WO2015056650A1 - Insulating film and production method therefor - Google Patents

Abstract

The present invention addresses the issue of providing an insulating film having both high heat insulating properties and high transparency, and a production method therefor. This insulating film has a polymer layer having a porous structure, formed upon a plastic film. This insulating film production method includes: (1) a step in which a block copolymer layer is formed upon the plastic film; (2) a step in which a microphase separated structure is formed upon the block copolymer layer; and (3) a step in which some or all of one polymer phase of the block copolymer layer having the microphase separated structure formed therein is removed and the polymer layer having these porous structure is formed.

Description

Insulating film and method for producing the same

The present invention relates to a heat insulating film and a method for producing the same.

Conventionally, in the construction field, the automobile field, etc., various methods have been used to efficiently obtain heat insulation from the viewpoint of ensuring comfort of living spaces including reduction of air conditioning costs (energy saving) and prevention of condensation. I came.
However, with respect to a part requiring visibility such as a window glass, a heat insulating material used for a wallpaper for a house is generally low in transparency and cannot be used from the viewpoint of visibility. Therefore, laminated glass, double-glazed glass, etc. have been developed as a means of heat insulation between the inside and outside of the window glass, but they are expensive. For sash windows, etc., construction of the window frame is necessary to provide them. The cost was even higher.
In addition, as a method of improving the inflow of heat from the window, there is a method of sticking a protective film in which a metal film is formed on a plastic film to the window. However, although this can suppress the inflow of heat, The effect of suppressing the outflow of was insufficient.
Patent Document 1 discloses a window-attached sheet that includes at least two resin films and has a spacer for forming an air layer between the two resin films, and is a resin film located indoors from the air layer. A window pasting sheet which is a heat insulating resin film having a far-infrared reflective film on one side is disclosed.
Patent Document 2 discloses a heat insulating film having heat insulating properties and transparency using silica hollow nanoparticles as a heat insulating material.

JP 2010-138659 A JP2011-10401A

However, the heat insulating films of Patent Documents 1 and 2 have a problem that heat insulating properties and transparency are not sufficient.
This invention makes it a subject to provide the heat insulation film which combined high heat insulation and high transparency, and its manufacturing method in view of the said problem.

As a result of intensive studies to solve the above problems, the inventors of the present invention have high heat insulation and high transparency by providing a block copolymer layer having a low thermal conductivity having a porous structure on a plastic film. The present invention was completed.
That is, the present invention provides the following [1] to [9].
[1] A heat insulating film in which a polymer layer having a porous structure is formed on a plastic film.
[2] The heat insulating film according to [1], wherein the porous structure is formed from a microphase separation structure of a block copolymer.
[3] The heat insulating film according to the above [1], wherein the porous structure is fine pores, and the mean pore diameter of the fine pores is 5 to 1000 nm.
[4] The heat insulating film according to [1], wherein the heat conductivity of the heat insulating film is 0.1 (W / m · K) or less.
[5] The block copolymer forms a phase-separated structure by self-organization, and is composed of AB type, ABA type, and B- type comprising units (A) and (B) that are incompatible with each other. A block copolymer of type AB, wherein the unit (A) and the unit (B) are respectively a styrene polymer, a poly (meth) acrylate ester, a polyvinylpyridine derivative, a conjugated diene polymer, a polyolefin. The heat insulating film according to [2], which is at least one selected from the group consisting of:
[6] The heat insulating film according to [1], further including an adhesive layer.
[7] The heat insulating film according to [1], wherein the heat insulating film is used as a window film.
[8] A method for producing a heat insulating film as described in [1] above,
(1) a step of forming a block copolymer layer on a plastic film, (2) a step of forming a microphase separation structure on the block copolymer layer, (3) one of the block copolymer layers on which the microphase separation structure is formed Removing a part or all of the polymer phase, and forming a polymer layer having a porous structure.
[9] The method for producing a heat insulating film according to the above [8], wherein the pores have the porous structure, and the average pore diameter of the pores is 5 to 1000 nm.

