the porous layer (I) does not occur, and excellent heat insulation is provided to prevent gas convection.
Although the manufacturing method of the resin film of this invention is mentioned later, it is preferable to extend | stretch the film provided with porous layer (I) and layer (II).

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. When 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. In addition, when there are two or more porous layers (I), 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 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 μm, more preferably 10 μm to 280 μm. 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 μm, and more preferably 2 to 95 μm. 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.
Here, when a plurality of porous layers (I) and (II) are arranged, the total thickness of each layer is used for calculation.

Hereinafter, the 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.

Hereinafter, each component constituting the laminated film will be described.

3. Porous layer (I)
The porous layer (I) constituting the laminated film of the present invention contains a propylene-based resin (A).
Hereinafter, each component which comprises a porous layer is demonstrated.

3-1. 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 α-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. By setting the Mw / Mn to 1.5 or more, sufficient extrudability can be obtained, and industrial mass production is possible. On the other hand, by setting Mw / Mn to 10.0 or less, sufficient mechanical strength can be ensured. Mw / Mn is measured by a GPC (gel per emission chromatography) method.

Further, 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. By setting the MFR to 0.5 g / 10 min or more, it has a sufficient melt viscosity at the time of molding and can ensure high productivity. On the other hand, by setting the MFR to 15 g / 10 min or less, sufficient strength can be ensured. 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).

In addition, 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 | mold catalyst, a metallocene catalyst Examples thereof include a polymerization method using a single site catalyst typified by the above.

Examples of the propylene-based resin (A) include, for example, trade names “Novatech PP” “WINTEC” (manufactured by Nippon Polypro), “Versify” “Notio” “Toughmer XR” (manufactured by Mitsui Chemicals), “Zeras”, “Thermo Run”. (Mitsubishi Chemical Co., Ltd.), “Sumitomo Noblen” “Tough Selenium” (manufactured by Sumitomo Chemical Co., Ltd.), “Prime Polypro” “Prime TPO” (manufactured by Prime Polymer Co., Ltd.), “Adflex” “Adsyl” “HMS-PP (PF814)” Commercially available products such as “Sun Aroma” and “Inspire” (Dow Chemical) can be used.

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 β crystals, which is one of crystal forms. In the formation of a porous structure using β crystals, since the β crystals in the propylene-based resin are converted into α 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 β crystal activity of the porous layer (I) can be regarded as an index indicating that the propylene-based resin was generating β 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 β-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 β 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 β 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 (Tmβ) derived from the β crystal of the propylene resin at the time of reheating is If detected, it is determined to have β crystal activity.

The presence or absence of the β crystal activity can also be determined by a diffraction profile obtained by X-ray diffraction measurement of a laminated film subjected to a specific heat treatment. Specifically, the heat treatment at 170 to 190 ° C., which exceeds the crystal melting peak temperature of the propylene-based resin, is performed, slowly cooled to form β crystals, and the grown porous film (I) of the laminated film is subjected to X-ray When diffraction measurement is performed and a diffraction peak derived from the (300) plane of the β crystal of the propylene-based resin is detected in the range of 2θ = 16.0 ° to 16.5 °, it is determined that there is β crystal activity. . For details on the β crystal structure and X-ray diffraction measurement of the propylene resin, see Macromol. Chem. 187, 643-652 (1986), Prog. Polym. Sci. Vol. 16, 361-404 (1991), Macromol. Symp. 89, 499-511 (1995), Macromol. Chem. 75, 134 (1964), and references cited therein.

As a method for obtaining the β crystal activity of the porous layer (I) described above, a method in which a substance that promotes the formation of α crystal of the propylene resin is not added to the resin composition constituting the porous layer (I), 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 β-crystal nucleating agent is added to the resin composition constituting the porous layer (I) The method etc. are mentioned. Among them, it is particularly preferable to obtain a β crystal activity by adding a β crystal nucleating agent to the resin composition constituting the porous layer (I). By adding a β crystal nucleating agent, the production of β crystals of a propylene resin can be promoted more uniformly and efficiently, and a laminated film having a porous layer (I) having β 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.

2-2. β-crystal nucleating agent The porous layer (I) preferably has the β-crystal activity in order to obtain a fine porous structure, and among them, it preferably includes a β-crystal nucleating agent. Examples of the β 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 β crystals of the propylene resin, and two or more types are mixed and used. May be.

Examples of the β crystal nucleating agent 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.
Among these, one or more selected from the group consisting of amide compounds, tetraoxaspiro compounds, and quinacridones are preferable.

Specific examples of commercially available β crystal nucleating agents include the β crystal nucleating agent “NJESTER NU-100” manufactured by Shin Nippon Rika Co., Ltd., and specific examples of propylene resins to which β crystal nucleating agents are added include Aristech. Examples thereof include polypropylene “Bepol B-022SP”, polypropylene manufactured by Borealis “Beta (β) -PP BE60-7032,” polypropylene manufactured by Mayzo “BNX BETAP-LN”, and the like.

