JPH11309813A - Hardcoat film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To give superior abrasion resistance and weatherability to a film, and lessen deterioration caused by even providing an optical catalyst layer by laminating in turn a UV ray cutting layer and a hardcoat layer containing a silicon compound having a siloxane combination on one surface of a transparent base material film. SOLUTION: A hardcoat film layer is manufactured by laminating by turns a UV ray cutting layer and a hardcoat layer containing a silicon compound having a siloxane combination on one surface of a transparent base material film. In this case, the UV ray cutting layer is preferable to be a layer consisting of one layer or two layer or more containing at least one kind selected from a UV ray diffuser and UV ray absorbent. The transparent base material film can be selected from a transparent plastic film, and as a concrete example thereof, there is a film of polyethylene, polypropylene or the like. Furthermore, given as a concrete example of the UV ray diffuser is powder obtained by minutely granulating titanium dioxide, zinc oxide, cerium oxide or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel hard coat film, and more particularly, it has excellent abrasion resistance and weather resistance, and is particularly suitable for attaching to the outer surface of a window glass or a plastic board for windows. Related to a hard coat film.

[0002]

2. Description of the Related Art Conventionally, plastic films have been used for attaching window glass and plastic boards for windows for various purposes. For example, sunlight entering a room through a window glass includes ultraviolet rays and infrared rays in addition to visible light rays. It has been pointed out that ultraviolet rays contained in sunlight cause sunburn and adverse effects on the human body have recently been pointed out, and it is well known that deterioration of contents due to deterioration of packaging materials due to ultraviolet rays is well known. on the other hand,
Infrared rays included in the sun also have a problem in that the indoor temperature rises due to direct sunlight and the cooling effect in summer is reduced. Therefore, in order to avoid such an undesirable situation, an ultraviolet shielding film or an infrared shielding film is used for attaching a window glass or a window plastic board. Also, in order to make the room hard to see from the outside, it is common practice to attach an internal anti-glare film to a window glass or a window plastic board. Furthermore, in order to prevent glass fragments from scattering when the window glass is damaged by a disaster such as an earthquake, a film for preventing glass fragments from scattering is used for attaching a window glass. In addition,
The above-mentioned ultraviolet shielding film, infrared shielding film, and internal visual protection film also have such a debris scattering prevention effect. These window glasses and films for attaching a plastic board for windows (hereinafter sometimes referred to as window films) are usually ionizing radiation-curable resins, such as polyester acrylate-based resins, for imparting abrasion resistance and the like to the surface thereof. A hard coat layer formed by applying an epoxy acrylate resin, a urethane acrylate resin, a polyol acrylate resin, or the like and curing the resin is provided. By the way, when an ultraviolet scattering agent is added to impart weather resistance to the hard coat layer, it causes a reduction in the abrasion resistance of the hard coat surface, and when an ultraviolet absorber is added, ionizing radiation It may be a factor that hinders curing and lowers scratch resistance. Therefore, it has been difficult to obtain satisfactory ultraviolet protection for the base film with the conventional hard coat film. Therefore, window film is
Generally, it is attached to the inner surface of a window glass or the like. This is because, when affixed to the outer surface, the hard coat layer and the base film provided on the film surface are significantly deteriorated by ultraviolet rays, and the surface is soiled, so that the life is extremely short. By the way, in recent years, semiconductors such as titanium dioxide have been found to have a strong photocatalytic action,
Research and development of photocatalysts have been actively conducted. This photocatalyst excites a semiconductor represented by, for example, titanium dioxide with light having an energy equal to or greater than its band gap, whereby electrons are generated in the conduction band and holes are generated in the valence band. It utilizes hole pairs, and by applying such photocatalysis,
For example, decomposing and removing various substances that are a problem on environmental pollution in wastewater and waste gas, and deodorizing, antifouling, antibacterial, and sterilizing are being studied. Further, as described above, when such a photocatalyst is irradiated with light having energy equal to or larger than the band gap, electrons are generated in a conductor of the photocatalyst, holes are generated in a valence band, and the electrons and / or electrons are generated. It is known that the function of the holes imparts polarity to the surface and makes the surface super-hydrophilic. Therefore, recently, it has been attempted to provide a photocatalyst layer on the surface of a window film by utilizing such superhydrophilicity and antifouling performance of the photocatalyst, and to attach the film to a front surface such as a glass window. In this trial, by repeating the irradiation of sunlight and rainfall, dirt (organic matter) adhering to the film surface is not cleaned, and the film is naturally cleaned using its superhydrophilicity and antifouling performance (self-cleaning). ), As well as to prevent fogging of the window glass and secure visibility in rainy weather. However, in the conventional window film, since the hard coat layer provided on the surface is mainly composed of the cured resin which is an organic substance as described above, when a photocatalyst layer is provided thereon, the photocatalytic action promptly causes the photocatalytic action. In addition to the deterioration of the hard coat layer, since the window film is directly exposed to ultraviolet light, the deterioration of the base film itself progresses quickly,
There is a problem that the life is extremely short.