According to the present invention, by using a micro phase separation structure by self-organization of a block copolymer (BCP) on a plastic film and forming a polymer layer having a porous structure, it has high heat insulation and high transparency. Insulating film can be provided.

It is sectional drawing which shows an example of the heat insulation film of this invention. It is explanatory drawing of the structure for measuring a temperature difference at the time of sticking the heat insulation film of this invention to the glass substrate through the adhesive layer. AFM photograph (a) after microphase separation of the block copolymer layer obtained in Example 1 of the present invention (measurement range: 1 μm × 1 μm), and AFM photograph (b) after UV-ozone treatment (measurement range: 1 μm) × 1 μm). An AFM photograph (a) after microphase separation of the block copolymer layer obtained in Example 2 of the present invention (measurement range: 1 μm × 1 μm) and an AFM photograph after oxygen plasma etching (measurement range: 1 μm × 1 μm) is there. In Example 3 of this invention, it is a SEM photograph (measurement range 1 micrometer x 1 micrometer) which shows the surface of the micropore obtained by the etching by the ultraviolet irradiation after micro phase separation.

[Insulation film]
The heat insulating film of the present invention is a heat insulating film in which a polymer layer having a porous structure is formed on a plastic film.

FIG. 1 shows an example of a cross-sectional view of the heat insulating film of the present invention. As shown in FIG. 1, the heat insulating film 1 is characterized in that a polymer layer 3 c having a porous structure is formed on a plastic film 2. Here, the “porous structure” is a structure in which, for example, nano-sized pores are extremely fine, and the fine pores are arranged independently of each other with a predetermined shape and interval. The porous film derived from the microphase separation structure of the block copolymer, which will be described later, is formed on the plastic film, so that a heat insulating film having both high heat insulating properties and high transparency can be obtained.

<Plastic film>
Examples of the resin constituting the plastic film include a thermosetting resin, a thermoplastic resin, and a photocurable resin. For example, polyolefin resins such as polyethylene and polypropylene; styrene resins such as polystyrene; acrylic resins such as polymethyl methacrylate; polyamide (nylon 6, nylon 66, etc.), poly m-phenylene isophthalamide, poly p-phenylene terephthal Amide resins such as amides; Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate; norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic rings Hydrocarbon polymer and cycloolefin polymers such as hydrides thereof; vinyl chloride; polyimide; polyamideimide; polyphenylene ether; polyether ketone; polyether ether ketone; Over preparative; polyphenylene sulfide; and two or more combinations of these polymers; polysulfones, polysulfone resins such as polyether sulfone, or the like. Among these, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyarylate are preferable because they are versatile and excellent in transparency.

<Block copolymer>
The block copolymer is not particularly limited as long as it forms a microphase-separated structure by self-organization and is formed by bonding the incompatible unit (A) and unit (B). Examples of the block copolymer include block copolymers such as AB type, ABA type, and BAB type. The block copolymer may include other units, for example, an ABC type, an ABCA type, or the like including the unit (C). Among these, from the viewpoint of ease of phase separation and control of fine pores, AB type, ABA type, and BAB type block copolymers are preferred, and AB type block copolymers are preferred. More preferred are block copolymers.

