JP5861338B2 - Weather resistant film - Google Patents

Description

  The present invention relates to a weather resistant film.

Conventionally, in order to impart surface protection properties such as scratch resistance to resin molded products, interior products, exterior products and the like, a protective layer is provided on the surfaces thereof.
On the other hand, entrance doors and exterior members of ordinary residences, interior and exterior members such as flooring and exterior walls of public facilities, and structures and structures installed outdoors are exposed to direct sunlight and wind and rain every day. Extremely severe weather resistance is required for exterior members, buildings, window glass and furniture (hereinafter referred to collectively as “interior / exterior materials, buildings, window glass and furniture”). ing.

In contrast, in Patent Document 1, for example, in a decorative sheet formed by laminating a plurality of layers including a pattern layer and / or a colored layer and a surface protective layer on a base material, at least one of the plurality of layers is hydroxyphenyl. A decorative sheet containing an ultraviolet absorber made of a triazine compound has been proposed, and the weather resistance is improved by the ultraviolet absorber.
Moreover, in patent document 2, it is a film which has a primer layer and a surface protective layer on a base material, Comprising: A base material consists of an olefin film, a primer layer contains carbon black, and a surface protective layer is an electron beam. A weather-resistant film obtained by crosslinking and curing a curable resin composition has been proposed.
Furthermore, in patent document 3, in the film which has a primer layer and a surface protective layer on a base material, the base material consists of an olefin film, and the primer layer contains an ultraviolet absorber made of a hydroxyphenyltriazine compound as a solid content of the primer layer. On the other hand, a weather resistant film containing 6 to 15% by mass and having a surface protective layer crosslinked and cured by an electron beam curable resin composition has been proposed.
However, with a film with a conventional protective layer for imparting weather resistance to the interior / exterior material, damage reduction when the interior / exterior material is damaged is not considered much, and it is exposed to sunlight and moisture, such as outdoors. In such places, the main focus has been on maintaining the appearance of the interior and exterior materials and the surface function of the protective layer for a long period of time, and no importance has been placed on maintaining the mechanical strength of the film for a long period of time.

JP 2006-306020 A JP 2008-155590 A JP 2008-230172 A

  An object of the present invention is to provide a weather resistant film capable of maintaining the appearance and mechanical strength for a long period of time in places exposed to sunlight or moisture such as outdoors.

As a result of intensive studies for maintaining the mechanical strength of the weather-resistant film in places exposed to sunlight or moisture, such as outdoors, the present inventors have found that the deterioration of the polyester resin film base material due to hydrolysis is mechanical strength. We focused on the significant contribution to the decline. As a result of intensive studies from this viewpoint, the present inventors have found that the above problem can be solved by disposing a new layer capable of suppressing hydrolysis. The present invention has been obtained based on this finding.
That is, the present invention provides a gas barrier layer, a primer layer containing a weathering agent, and a surface protective layer made of a cross-linked cured product of an ionizing radiation curable resin composition containing a weathering agent on a substrate sheet made of a polyester resin film. The present invention provides a weather resistant film characterized in that it is provided in this order and an interior / exterior material formed by attaching the weather resistant film.

  ADVANTAGE OF THE INVENTION According to this invention, the weather resistant film which can maintain an external appearance and mechanical strength over a long period of time can be provided.

It is a schematic diagram which shows the structure of the embodiment of the weather resistant film of this invention.

[Weather-resistant film]
Hereinafter, the weather-resistant film of the present invention will be described with reference to the drawings. FIG. 1 is a schematic view showing an example of a preferred embodiment of the weather resistant film of the present invention.
The weather resistant film 1 of the present invention is a crosslinked cured product of an ionizing radiation curable resin composition containing a gas barrier layer 3, a primer layer 4 containing a weathering agent, and a weathering agent on a base sheet 2 made of a polyester resin film. The surface protective layer 5 is made of this order. In the weather resistant film 1 of the present invention, the gas barrier layer 3 is disposed between the base material 2 and the primer layer 4, thereby preventing the permeation of water vapor and suppressing the progress of hydrolysis of the polyester resin of the base material sheet 2. Therefore, the strength of the base sheet 2 can be maintained over a long period due to a synergistic effect with the suppression of light deterioration by the weathering agent contained in the surface protective layer 5 and the primer layer 4.
In addition, the weather resistant film 1 of the present invention is provided with the primer layer 4 and the surface protective layer 5 that function as a weather resistance imparting layer on the gas barrier layer, thereby suppressing the photodegradation of the gas barrier layer 3 itself. Adhesion with the surface protective layer 5 is also improved.
Furthermore, by providing the surface protective layer 5, the gas barrier layer 3 is protected from external stresses such as chemicals / solvents and scratches.
Then, by laminating the base material sheet 2 / gas barrier layer 3 / primer layer 4 / surface protective layer 5 in this order, (1) the gas barrier layer 3 can be protected from ultraviolet rays, and the above-mentioned organic material gas barrier layer that is weak against ultraviolet rays 3 can also be used. (2) By providing the surface protective layer 5, surface properties such as scratch resistance and chemical resistance can be imparted to the weather resistant film 1.