[0003]

Under such circumstances, the present invention has excellent abrasion resistance and weather resistance, and even if a photocatalytic layer is provided on the surface, deterioration due to the photocatalytic layer is small. It is also possible to provide a layer having antibacterial properties, and it has been made for the purpose of providing a hard coat film particularly suitable for sticking to the outer surface of a window glass or a plastic board for windows.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to develop a hard coat film having excellent performance as described above. It has been found that a laminated film having a hard coat layer made of the above material sequentially and a release sheet provided on the opposite surface thereof via an adhesive layer if desired can be adapted to the purpose, and based on this finding, the present invention Was completed. That is, the present invention provides (1) a hard coat film, in which an ultraviolet shielding layer and a hard coat layer containing a silicon compound having a siloxane bond are sequentially provided on one surface of a transparent base film. To provide. Further, a preferred embodiment of the present invention is:
(2) The hard coat film according to (1), wherein the ultraviolet shielding layer is a layer comprising one or more layers containing at least one selected from an ultraviolet scattering agent and an ultraviolet absorber. The hard coat film according to (2), wherein the ultraviolet shielding layer is a layer containing an inorganic ultraviolet scattering agent in a silicon-based binder;
The hard coat film according to item (2), which is a layer containing an ultraviolet absorber in an organic binder, and (5) the ultraviolet shielding layer contains an ultraviolet absorber in the organic binder from the base film side. The hard coat film according to (2), which has a two-layer structure in which a layer and a layer containing an inorganic ultraviolet scattering agent in a silicon-based binder are sequentially laminated.
(6) The hard coat film according to any one of (1) to (5), wherein a primer layer is provided between the ultraviolet shielding layer and the base film, and (7) a hard coat layer containing a silicon compound having a siloxane bond. Is an inorganic silica-based compound and / or
Alternatively, the hard coat film according to any one of (1) to (6), which is a layer containing a polyorganosiloxane-based compound as a main component, and (8) a transparent substrate film on the surface opposite to the surface on which the hard coat layer is provided. The hard coat film according to any one of (1) to (7), wherein a release sheet is provided via an adhesive layer. (9) Nos. (1) to (8) used for attaching an outer surface of a window glass or a plastic board for windows.
The hard coat film described in the above item.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The transparent base film used for the hard coat film of the present invention is not particularly limited.
It can be appropriately selected and used from various transparent plastic films depending on the situation. Examples of the transparent plastic film include polyethylene, polypropylene, poly-4-methylpentene-1, polybutene-1
Polyolefin resins such as polyethylene terephthalate, polyester resins such as polyethylene naphthalate, polycarbonate resins, polyvinyl chloride resins, polyphenylene sulfide resins, polyether sulfone resins, polyethylene sulfide resins,
A film made of a polyphenylene ether-based resin, a styrene-based resin, an acrylic-based resin, a polyamide-based resin, a polyimide-based resin, a cellulose-based resin such as cellulose acetate, or a laminated film thereof is used. The thickness of the transparent substrate film is not particularly limited and may be appropriately selected depending on the purpose of use.