The content of the β-crystal nucleating agent in the porous layer (I) can be appropriately adjusted depending on the type of the β-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, β-crystals of propylene resin can be generated and grown sufficiently at the time of production, sufficient β-crystal activity can be secured, and sufficient β-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 β crystal nucleating agent on the film surface.

4). Layer (II) (Protective layer)
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.
Preferably, 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. It is preferable that the layer (II) has no pores of 1 μm ² or more. By being such a layer (II), the penetration of the pressure-sensitive adhesive is suppressed, the pores derived from the internal porous structure are maintained, and the heat insulating property does not deteriorate.

4-1. 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. By selecting 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. Moreover, when apply | coating an adhesive, the penetration | invasion of the adhesive to a porous layer can be suppressed and a heat insulation fall can be prevented.

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%.

5). Layer (III) (adhesive layer or adhesive layer)
By providing the layer (II) with the layer (III) (adhesive layer or adhesive layer), the laminated film of the present invention can easily impart heat insulation to various members bonded through the layer (III). In particular, 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 μm 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 acrylic pressure-sensitive adhesive obtained by copolymerizing with.

In order to obtain higher adhesive strength, 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 agent mainly composed of a crosslinking agent, an aldehyde crosslinking agent, an oxazoline crosslinking agent, a metal alkoxide crosslinking agent, a metal chelate crosslinking agent, a metal salt crosslinking agent, an ammonium salt crosslinking agent, or the like may be added. . These other components can be used alone or in combination of two or more.

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. Various additives such as an agent, a lubricant, a flame retardant, and an elastomer may be appropriately included. Moreover, other resin compositions may be contained to such an extent that the property is not impaired.

6). 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 (hereinafter sometimes referred to as “the film production method”) includes a layer containing a propylene resin (A) as a main component and a β crystal nucleating agent (C). Forming a non-stretched film having (i) and a layer (ii) mainly composed of the propylene-based resin (B) on at least one side of the layer (i), and stretching the unstretched film It has the extending process which creates a resin film, and also the application | coating process which apply | coats an adhesive agent or an adhesive to the surface of the said layer (ii) of this resin film, and forms a layer (iii).

The film production method may include the above-described steps, and may further include other steps, treatments, and the like.

Moreover, in this invention, in the range which does not impair the effect of this invention, components other than propylene resin (A), propylene resin (B), and (beta) crystal nucleating agent (C), for example, propylene polymer (A It is permissible to mix other resins other than).
Other 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, fluorine-based resins.

In addition, in the present invention, in addition to the components described above, additives that are generally blended can be added as appropriate within a range that does not significantly impair the effects of the present invention. Examples of 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.

When kneading, the machine to be used is not particularly limited. For example, a known extruder such as a single screw extruder, a twin screw extruder, or a multi-screw extruder can be used. Further, depending on the equipment structure and necessity, a pressure reducer may be connected to the vent port to remove moisture and low molecular weight substances.

Hereinafter, the film forming process and the stretching process will be described sequentially.

(1) 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.

When adopting the T-die method as a specific method for forming a film, a sheet-like molten resin extruded from the T-die is laminated and adhered onto a rotating cast roll (chill roll, cast drum). The method of shape | 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.
When forming the film while cooling the kneaded product, 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. In the present invention, 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. Thus, it is preferable to obtain a laminated non-porous film having a high crystallinity.

In the unstretched film to be obtained, the thickness of the effective portion excluding both ends is preferably 50 μm to 1000 μm, more preferably 80 μm or more and 800 μm or less, and particularly preferably 100 μm or more or 600 μm or less.
If the unstretched film thickness is 50 μm or more, the film is too thin to prevent breakage during stretching. If the unstretched film thickness is 1000 μm 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.

In the unstretched film, 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. When 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.
Here, when a plurality of layers (I) and (II) are arranged, 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 μm. The lower limit of this thickness is more preferably 55 μm, still more preferably 60 μm. On the other hand, the upper limit is more preferably 580 μm, still more preferably 550 μm. The laminated film which has favorable heat insulation is obtained because the thickness of layer (I) is 50 micrometers or more. On the other hand, when the thickness of the layer (I) is 600 μm or less, a stretched film having a thickness of 300 μm or less after stretching can be obtained.

The unstretched film preferably has a layer (II) of 5 to 300 μm. The lower limit of this thickness is more preferably 10 μm and even more preferably 20 μm. On the other hand, the upper limit is more preferably 250 μm, and still more preferably 200 μm. By having the layer (II) of 5 μm or more, the porous layer can be closed after stretching, and a laminated film having a protective layer is obtained. On the other hand, the laminated film which suppressed the heat insulation fall is obtained because it is 300 micrometers or less layer (II).