<Base material sheet>
As for the base material sheet 2 used by this invention, a polyester resin film is used for the base material at the point of intensity | strength, transparency, and a price. Examples of the polyester resin include polyethylene terephthalate resin, polybutylene terephthalate resin, polytrimethylene terephthalate resin, and the like. Among these, polyethylene terephthalate resin (hereinafter sometimes abbreviated as “PET”) is particularly preferable.
Moreover, what was called an easily-adhesive process, such as a corona discharge process and a plasma process, may be made, and an easily-adhesive layer, such as an anchor layer, may be provided on the surface.
50-100 micrometers is preferable and, as for the thickness of a resin film, 50-75 micrometers is more preferable. If it is 50 μm or more, even when it is used as a window covering scattering prevention film, which is one of the main uses of the weather resistant film 1, it is suitably prevented from scattering due to breaking when the glass is broken. Can serve a function. Moreover, if it is 100 micrometers or less, it will become advantageous in cost.

《Gas barrier layer》
The material constituting the gas barrier layer 3 may be an organic material or an inorganic material as long as it has gas barrier properties and is transparent. For example, polyvinylidene chloride (PVDC), polyvinyl alcohol (PVA), ethylene / vinyl alcohol copolymer (EVOH), polyacrylonitrile (PAN) and the like are preferable for organic materials, and silica vapor deposition for inorganic materials. Examples thereof include a film and an alumina vapor deposition film. In general, the organic material is excellent in flexibility, but the gas barrier performance is lower than that of the inorganic material. Among the above-mentioned organic materials, PVA and EVOH are preferable because PVA and EVOH have low barrier performance in a high humidity environment. On the other hand, the inorganic material is excellent in gas barrier performance, but lacks flexibility, and there is a possibility that cracking occurs during bending and the gas barrier performance is lowered. Among the above-mentioned inorganic materials, a silica deposited film that is more suitable for post-processing is preferable. It is desirable that the gas barrier layer is appropriately selected from these characteristics. The thickness is preferably 2 to 20 μm for the organic material and 0.01 to 1 μm for the inorganic material from the viewpoints of transparency, coloring prevention, gas barrier properties, and the like. Moreover, you may give an undercoat suitably in order to ensure adhesiveness with a base material.

A silica vapor deposition film or an alumina vapor deposition film is produced by a known method, for example, PVD method (Physical Vapor Deposition), CVD method (Chemical Vapor Deposition), or PE-CVD (Plasma enhanced CVD). .
The coating method in the case of an organic material is applied using a known coating apparatus, for example, a knife coater, a comma coater, a gravure coater, a roll coater or the like.

<< Primer layer >>
The primer layer 4 is disposed for the purpose of improving the adhesion between the gas barrier layer 3 and the surface protective layer 5 and for improving the weather resistance by adding a weathering agent. The material which comprises the primer layer 4 should just be a material containing a weathering agent, and is not restrict | limited in particular. For example, polyurethane resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, chlorinated polypropylene resin, acrylic resin, polyester resin, polyamide resin, butyral Examples thereof include resins, polystyrene resins, nitrocellulose resins, cellulose acetate resins, and urethane / acrylic copolymer resins. These resins can be used alone or as a mixture of two or more.
Of these, urethane / acrylic copolymer resins are particularly preferable because they have flexibility, toughness, and elasticity. In consideration of the environment, it is preferable not to use a resin system containing chlorine.