0 μm, preferably in the range of 10 to 100 μm. The transparent substrate film may be colored or vapor-deposited as desired, and may contain an ultraviolet absorber. Further, for the purpose of improving the adhesion to a layer provided on the surface, one or both surfaces can be subjected to a surface treatment by an oxidation method, a roughening method, or the like, if desired. Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet method), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and examples of the unevenness method include a sand blast method and a solvent treatment method. Is mentioned. These surface treatment methods are appropriately selected according to the type of the base film, but generally, the corona discharge treatment method is preferably used from the viewpoint of effects and operability. In the hard coat film of the present invention, an ultraviolet shielding layer and a hard coat layer are sequentially provided on one surface of the transparent base film. The ultraviolet shielding layer is a layer containing at least one selected from an ultraviolet scattering agent and an ultraviolet absorbing agent as an ultraviolet shielding material. And the deterioration of the base film due to ultraviolet rays is suppressed. here,
By scattering ultraviolet rays,
It is a material that provides an ultraviolet blocking effect, and an inorganic material such as a metal oxide powder is mainly used. Examples of the ultraviolet scattering agent include fine particles of titanium dioxide, zinc oxide, cerium oxide, etc., or hybrid inorganic powders obtained by compounding titanium dioxide fine particles with iron oxide, and the surface of cerium oxide fine particles. Hybrid inorganic powders coated with non-crystalline silica are exemplified. The UV scattering effect is greatly affected by the particle size,
In the present invention, the average particle size of the ultraviolet scattering agent,
It is preferably 3 μm or less, and particularly preferably in the range of 1 nm to 1.5 μm. On the other hand, ultraviolet absorbers absorb ultraviolet rays having high energy, convert them to harmless energy, and re-radiate them, thereby providing an ultraviolet blocking effect and improving the light resistance and weather resistance of plastics. ,
In general, salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, and others can be roughly classified. Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, p-octylphenyl salicylate, and pt-butylphenyl salicylate. Examples of the benzophenone-based ultraviolet absorber include 2,2'-dihydroxy-4-. Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-
Hydroxy-4-octoxybenzophenone and the like. Examples of the benzotriazole-based ultraviolet absorber include 2- (2'-hydroxy-3 ', 5'-di-
tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ' -Tert-
Amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 '-Isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-
tert-butylphenyl) benzotriazole, 2-
(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-5 '-(1,1,
3,3-tetramethyl) phenyl] benzotriazole and the like. Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate and 2-cyano-3,3-diphenylacryl. And 2-ethylhexyl acid. Further, as other ultraviolet absorbers, for example, resorcinol monobenzoate, 2,4-di-t-butylphenyl-3,5-
Di-t-butyl-4-hydroxybenzoate, N-
(2-ethylphenyl) -N '-(2-ethoxy-5-
(t-butylphenyl) oxalic acid diamide and the like.

[0006] As a light stabilizer, a light stabilizer such as a hindered amine type which improves light resistance and weather resistance may be used in combination with the above-mentioned ultraviolet absorber, if desired.
In the present invention, these ultraviolet shielding materials may be used alone or in combination of two or more.
The content of the ultraviolet shielding material in the ultraviolet shielding layer is not particularly limited, and is appropriately selected depending on the type of the ultraviolet shielding material, the type of the base film, and the like.
The range is from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight. When the ultraviolet shielding material is an ultraviolet scattering agent, its content is preferably in the range of 0.1 to 10% by weight, and particularly preferably in the range of 1 to 5% by weight. On the other hand, when the ultraviolet shielding material is an ultraviolet absorber or a light stabilizer, its content is preferably in the range of 0.01 to 10% by weight, particularly preferably in the range of 0.05 to 5% by weight.