Unit (A) and unit (B) include polystyrene, o-polymethylstyrene, p-polymethylstyrene, polypropylstyrene, polymethoxystyrene, and derivatives thereof; poly (meth) acrylate , Ethyl poly (meth) acrylate, t-butyl poly (meth) acrylate, cyclohexyl poly (meth) acrylate, benzyl poly (meth) acrylate, poly (meth) acrylate containing poly (meth) acrylate, and derivatives thereof Poly (meth) acrylic acid esters such as polyvinyl pyridine derivatives such as polyvinyl pyridine and derivatives thereof; polyisoprene, polybutadiene, polypentadiene, polyhexadiene, polycyclopentadiene, polycyclohexadiene, polycyclohepta Ene, conjugated diene polymers such as poly cyclooctadiene and derivatives thereof; polyolefins such as polyethylene; and the like.
Specific examples of the block copolymer include polystyrene-polyisoprene (PS-b-PI), polystyrene-polybutadiene (PS-b-PBD), polystyrene-polyisoprene-polybutadiene-polystyrene (SIBS resin), polyvinylpyridine-polybutadiene (PVP). -B-PBD), polyvinylpyridine-polyisoprene (PVP-b-PI), polymethyl methacrylate-polyisoprene (PMMA-b-PI), polymethyl methacrylate-polystyrene (PMMA-b-PS), polymethyl methacrylate- Examples thereof include polybutadiene (PMMA-b-PB), polymethyl methacrylate-hedral oligomeric silsesquioxane-containing polymethacrylate (PMMA-b-PMAPOSS), and the like. Of these, polystyrene-polyisoprene (PS-b-PI), polymethyl methacrylate-polystyrene from the viewpoints of heat resistance, weather resistance, thermal conductivity, ease of phase separation, and ease of control of micropores. (PMMA-b-PS), polymethyl methacrylate-hedral oligomeric silsesquioxane-containing polymethacrylate (PMMA-b-PMAPOSS) is preferred, and polymethyl methacrylate-polyisoprene (PMMA-b-PI) is more preferred. is there.
The block copolymer may be a polymer obtained by polymerization or a commercially available product. The polymerization method is not particularly limited, and a known method can be used. For example, the polymerization method can be obtained by synthesis by living anion polymerization using sec-butyllithium as an initiator.

At least one of the unit (A) and the unit (B) constituting the block copolymer is a monomer having a polymer glass transition temperature of preferably 50 ° C. or higher, more preferably 80 ° C. or higher, and further preferably 90 ° C. or higher. It is preferable that it is comprised. The upper limit of the glass transition temperature is not particularly limited, but is usually 200 ° C. or lower. If glass transition temperature is the said range, it is excellent in heat resistance and can be preferably used as a heat insulation film. The glass transition temperature can be measured using a differential scanning calorimeter (DSC).

<Polymer layer having a porous structure> A polymer layer having a porous structure can be obtained by utilizing a microphase separation structure by self-organization of the block copolymer.
In general, a block copolymer has a characteristic microdomain structure with a predetermined order when different types of blocks are not mixed with each other and phase-separated. This is called a microphase-separated structure, and takes, for example, a structure in which two types of polymers constituting a block copolymer are phase-separated on the scale of the molecular chain length, that is, on the order of several tens of nanometers.
The microphase separation structure varies depending on the composition of the block copolymer, and can be classified into a lamellar structure, a cylinder structure, a spherical structure, a gyroid structure, and the like. More specifically, the microphase-separated structure also varies depending on the types of monomers constituting the block copolymer, their combination, volume fraction, and the type of solvent for dissolving the different polymer used during film formation. Among the various microphase-separated structures, the block copolymer used in the present invention is, for example, a matrix (phase) in which a cylindrical (cylinder) structure (phase) composed of conjugated diene polymer units is composed of styrene polymer units. A microphase separation structure having a cylinder structure as present therein is formed.
Specifically, the polymer layer having a porous structure forms a block copolymer layer on the plastic film, and the block copolymer layer is microphase-separated by annealing in a solvent atmosphere, for example. The block copolymer layer can be formed by removing part or all of one polymer phase.

The porous structure preferably has fine pores having an average pore diameter of 5 to 1000 nm, more preferably 10 to 300 nm, and still more preferably 30 to 150 nm. When the average pore diameter is in the above range, a heat insulating film having excellent heat insulating properties and transparency can be obtained. Here, the average pore diameter is 50 micropores randomly on an output screen (measurement range: 1 μm × 1 μm) obtained by observing the surface of the block copolymer layer with an atomic force microscope (AFM) and processing the observation result. Are extracted, the maximum and minimum diameters of each micropore are read, the center value of each individual pore diameter is determined, and then the average value is calculated by simple averaging over the total number measured.
The shape of the micropore is not particularly limited, and is, for example, a columnar shape such as a cylindrical shape or a prismatic shape; an inverted conical shape such as an inverted cone or an inverted pyramid; an inverted frustum shape such as an inverted pyramid or an inverted truncated cone; a groove shape or the like And a combination of these may be used.
The thickness of the block copolymer layer is preferably 0.01 to 500 μm, more preferably 0.01 to 100 μm, and still more preferably 0.02 to 10 μm. If thickness is this range, the heat insulation film which is excellent in both heat insulation and transparency can be obtained.