The urethane / acrylic copolymer resin includes polycarbonate urethane / (meth) acrylic copolymer resin, polyester urethane / (meth) acrylic copolymer resin, or polycarbonate urethane (meth) acrylate and acrylic polyol. It is preferable to use a resin, and a polycarbonate-based urethane / (meth) acrylic copolymer resin is more preferable. By forming the primer layer 4 using these resins, stress relaxation properties are imparted, and those having excellent weather resistance are obtained.
The primer layer 4 needs to contain a weathering agent. As the weathering agent, at least one selected from an ultraviolet absorber (hereinafter sometimes abbreviated as “UVA”) and a hindered amine light stabilizer (hereinafter sometimes abbreviated as “HALS”) is used. preferable. The weathering agent will be described in detail later. In addition, other known additives may be added.
1-10 micrometers is preferable and, as for the thickness of the primer layer 4, 3-6 micrometers is more preferable. If it is 1 μm or more, sufficient weather resistance is obtained, and if it is 10 μm or less, it is advantageous in terms of economy.
The primer layer 4 is formed by using the resin composition as it is or dissolved or dispersed in a solvent by a known printing method or coating method such as knife coating, comma coating, gravure coating, roll coating, etc. , By applying to the gas barrier layer 3.
Further, when the primer layer 4 is laminated on the gas barrier layer 3, the surface of the gas barrier layer 3 is subjected to so-called corona discharge treatment, plasma treatment, ozone / ultraviolet light in order to ensure adhesion between the gas barrier layer 3 and the primer layer 4. The adhesion between the primer layer 4 can be further enhanced by a treatment such as a treatment.

<Surface protective layer>
The surface protective layer 5 is a layer that imparts hard coat properties such as scratch resistance, solvent resistance, and antifouling properties in addition to weather resistance, and is provided on the primer layer 4 as shown in FIG. It is done.
The surface protective layer 5 needs to contain a weathering agent. As a weathering agent, it is preferable to contain at least one selected from UVA and HALS as in the primer layer 4. A reactive thing is preferable from a viewpoint of bleed-out prevention.
As described above, the surface protective layer 5 is formed by crosslinking and curing an ionizing radiation curable resin composition containing a weathering agent. As the ionizing radiation curable resin, an ionizing radiation curable resin having a (meth) acryloyl group is preferable, and a polymerizable oligomer or prepolymer conventionally used as an ionizing radiation curable resin, particularly a polyfunctional polymerizable resin. It can be used by appropriately selecting from oligomers or prepolymers.

Examples of the polymerizable oligomer or prepolymer include oligomers and prepolymers having a radically polymerizable unsaturated group in the molecule, such as epoxy (meth) acrylate, urethane (meth) acrylate, and polyether urethane (meth) acrylate. Preferred examples include caprolactone-based urethane (meth) acrylate, polyester (meth) acrylate-based, polyether (meth) acrylate-based oligomers and prepolymers. Among these, polyfunctional urethane (meth) acrylate-based is weather resistant. It is preferable from the viewpoint of achieving both compatibility and hard coat properties, and in particular, a tetrafunctional or higher urethane (meth) acrylate oligomer is preferable from the viewpoint of enhancing the hard coat properties. By improving the hard coat properties, it is possible to prevent scratches and suppress deterioration of visibility due to scratches.
As the urethane (meth) acrylate oligomer, a caprolactone-based urethane (meth) acrylate oligomer is preferable.
In the present invention, “(meth) acrylate” means “acrylate or methacrylate”. In addition, polyfunctional means “bifunctional” or more, and usually, a 20-functional or lower polymerizable oligomer or prepolymer, particularly a 20-functional or lower urethane (meth) acrylate oligomer is used.
The molecular weight of the polymerizable oligomer is preferably about 1000 to 5000.

  In addition to the above polyfunctional polymerizable oligomers, the ionizing radiation curable resin may be a polymer such as polybutadiene (meth) acrylate having a high hydrophobicity having a (meth) acrylate group in the side chain of the polybutadiene oligomer. Urethane (meth) acrylate can be used together, and weather resistance can be further improved by using together. Of these, caprolactone-based ones are more preferable in terms of improving weather resistance.

  In the present invention, a diluent such as a monofunctional (meth) acrylate such as methyl (meth) acrylate is used together with the polyfunctional urethane (meth) acrylate for the purpose of adjusting the viscosity thereof. They can be used in combination as long as the object of the present invention is not impaired. A monofunctional (meth) acrylate may be used individually by 1 type, may be used in combination of 2 or more type, and may use low-molecular-weight polyfunctional (meth) acrylate together. Moreover, as a diluent, the applicability | paintability of a resin composition can also be ensured using a normal organic solvent other than said monomer.