(2) Stretching process Next, the obtained nonporous film-like material is subjected to uniaxial stretching or biaxial stretching. Uniaxial stretching may be longitudinal uniaxial stretching or transverse uniaxial stretching. Biaxial stretching may be simultaneous biaxial stretching or sequential biaxial stretching. In the case of producing a laminated film having a protective layer, which is the object of the present invention, 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. In addition, extending | stretching to the flow direction (MD) of a film-like thing is called "longitudinal stretching", and extending | stretching to the orthogonal | vertical direction (TD) with respect to a flow direction is called "lateral stretching."

When using sequential biaxial 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 | rupture at the time of extending | stretching by setting it as 60 degreeC or more, it is preferable.

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. When the stretch ratio per uniaxial stretching is 1.1 times or more, whitening proceeds and sufficient porosity is achieved by stretching. Moreover, by setting it as 10 times or less, the deformation | transformation of a void | hole is suppressed and the laminated | multilayer film fully whitened can be obtained.

The transverse stretching temperature is preferably 100 to 160 ° C, more preferably 110 to 150 ° C. When the transverse stretching temperature is within the specified range, 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. By stretching at a prescribed transverse stretching ratio, it is possible to have a sufficient porosity without deforming pores generated during longitudinal stretching.

(3) Application process In the application process, 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.

Furthermore, 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.

6). Laminated body for image display apparatus, image display apparatus The laminated body for image display apparatus of the present invention 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.

Examples and Comparative Examples are shown below, and the laminated film of the present invention will be described in more detail. However, the present invention is not limited at all.

<Porous layer (I)>
(Propylene resin (A))
A-1: Homopolypropylene (Novatech PP FY6HA, MFR: 2.4 g / 10 min [230 ° C., 2.16 kg load], Mw / Mn = 3.2, manufactured by Nippon Polypro Co., Ltd.)
(Β crystal nucleating agent)
C-1; 3,9-bis [4- (N-cyclohexylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5,5] undecane
(Antioxidant)
D-1; tris (2,4-di-t-butylphenyl) phosphite and tetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionic acid] pentaerythritol 1: 1 mixture (IRGANOX-B225, manufactured by BASF)
(Elastomer)
E-1: Styrene-ethylene / propylene-styrene block copolymer (SEPS, SEPTON 2005, MFR: not flowing, manufactured by Kuraray Co., Ltd.)

<Layer (II)>
(Propylene resin (B))
B-1: random polypropylene (Prime TPO F3910, MFR: 4.5 g / 10 min, manufactured by Prime Polymer Co., Ltd.)

<Adhesive layer (III)>
As a rubber component of the pressure-sensitive adhesive, 100% by mass of a styrene-based elastomer (styrene-ethylene / butylene-styrene block copolymer, grade name: SEPTON 8006, styrene content = 33%, MFR = non-flowing, manufactured by Kuraray Co., Ltd.) Liquid plastic isoprene resin (hydrogenated liquid isoprene rubber, Claprene LIR-290, number average molecular weight 31,000) as plasticizer and toluene (manufactured by Nacalai Tesque, concentration: 99.0% or more, SP) Value: 18.2) was added to a solid content concentration of 12% and mixed to prepare a coating pressure-sensitive adhesive (F-1) for forming a pressure-sensitive adhesive layer (III).

Example 1
100 parts by mass of propylene resin (A-1), 0.2 part by mass of β-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. Formed with a T-die with a lip opening of 1 mm using propylene resin (B-1) for the front and back layer side extruder and the mixture 1 for the middle layer side extruder, led to the cast roll and laminated non-porous film-like material (Unstretched film) was obtained. 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 thickness shown in the column “Layer (II) / Layer (I) / Layer (II) Thickness Ratio”. Thereafter, 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. and a preheating time of 12 seconds in a film tenter facility (manufactured by Kyoto Machine Co., Ltd.), and then stretched 3.5 times in the transverse direction at a stretching temperature of 150 ° C. Heat treatment was performed at 0 ° C. to obtain a resin film (stretched film). The evaluation results of the obtained resin film are summarized in Table 1. Moreover, the cross-sectional image which image | photographed the cross section which cut | disconnected the obtained resin film in TD direction with the scanning electron microscope (SEM) is shown in FIG.

On one side of the obtained resin film, 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.

Regard the films obtained in Examples and Comparative Examples, 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.
In addition, 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). Furthermore, regarding Example 1, the film provided with the adhesive layer (III) was also measured.

(1) Film thickness For the unstretched film (laminated non-porous film-like material) and resin film of Examples and Comparative Examples, 10 points were randomly measured using a dial gauge of 1/1000 mm, and the average value was measured. It was.