The heat insulating film of the present invention preferably has a thermal conductivity of 0.1 (W / m · K) or less, more preferably 0.07 (W / m · K) or less, and 0.05 ( W / m · K) or less is particularly preferable. If the thermal conductivity is within this range, high heat insulation can be obtained.

The heat insulating film of the present invention preferably has a haze of 2% or less, and more preferably a haze of 1.5% or less. When the haze is within this range, high transparency can be maintained.

<Adhesive layer> It is preferable that the heat insulation film of this invention has an adhesive layer further. With the pressure-sensitive adhesive layer, for example, a heat insulating film can be easily attached to a window glass or the like.
It does not specifically limit as an adhesive which comprises an adhesive layer, For example, an acrylic adhesive, a rubber adhesive, a urethane adhesive, a silicone adhesive, etc. are mentioned.
Specifically, as shown in FIG. 1, an adhesive layer 4 may be formed on the surface of the plastic film 2 opposite to the surface on which the polymer layer 3c having the porous structure is formed. The pressure-sensitive adhesive layer 4 may be formed on the surface of the plastic film 2 on which the polymer layer 3c having the porous structure is formed.

Among the above-mentioned pressure-sensitive adhesives, acrylic pressure-sensitive adhesives are more preferable in consideration of heat insulation, heat resistance, environmental resistance, cost, and transparency.
In addition, the said adhesive may be used independently and may use 2 or more types together.

The pressure-sensitive adhesive is within the range in which the object of the present invention is not impaired, for example, tackifier, plasticizer, photopolymerizable compound, photoinitiator, foaming agent, polymerization inhibitor, anti-aging agent, filler, cup Other components such as a ring agent and an antistatic agent may be added.
The thickness of the pressure-sensitive adhesive layer is preferably 1 to 200 μm, more preferably 10 to 100 μm. When the thickness of the pressure-sensitive adhesive layer is within this range, adhesion strength with a glass material or the like is ensured without impairing heat insulation and transparency.

The heat insulating film of the present invention is used in the construction field, the automobile field, etc. by being attached to a window glass or the like, thereby reducing the heating and cooling costs and suppressing the condensation in the interior or the interior of the vehicle. Comfort can be improved.

[Method for producing heat insulating film]
The method for producing a heat insulating film of the present invention is a method for producing a heat insulating film in which a polymer layer having a porous structure is formed on a plastic film,
(1) forming a block copolymer layer on a plastic film;
(2) forming a microphase separation structure in the block copolymer layer;
(3) removing a part or all of one polymer phase of the block copolymer layer in which the microphase-separated structure is formed to form a polymer layer having a porous structure;
It is a manufacturing method of the heat insulation film containing this.
The manufacturing method of this invention is demonstrated using FIG.

(1) Block Copolymer Layer Forming Step In the block copolymer layer forming step, a block copolymer solution prepared by dissolving the block copolymer described above in, for example, an organic solvent is applied onto the plastic film 2 of FIG. Is a step of forming. As a method for forming the block copolymer layer, a solution obtained by dissolving the above block copolymer in an organic solvent is applied onto a plastic film by a known method, and dried as necessary to form a block copolymer layer. Examples of the coating method that covers a desired thickness, for example, a range of 0.01 to 500 μm, which is the preferred thickness of the present invention, include spin coating, roll coating, dip coating, die coating, gravure coating, and the like. Not. In the case where a block copolymer layer of the order of several tens of nm is uniformly formed over the entire surface of the substrate, spin coating, die coating, and gravure coating are particularly preferably used.
Examples of the solvent for dissolving the block copolymer used in the present invention include cyclopentanone, toluene, ethyl acetate, chloroform, THF, benzene, and cyclohexanone from the viewpoint of obtaining a microphase separation structure having a cylinder structure. From the viewpoint of evaporation rate, cyclopentanone is preferred.
Further, from the viewpoint of uniformly forming a block copolymer layer having a thickness of the order of several tens of nm, the concentration of the block copolymer in the block copolymer solution is preferably 0.1 to 10% by mass, and more preferably 0. 2 to 5% by mass.