The ultraviolet shielding layer in the hard coat film of the present invention is a layer comprising an appropriate binder and the ultraviolet shielding material contained therein, and may be a single layer or, if necessary, two or more layers, for example, It may have a laminated structure of 2 to 10 layers. The binder is not particularly limited, and any of inorganic and organic substances can be used.However, when the ultraviolet shielding material is an ultraviolet scattering agent for inorganic particles, a silicon-based binder is preferable.
In the case of an ultraviolet absorber, an organic binder is preferred. As the constitution of the ultraviolet shielding layer, for example, (1) a layer containing an inorganic ultraviolet scattering agent in a silicon binder,
(2) a layer containing an ultraviolet absorber in an organic binder; and (3) a layer containing an ultraviolet absorber in an organic binder from the substrate film side, and an inorganic ultraviolet scattering agent in a silicon binder. A two-layer structure obtained by sequentially laminating the containing layers is preferable. The silicon-based binder is not particularly limited, and examples thereof include inorganic silica-based (including polysilicic acid), polyorganosiloxane-based, and a mixture thereof. These can be manufactured by various conventionally known methods. For example, the general formula _{^{[1] R 1 n Si (}} OR 2) 4-n ... [1] [R ¹ in the formula is a non-hydrolyzable group, an alkyl group,
Substituted alkyl group (substituent: halogen atom, epoxy group,
(Meth) acryloyloxy group), alkenyl group,
An aryl group or an aralkyl group, R ² is a lower alkyl group, and n is an integer of 0 or 1-3. When there are a plurality of R ¹ and OR ² , a plurality of R ¹ may be the same or different, and a plurality of OR ² may be the same or different. Is preferably partially or completely hydrolyzed using an inorganic acid such as hydrochloric acid or sulfuric acid, or an organic acid such as oxalic acid or acetic acid, and polycondensed. In this case, if the compound in which n is 0, that is, tetraalkoxysilane is completely hydrolyzed, an inorganic silica-based binder can be obtained.
A polyorganosiloxane binder or a mixed binder of inorganic silica and polyorganosiloxane is obtained. On the other hand, a compound in which n is 1 to 3 has a non-hydrolyzable group, so that a polyorganosiloxane binder can be obtained by partial or complete hydrolysis. At this time, an appropriate organic solvent may be used in order to perform the hydrolysis uniformly.

Examples of the alkoxysilane compound represented by the general formula [1] include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane and tetraisosilane. Butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltri Ethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ- Taku Leroy Le trimethoxysilane, dimethyl dimethoxysilane, methylphenyl dimethoxysilane, vinyltrimethoxysilane,
Examples include vinyltriethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, trivinylmethoxysilane, and trivinylethoxysilane. These may be used alone or in combination of two or more. At this time, if necessary, an appropriate amount of an aluminum compound such as aluminum chloride or trialkoxy aluminum can be added. Further, as another method, sodium metasilicate, sodium orthosilicate or water glass (a mixture of sodium silicate) is used as a silicon compound as a raw material, and an acid such as hydrochloric acid, sulfuric acid, or nitric acid or a metal compound such as magnesium chloride or calcium sulfate is used. And a hydrolysis method. By this hydrolysis treatment, free silicic acid is produced, which is easily polymerized and is a mixture of chain-like, cyclic and mesh-like ones, depending on the type of raw material. Polysilicic acid obtained from water glass has the general formula [2]