In the resin composition for forming the surface protective layer 5, at least one selected from a silicone-based surfactant, a fluorine-based surfactant, and a silicone (meth) acrylate may be added as a water-repellent additive. . Thereby, water can be kept close and it can have higher moisture-proof property. In addition, the antifouling property is improved, and the visibility can be prevented from being lowered due to the contamination.
The water-repellent additive is preferably contained in the surface protective layer 5 in an amount of 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin. It is particularly preferable to contain 0.5 to 10 parts by mass.

  In addition, the resin composition for forming the surface protective layer 5 can contain a scratch-resistant filler in order to further improve the hard coat property. A known additive other than the above may be added to the resin composition for forming the surface protective layer 5.

  The thickness of the surface protective layer 5 is preferably 3 to 15 μm, and more preferably 3 to 10 μm. If it is 3 micrometers or more, it can fully function as a surface protective layer, and if it is 15 micrometers or less, adhesiveness with the primer layer 4 will become favorable and it is advantageous also to economical efficiency.

(Weatherproofing agent)
Of the weathering agents used in the primer layer 4 and the surface protective layer 5, the UVA may be either inorganic or organic. The inorganic UVA may be titanium dioxide or cerium oxide having an average particle size of about 5 to 120 nm. Zinc oxide or the like can be preferably used. Examples of the organic UVA include benzotriazole UVA, triazine UVA, benzophenone UVA, salicylate UVA, acrylonitrile UVA, and the like. Of these, triazine-based UVA is preferable because it has a high ultraviolet-absorbing ability and does not easily deteriorate against high energy such as ultraviolet rays.

Specific examples of the triazine UVA include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, 1,3,5-triazine. -2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tri [[3,5-bis- (1,1-dimethylethyl) -4-hydroxyphenyl] methyl], and benzo Triazoles, specifically 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, polyethylene glycol 3- [ 3- (benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionic acid ester and the like.
The UVA is preferably contained in the primer layer 4 and the surface protective layer 5 in an amount of 0.1 to 25 parts by mass, and 0.5 to 25 parts by mass with respect to 100 parts by mass of the resin forming each layer. It is more preferable to contain 0.5 to 20 parts by mass.

Next, as HALS, specifically, 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2′-n-butylmalonate bis (1,2,2,6,6- Pentamethyl-4-piperidyl), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1 , 2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) ) Amino] -6- (2-hydroxyethylamine) -1,3,5-triazine), tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetra Carboxele And 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate.
Moreover, as a commercial item, the product name "Tinuvin 123", "Tinubin 144", "Tinubin 292", "Tinubin 111FDL", etc. by Ciba Specialty Chemicals are mentioned.
HALS is preferably contained in the primer layer 4 and the surface protective layer 5 in an amount of 0.05 to 15 parts by mass, and 0.5 to 15 parts by mass with respect to 100 parts by mass of the resin forming each layer. Is more preferable, it is more preferable to contain 1-15 mass parts, and it is especially preferable to contain 1-10 mass parts.

Further, as UVA or HALS, reactive UVA or reactive HALS having a polymerizable group such as a (meth) acryloyl group in the molecule can also be used. In particular, reactive UVA or reactive HALS is preferably used for the surface protective layer 5 from the viewpoint of preventing bleed out.
Examples of the reactive UVA include a product name “RUVA-93” manufactured by Otsuka Chemical Co., Ltd., a product name “UVA-633L” {2-hydroxy-4- (methacryloyloxyethoxy) benzophenone) methyl methacrylate Polymer} and the like.
As reactive HALS, the brand name "Sanol LS-3410" by Nippon Emulsifier Co., Ltd. is mentioned, for example.

(Water repellent additive)
Examples of silicone surfactants added as a water repellent additive to the resin composition for forming the surface protective layer 5 include Shin-Etsu Chemical Co., Ltd., trade names “KP-301” and “KP-341”; Available as Dow Corning, trade names “57 ADDITIVE” and “8029 ADDITIVE”.
As the fluorosurfactant, trade names “Zonyl FSN”, “Zonyl FSA”, “Zonyl FSE”, “Zonyl FSO”, “Zonyl FS-300” manufactured by DuPont, AGC Seimi Chemical Co., Ltd., trade name “Surflon S-242”, “Surflon S-243”, “Surflon S-420”, “Surflon S-611”, “Surflon S-651”, “Surflon S-386”; F-444 "; available from Daikin Industries, Ltd. as" DS "series.