(2) Microphase separation structure formation process The microphase separation structure formation process is a process of forming the microphase separation structure 3b in the block copolymer layer 3a obtained in the block copolymer layer formation process. The method for forming the microphase separation structure is not particularly limited, but a method of maintaining the block copolymer layer in a solvent vapor atmosphere for a certain period of time (solvent annealing method) is preferable. By using the solvent annealing method, the self-assembly of the block copolymer tends to proceed in the film thickness direction, and a microphase-separated structure with a controlled depth, average diameter, shape, etc. is efficiently formed in the block copolymer layer. be able to. Examples of the solvent used in the solvent annealing include toluene, a mixed solvent of toluene and hexane, carbon disulfide, benzene, and THF. In this step, a desired microphase separation structure can be formed by appropriately selecting or adjusting the type of solvent and annealing conditions.

(3) Porous structure forming step The porous structure forming step removes a part or all of one polymer phase of the block copolymer layer in which the microphase separation structure obtained in the microphase separation structure formation step is formed, This is a step of forming a polymer layer 3b having a porous structure.
A method for removing a part or all of one of the block copolymer layers is not particularly limited, and examples thereof include a method of etching by ozone treatment, UV ozone treatment, oxygen plasma treatment, ultraviolet irradiation treatment, and the like. In this step, a desired porous structure can be formed by appropriately selecting or adjusting an etching method and etching conditions. Furthermore, it is preferable to perform cleaning, rinsing and the like in order to remove the wall surface of the porous structure formed by etching and etching residues. The cleaning liquid may be appropriately selected according to the plastic substrate material and etching residue, and examples thereof include hexane, acetic acid, alcohols (methanol, IPA, etc.), and the like.

The porous structure is a micropore, and the average pore diameter of the micropore is 5 to 1000 nm. When the average pore diameter is in the above range, a heat insulating film having excellent heat insulating properties and transparency can be obtained.

According to the production method of the present invention, a heat insulating film having high heat insulating properties and high transparency can be obtained.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The measurement of the thermal conductivity of the block copolymer layer of the heat insulation film obtained in the Example and the comparative example, and the heat insulation evaluation of the sample for heat insulation evaluation produced using the heat insulation film were carried out by the following methods.
(A) Measurement of thermal conductivity The thermal conductivity of the polymer layers of the heat insulating films obtained in Examples and Comparative Examples was calculated using the 3ω method (see paragraph [0034] of JP2013-183088, etc.).
(B) Thermal insulation evaluation As shown in FIG. 2, the adhesive layer 4 (thickness: 20 micrometers) is laminated | stacked on the thermal insulation film 1 produced by the Example and the comparative example, and it affixes on the glass substrate 5 (thickness: 700 micrometers). A sample for thermal insulation evaluation was prepared. Next, the heat insulating film surface 6 side in contact with the atmosphere was heated and held at 100 ° C. with a hot plate, and the temperature after 1 hour on the glass substrate surface 7 side in contact with the atmosphere was measured.
(C) Haze measurement The haze value of the heat insulating films obtained in Examples and Comparative Examples was determined according to JIS K 7136 using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name “NDH-2000”). ,It was measured.