(2) 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
(Ii) 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

(3) Abundance ratio of pores A cross section of the measurement sample cut in the TD direction was measured with a scanning electron microscope (SEM) ("S-4500 manufactured by Hitachi High-Technologies Corporation") and the porous layers (I) and (II) ) Was visually confirmed. Regarding the porous layer (I), image processing was performed using image analysis software “SPIP (version 6.6.4)” manufactured by Image Metrology. As an 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 area is selected in the output without defining the hole range by a filter. After measuring the area of each pore, the abundance ratio (N _A ) of pores having a pore area of 3 μm 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.

(4) 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.

(5) Thermal conductivity After cutting a measurement sample into 10 mm square and measuring the thickness with a micrometer, the sample was blackened with graphite spray, and then heated using a xenon flash method (manufactured by NETZSCH, model: LFA447 nanoflash). The diffusion rate was evaluated. The thermal conductivity was determined from the product of this value calculated from the size and mass, the bulk density, and the specific heat measured with a differential scanning calorimeter (DSC Pyris 1 manufactured by Perkin Elmer).

(6) Solvent soaking The following 3 types of solvents having different solubility parameters (SP values) were dripped into the measuring sample, and the solvent soaking into the measuring sample was visually evaluated. The evaluation criteria are specified below. For details regarding the SP value, values specified in the durability of the polymer material (Industry Research Committee, 1993) and the like were used as a reference.
(1) Normal hexane (Nacalai Tesque, concentration: 95.0% or more, SP value: 14.7)
(2) Acetone (Nacalai Tesque, concentration: 99.0% or more, SP value: 20.1)
(3) Ethanol (Nacalai Tesque, concentration: 99.5% or more, SP value: 26.2)
A: Solvent remains on the surface and does not cause stain on the film C: Solvent does not remain on the surface and causes stain on the film Dropping a solvent with a different SP value on the measurement sample and confirming the penetration Thus, with respect to the solvents within the above three SP value ranges, it is possible to easily confirm the presence or absence of permeation into the measurement sample.

(7) Porosity of resin film after application of adhesive (P2)
The prepared pressure sensitive adhesive (F-1) was applied to each resin film using a 50th bar coater on the measurement sample, dried at 80 ° C. for 1 minute, and then a PET film (manufactured by Mitsubishi Plastics, Dia. Foil S100-50, thickness = 50 μm) was applied as a measurement sample. In the same manner, 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. Based on the density of the resin composition constituting the resin film, the mass W0 when the porosity was 0% was calculated, and the porosity P2 was calculated from these values based on the following formula.
Porosity (%) = {(W0−W2) / W0} × 100
From the porosity P1 (%) of the resin film and the porosity P2 (%) of the resin film when a pressure-sensitive adhesive is applied to one side of the laminated film, by comparing according to the following formula (2), The penetration of the adhesive was evaluated.
Formula (2): P1-P2 <3
Y: Formula (2) is satisfy | filled.
N: Expression (2) is not satisfied.

(8) β crystal activity The presence or absence of β 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. β crystals were produced and grown. Furthermore, when the temperature of the resin film is raised again from 25 ° C to 240 ° C at a heating rate of 10 ° C / min, the crystal melting peak temperature (145 to 160 ° C) derived from the β crystal of the propylene-based resin is detected when the temperature is raised again. Was determined to have β crystal activity.
Table 1 shows the resin film having β crystal activity as Y and the resin film not having β crystal activity as N.

Table 1 shows the evaluation results regarding the examples and comparative examples. In Table 1, 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.
In Example 1, the thickness, porosity, air permeability, and pore abundance ratio (N _A ) in the state provided with the adhesive layer were 80 μm 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.

Claims

A porous layer (I) mainly composed of a propylene-based resin (A);
A layer (II) mainly composed of a propylene-based resin (B) on at least one surface of the porous layer (I);
Having an adhesive layer or an adhesive layer on the layer (II);
A laminated film having an air permeability of 1000 seconds / dL or more and a porosity of 50% or more.
The laminated film according to claim 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.
The laminated film according to claim 1 or 2, wherein the thickness is from 1 µm to 300 µm.
The laminated film according to any one of claims 1 to 3, which satisfies the formula (1).
Formula (1): N A ≦ 1
[N A represents the abundance ratio of the porous layer (I) of at open area 3 [mu] m 2 or more in a cross section hole (pieces / 100 [mu] m 2). ]
The porosity P1 (%) of the resin film having the porous layer (I) and the layer (II) and the porosity P2 (%) of the resin film in the laminated film satisfy the following formula (2). 5. The laminated film according to any one of 1 to 4.
Formula (2): P1-P2 <3
At least one surface of the laminated film according to any one of claims 1 to 5,
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 claim 6.