  The silicone (meth) acrylate added as a water-repellent additive to the resin composition for forming the surface protective layer 5 may be monofunctional, bifunctional, or trifunctional or more polyfunctional. Of these, a modified silicone oil in which a (meth) acryl group is introduced at one or both ends is preferable. The structure of this modified silicone oil is roughly divided into a side chain type, both terminal types, one terminal type, and both side chain terminal types depending on the bonding position of the organic group to be substituted. There is no particular limitation. Moreover, as a functional group equivalent (molecular weight / functional group number) of silicone (meth) acrylate, what has the conditions of 100-20000, for example, Preferably it is 100-10000 is mentioned.

(Scratch resistant filler)
The scratch-resistant filler used in the present invention includes inorganic and organic fillers. Examples of inorganic substances include spherical particles such as α-alumina, silica, kaolinite, iron oxide, diamond, and silicon carbide. Examples of the particle shape include a sphere, an ellipsoid, a polyhedron, a scale shape, and the like. Although there is no particular limitation, a spherical shape is preferable.
On the other hand, organic fillers include synthetic resin beads such as cross-linked acrylic resin and polycarbonate resin. As for the particle size, those having a primary particle size of usually 5 to 1000 nm are preferably used, more preferably 10 to 50 nm, and particularly preferably 10 to 30 nm. The blending amount is preferably about 1 to 20 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.

(Other additives)
In the present invention, if desired, the ionizing radiation curable resin composition for the surface protective layer 5 or the primer layer resin may contain various additives as long as the performance is not impaired. Examples of various additives include polymerization inhibitors, crosslinking agents, antistatic agents, adhesion improvers, antioxidants, leveling agents, thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, and solvents. Etc.
When an ultraviolet curable resin is used as the ionizing radiation curable resin, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the curable resin. The initiator for use can be appropriately selected from those conventionally used.

Application of the ionizing radiation curable resin composition for forming the surface protective layer is performed such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating so that the thickness after curing is preferably 3 to 15 μm. It is carried out by a known method, preferably gravure coating. Moreover, it is more preferably 3 to 10 μm from the viewpoint of obtaining excellent weather resistance and its durability, as well as scratch resistance, transparency and specularity.
In addition, when a resin composition contains a solvent, after application | coating, it is preferable to irradiate ionizing radiation, after heat-drying a coating layer previously with a hot air dryer etc.

  The uncured resin layer formed by applying the above resin composition is crosslinked and cured by irradiating ionizing radiation or the like, whereby the surface protective layer 5 is formed. Here, when an electron beam is used for curing, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but it is preferable to cure the uncured resin layer at an acceleration voltage of about 70 to 300 kV. .

  The irradiation dose is preferably such that the crosslinking density of the ionizing radiation curable resin is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 30 to 200 kGy (3 to 20 Mrad).

  The electron beam source is not particularly limited, and for example, various electron beam accelerators such as a Cockloft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. be able to.

  When ultraviolet rays are used as ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp etc. are used.

  Further, when the surface protective layer 5 is laminated on the primer layer 4, the surface of the primer layer 4 is so-called corona discharge treatment, plasma treatment, chromium, in order to ensure adhesion between the surface protective layer 5 and the primer layer 4. Oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment, etc. can be used to further enhance the adhesion between the surface protective layer and the primer layer 4 is kept in a semi-cured state. After the surface protective layer 5 is applied, the surface protective layer 5 is cured by irradiating with ionizing radiation and curing the surface protective layer 5 so as to enhance the adhesion between the two. You can also.

  An adhesive layer (not shown) may be provided on the surface of the weather resistant film 1 of the present invention on the base sheet 2 side. By setting it as such a structure, it can stick to a to-be-adhered thing. The weather-resistant film thus obtained can be used by being attached to, for example, an exterior material or an interior material, and forms various interior / exterior materials. In particular, it is suitably used as a weather resistant film for preventing scattering of window glass that requires long-term weather resistance.