Example 1
As a block copolymer, a cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.) is a block copolymer (manufactured by Polymer source, P4014-PIp) formed by combining a polystyrene unit (molecular weight: 72000) and a polyisoprene unit (molecular weight: 13000). And a solution with a concentration of 1% by mass was prepared. The prepared solution was applied on a polyethylene terephthalate film (thickness: 100 μm) by spin coating to form a block copolymer layer having a thickness of 150 nm. Next, using a solution of toluene / hexane = 70/30% by volume, a solvent annealing treatment was performed for 30 minutes in a solvent vapor atmosphere, thereby forming a microphase separation structure in the block copolymer layer. The surface of the block copolymer layer having a microphase separation structure was observed with AFM. FIG. 3A shows an AFM photograph (measurement range: 1 μm × 1 μm).
Then, using an ozone irradiation device (Samco, UV-Ozone dry stripper), UV ozone irradiation is performed for 30 seconds, a portion of the isoprene unit of the block copolymer layer is selectively etched, and washed with a hexane solvent. A heat insulating film was produced by obtaining a polymer layer having a porous structure composed of fine holes. The surface of the polymer layer of the obtained heat insulating film was observed with AFM. FIG. 3B shows an AFM photograph (measurement range: 1 μm × 1 μm).
A pressure-sensitive adhesive layer (thickness: 20 μm) made of an acrylic pressure-sensitive adhesive is laminated on the surface of the obtained heat insulating film plastic film opposite to the surface on which the polymer layer having the porous structure is formed. A heat insulating film with a layer was produced.
Table 1 shows the average pore diameter of the micropores of the polymer layer of the heat insulation film, the thermal conductivity, the haze value of the heat insulation film, and the heat insulation evaluation result (temperature of the glass substrate) of the heat insulation film with the pressure-sensitive adhesive layer.

(Example 2)
As a block copolymer, a block copolymer (trade name P9701-MMAPOSSMA, manufactured by Sowa Kagaku Co., Ltd.) formed by combining a polymethyl methacrylate unit and a polymethacrylate unit containing a helical oligomeric silsesquioxane is cyclopentanone (Tokyo Kasei). And a solution having a solution concentration of 0.5% by mass was prepared. The prepared solution was applied onto a polyethylene terephthalate film (thickness: 100 μm) by a spin coating method to form a block copolymer layer having a thickness of 30 nm. Next, a microphase separation structure was formed in the block copolymer layer by performing a solvent annealing treatment for 20 minutes in a solvent vapor atmosphere using a carbon disulfide solvent. The surface of the block copolymer layer having a microphase separation structure was observed with AFM. FIG. 4A shows an AFM photograph (measurement range: 1 μm × 1 μm).
Thereafter, using a reactive ion etching apparatus (Samco, UV-Ozone dry stripper), oxygen plasma etching is performed for 10 seconds under the conditions of an output of 100 W, a vacuum pressure of 5 Pa, and an oxygen flow rate of 10 ccm. A heat insulating film was produced by selectively etching a part of the polymethylmethacrylate unit and washing with a hexane solvent to obtain a polymer layer having a porous structure composed of fine pores. The surface of the polymer layer of the obtained heat insulating film was observed with AFM. FIG. 4B shows an AFM photograph (measurement range: 1 μm × 1 μm).
A pressure-sensitive adhesive layer (thickness: 20 μm) made of an acrylic pressure-sensitive adhesive is laminated on the surface of the obtained heat insulating film plastic film opposite to the surface on which the polymer layer having the porous structure is formed. A heat insulating film with a layer was produced.
Table 1 shows the average pore diameter of the micropores of the polymer layer of the heat insulation film, the thermal conductivity, the haze value of the heat insulation film, and the heat insulation evaluation result (temperature of the glass substrate) of the heat insulation film with the pressure-sensitive adhesive layer.

Example 3
As a block copolymer, a block copolymer (P2400-SMMA, manufactured by Sowa Kagaku Co., Ltd.) formed by combining a polymethyl methacrylate unit (PMMA unit) and a polystyrene unit is dissolved in toluene to prepare a solution having a concentration of 1% by mass. did. The prepared solution was applied onto a polyethylene terephthalate film (thickness: 100 μm) by a spin coating method to form a block copolymer layer having a thickness of 150 nm. Subsequently, it heat-processed for 10 minutes at 120 degreeC above glass transition temperature on a hotplate, and formed the micro phase-separation structure in the block copolymer layer.
After that, by irradiating the block copolymer layer with ultraviolet light at an illuminance of 10 mW / cm ² for 2 minutes, a part of the PMMA unit of the block copolymer layer is selectively etched, washed with an acetic acid solvent, and porous comprising fine pores. The heat insulation film was produced by obtaining the polymer layer which has a structure. The surface of the polymer layer of the obtained heat insulation film was observed with SEM. FIG. 5 shows an SEM photograph (measurement range: 1 μm × 1 μm).
A pressure-sensitive adhesive layer (thickness: 20 μm) made of an acrylic pressure-sensitive adhesive is laminated on the surface of the obtained heat insulating film plastic film opposite to the surface on which the polymer layer having the porous structure is formed. A heat insulating film with a layer was produced.
Table 1 shows the average pore diameter of the micropores of the polymer layer of the heat insulation film, the thermal conductivity, the haze value of the heat insulation film, and the heat insulation evaluation result (temperature of the glass substrate) of the heat insulation film with the pressure-sensitive adhesive layer.

(Comparative Example 1)
In Example 1, a heat insulating film was produced in the same manner as in Example 1 except that only the block copolymer layer was formed and no porous structure was formed. A pressure-sensitive adhesive layer (thickness: 20 μm) made of an acrylic pressure-sensitive adhesive is laminated on the surface opposite to the surface on which the block copolymer layer having no porous structure of the plastic film of the obtained heat insulating film is formed, The heat insulation film for a comparison with an adhesive layer was produced.
Table 1 shows the thermal conductivity of the block copolymer layer of the heat insulation film for comparison, the haze value of the heat insulation film for comparison, and the heat insulation evaluation result (temperature of the glass substrate) of the heat insulation film for comparison with the adhesive layer.

In Examples 1 to 3, the thermal conductivity is lower than that of Comparative Example 1, and the temperature rise is apparent from the temperature of the surface on the side of the heat insulating film affixed to the glass substrate and the temperature of the surface on the side of the glass substrate. It turned out to be very low. Moreover, it turned out that a haze value is substantially maintained and transparency is high.

 

 

Since the heat insulating film of the present invention has excellent heat insulating properties and high transparency, it can be applied to a heat insulating film for windows in the architectural field, the automobile field, and the like.

1: heat insulation film 2: plastic film 3a: block copolymer layer 3b: block copolymer layer 3c having a micro phase separation structure: polymer layer 4 having a porous structure 4: adhesive layer 5: glass substrate 6: heat insulation film surface 7 in contact with the atmosphere : Glass substrate surface in contact with air

Claims (9)

A heat insulating film in which a polymer layer having a porous structure is formed on a plastic film. The heat insulating film according to claim 1, wherein the porous structure is formed from a microphase separation structure of a block copolymer. The heat insulating film according to claim 1, wherein the porous structure is a fine pore, and the mean pore diameter of the fine pore is 5 to 1000 nm. The heat insulation film of Claim 1 whose heat conductivity of a heat insulation film is 0.1 (W / m * K) or less. The block copolymer forms a phase-separated structure by self-assembly, and is composed of AB type, ABA type, and BAB type, which are incompatible units (A) and (B). A block copolymer of any type, wherein the unit (A) and the unit (B) are each composed of a styrenic polymer, a poly (meth) acrylic acid ester, a polyvinylpyridine derivative, a conjugated diene polymer, and a polyolefin. The heat insulation film of Claim 2 which is at least 1 sort chosen from. The heat insulating film according to claim 1, further comprising an adhesive layer. The heat insulating film according to claim 1, wherein the heat insulating film is used as a window film. It is a manufacturing method of the heat insulation film described in Claim 1,
(1) forming a block copolymer layer on a plastic film;
(2) forming a microphase separation structure in the block copolymer layer;
(3) removing a part or all of one polymer phase of the block copolymer layer in which the microphase-separated structure is formed to form a polymer layer having a porous structure;
The manufacturing method of the heat insulation film containing this. The method for producing a heat insulating film according to claim 8, wherein the pores have a porous structure, and the average pore diameter of the pores is 5 to 1000 nm.

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