It does not specifically limit as an adhesive used for an adhesion layer, Adhesives, such as an acrylic type, a urethane type, a silicone type, and a rubber type, can be selected suitably and can be used. Among these, from the viewpoint of weather resistance and the like, an acrylic pressure-sensitive adhesive mainly composed of a polymer or copolymer of an acrylic monomer such as acrylic acid ester or methacrylic acid ester is preferable, and in particular, n-butyl acrylate, 2- Ethylhexyl acrylate and the like are suitable.
Moreover, a crosslinking agent can also be added and specifically, an isocyanate type, a metal chelate, an epoxy type, and a melamine type are mentioned.
The application amount of the pressure-sensitive adhesive is preferably in the range of 10 to 30 g / m ² by dry weight. If it is 10 g / m ² or more, sufficient adhesive strength can be obtained, and if it is 30 g / m ² or less, the pressure-sensitive adhesive does not protrude during printing.
The pressure-sensitive adhesive is applied by a method in which the pressure-sensitive adhesive is diluted with a solvent such as ethyl acetate or toluene to prepare a coating solution having a solid content of 20 to 60% by mass and this coating solution is applied to a release sheet. Can do. Examples of the application device for the pressure-sensitive adhesive include known coating devices such as a knife coater, a comma coater, a gravure coater, and a roll coater.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.

(Evaluation method)
(1) Weather resistance (appearance)
The appearance of the weather resistant sheets obtained in Examples and Comparative Examples was visually observed after 500 hours of the super UV test (super accelerated weather resistance test), and evaluated according to the following criteria.
◎: No change in appearance was confirmed ○: Although a slight change in appearance was confirmed, there was no practical problem ×: A change in appearance was confirmed (2) Weather resistance (mechanical strength)
The weather resistant sheets obtained in Examples and Comparative Examples were evaluated for tensile fracture stress (tensile stress at the time of specimen breakage) by a tensile test after 500 hours of super UV test (super accelerated weather resistance test). Judged by the criteria of.
◎: Maintain 50% or more before the test ○: Maintain 20% or more to less than 50% before the test ×: Less than 20% before the test

(3) Adhesiveness The weather-resistant sheet obtained in Examples and Comparative Examples was cross-cut, and the operation of affixing Cellotape (registered trademark) made by Nichiban on its surface and abruptly peeling was performed 5 times. At this time, whether or not each layer provided on the base material was peeled was visually observed and evaluated according to the following criteria.
A: No peeling of the layer was confirmed.
○: Almost no peeling of the layer was confirmed.
Δ: Some peeling of the layer was confirmed, but there was no practical problem.
X: Remarkable peeling of the layer was confirmed.

(4) Scratch resistance (steel wool resistance)
The weather resistant sheets obtained in Examples and Comparative Examples were rubbed 10 times with steel wool (# 0000), and then the surface of the weather resistant sheet was visually observed and evaluated according to the following criteria.
(Double-circle): The damage was not attached by the load of 300g.
○: No damage was observed at a load of 200 g.
Δ: No damage was observed at a load of 100 g.
X: Scratched with a load of 100 g.

Example 1
Polyethylene terephthalate having a thickness of 50 μm was used for the base film, and a PVDC resin was applied at a coating amount of 5 g / m ² by gravure coating on one side of the base film to provide a gas barrier layer having a thickness of 5 μm. Subsequently, a primer layer made of the following resin composition was sequentially laminated on the gas barrier layer at a film thickness of 5 μm (application amount 5 g / m ² ) and a surface protective layer made of the following resin composition at an application amount of 5 g / m ^2. Finally, an electron beam was irradiated under the conditions of 165 keV and 5 Mrad (50 kGy) to crosslink and cure the electron beam curable resin composition to obtain a weather resistant film having a surface protective layer having a thickness of 5 μm. The weather resistance (appearance), weather resistance (mechanical strength), adhesion and scratch resistance of the obtained weather resistant film were evaluated by the above methods.
The composition for forming the primer layer is as follows.
Polyurethane-based urethane / acrylic copolymer resin Mass ratio of urethane component to acrylic component in polycarbonate-based urethane acrylic copolymer resin: 70/30
Hydroxyphenyltriazine-based UV absorber: 15 parts by mass Product name “Tinuvin 400” manufactured by BASF Japan Ltd. Hydroxyphenyltriazine-based UV absorber: 5 parts by mass Product name “Tinuvin 479” manufactured by BASF Japan Ltd. Hindered amine light stabilizer Agent: 6 parts by mass Product name “Tinuvin 123”, manufactured by BASF Japan Ltd. Curing agent: Hexanemethylene diisocyanate: 6 parts by mass The resin composition of the surface protective layer is as follows.
Bifunctional caprolactone-based urethane acrylate oligomer: 100 parts by weight Hydroxyphenyltriazine-based ultraviolet absorber: 3 parts by weight Product name “Tinuvin 479”, manufactured by BASF Japan Ltd. Light stabilizer having a reactive functional group (reactive HALS): 3 Parts by mass 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate,
Product name “Sanol LS-3410”, manufactured by Nippon Emulsifier Co., Ltd. Silicone surfactant: 1 part by mass Product name “KP-301”, manufactured by Shin-Etsu Chemical Co., Ltd.

Reference example 1
A weather resistant film was obtained in the same manner as in Example 1 except that a 10 nm thick silica deposited film formed by vapor deposition was used as the gas barrier layer. The results evaluated in the same manner as in Example 1 are shown in Table 1.
Example 3
The surface protective layer is 100 parts by mass of a hexafunctional caprolactone-based urethane acrylate oligomer, the addition amount of an ultraviolet absorber (trade name “Tinuvin 479”) is 1 part by weight, and a light stabilizer having a reactive functional group (trade name “Sanol LS-3410”). ]) Was obtained in the same manner as in Example 1 except that 3 parts by mass of the mixture was used. The results evaluated in the same manner as in Example 1 are shown in Table 1.

Comparative Example 1
A weather resistant film was obtained in the same manner as in Example 1 except that the barrier layer was not provided. The results evaluated in the same manner as in Example 1 are shown in Table 1.
Comparative Example 2
A weather resistant film was obtained in the same manner as in Example 1 except that the primer layer was not provided. The results evaluated in the same manner as in Example 1 are shown in Table 1.

As is clear from Table 1 , the weather resistant films of Examples 1 and 3 and Reference Example 1 were all good in weather resistance (appearance), weather resistance (mechanical strength), adhesion and scratch resistance. . On the other hand, since the film of Comparative Example 1 had no gas barrier layer, the mechanical strength was significantly reduced. And since the film of the comparative example 2 did not have a primer layer, the film turned yellow and the external appearance deteriorated, and the mechanical strength also decreased.
In addition, the weather-resistant films of Examples 1 and 3 and Reference Example 1 were respectively attached to glass via an adhesive layer (2-ethylhexyl acrylate) to produce a window glass with a scattering prevention function, and a super UV test (ultra-UV test) Accelerated weather resistance test) When evaluated after 500 hours, the transparency of the weather resistant film was maintained, and even if the glass was broken, the mechanical strength was high, so that scattering of the glass could be suitably prevented.

  Since the weather resistant film of the present invention can maintain weather resistance for a long period of time, it is suitably used for entrance doors and exterior materials of general residences, interior and exterior such as floor materials and exterior walls of public facilities, and is used in buildings and outdoors. It is suitably used for parts exposed to direct sunlight and wind and rain, such as installed structures, window glass, and furniture, and forms various interior and exterior materials. In particular, it is suitably used as a window glass with a scattering prevention function.

1. 1. Weather resistant film 2. Base sheet 3. Gas barrier layer Primer layer 5. Surface protective layer

Claims (7)

On a base sheet made of a polyester resin film, a gas barrier layer, a primer layer containing a weathering agent, and a surface protective layer made of a crosslinked cured product of an ionizing radiation curable resin composition containing a weathering agent are provided in this order. The weather barrier film is characterized in that the gas barrier layer comprises at least one selected from polyvinylidene chloride, polyvinyl alcohol, ethylene / vinyl alcohol copolymer and polyacrylonitrile . The weather resistant film according to claim 1, wherein the primer layer contains a polycarbonate-based urethane / (meth) acrylic copolymer resin .   The weatherable film according to claim 1 or 2, wherein the weathering agent is at least one selected from an ultraviolet absorber and a hindered amine light stabilizer.   The weatherable film according to any one of claims 1 to 3, wherein the ionizing radiation curable resin composition contains a tetrafunctional or higher urethane (meth) acrylate oligomer.   The weather resistant film according to any one of claims 1 to 4, wherein the surface protective layer contains at least one selected from a silicone-based surfactant, a fluorine-based surfactant, and a silicone (meth) acrylate.   The weather resistant film according to any one of claims 1 to 5, further comprising an adhesive layer on a back surface side of the base sheet.   The interior / exterior material formed by sticking the weather-resistant film in any one of Claims 1-6.

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