Embedded image (Wherein m represents the degree of polymerization and R is a metal such as hydrogen, silicon or magnesium or aluminum). In this way, a complete inorganic silica-based binder is obtained. Silica gel (SiO _X · nH ₂ O) is used as an inorganic silica-based binder.
Can also be used. This ultraviolet shielding layer is not necessary because the hard coat performance is strong, but rather, from the viewpoint of adhesion, a polyorganosiloxane binder or a mixed binder of inorganic silica and polyorganosiloxane rather than a complete inorganic silica binder. Is preferred.
On the other hand, the organic binder is not particularly limited, and conventionally known ones, such as an acrylic resin, a polyester resin, a polyurethane resin, a butyral resin, and the like, further include a cured product of an ionizing radiation-curable resin. it can. Here, the ionizing radiation-curable resin is a resin that is cured by irradiation with ultraviolet rays, electron beams, or the like, and among them, particularly, an ultraviolet-curable resin that has been frequently used for forming a hard coat layer of an indoor window film. Is preferred. Examples of the ultraviolet curing resin include an ultraviolet curing polyester acrylate resin, an ultraviolet curing epoxy acrylate resin, and an ultraviolet curing urethane acrylate resin. Various monofunctional monomers or polyfunctional monomers such as an ester of a polyhydric alcohol and (meth) acrylic acid can be added to the UV-curable resin, if necessary. For example, acetophenones, benzophenones, benzoins, phenyl ketones and the like are used.

The ultraviolet shielding layer in the present invention is prepared by preparing a coating solution containing the binder and the ultraviolet shielding material, and using a conventionally known method such as a bar coating method, a knife coating method, a roll coating method, a blade coating method, and a die coating method. By using a gravure coating method or the like, coating on a base film, irradiating with heating or ionizing radiation, and curing,
Can be formed. The thickness of this ultraviolet shielding layer is usually in the range of 0.1 to 20 μm, preferably 0.5 to 10 μm. In the present invention, a primer layer can be provided between the ultraviolet shielding layer and the substrate film, if desired, in order to improve the adhesion between the ultraviolet shielding layer and the substrate film. This primer layer is particularly effective when the ultraviolet shielding layer is provided in the case of the above-mentioned constitution (1), that is, a layer containing an inorganic ultraviolet scattering agent in a silicon-based binder. The primer is not particularly limited, and a conventionally known primer such as an acrylic, polyester, polyurethane, silicone, or rubber primer can be used. Based and polyester based primers are preferred. If necessary, the primer may contain an ultraviolet absorber or a light stabilizer. The thickness of the primer layer is preferably in the range of 0.1 to 10 μm, particularly preferably 0.1 to 10 μm, from the viewpoint of uniform coating properties and adhesion.
A range of 5 to 5 μm is preferred. Further, as the antibacterial agent, a silver-based inorganic antibacterial agent using zirconium phosphate as a carrier, a silver-based inorganic antibacterial agent using zeolite as a carrier, a silver-based inorganic antibacterial agent using calcium phosphate as a carrier, and silica gel as a carrier. Various antibacterial agents, such as silver-based inorganic antibacterial agents such as silver-based inorganic antibacterial agents, amino acid-based organic antibacterial agents containing an amino acid compound, and nitrogen-containing sulfur-based organic antibacterial agents containing a nitrogen-containing sulfur-based compound. What is necessary is just to mix | blend in a resin composition an appropriate amount according to the kind of antibacterial agent used, the antibacterial property required, the holding time, etc. In the hard coat film of the present invention, a hard coat layer is provided on the ultraviolet shielding layer thus formed. The hard coat layer is a layer containing a silicon compound having a siloxane bond, and preferably includes, for example, a layer mainly containing an inorganic silica-based compound (including polysilicic acid) and / or a polyorganosiloxane-based compound. it can. The inorganic silica-based compound and the polyorganosiloxane-based compound can be similarly produced by the method described for the silica-based binder. In this hard coat layer, since the hard coat performance is regarded as important, a layer containing as much inorganic silica-based compound as possible is preferable as long as necessary adhesion is maintained.
The hard coat layer may contain the above-mentioned inorganic ultraviolet scattering agent and the like, if desired, as long as the scratch resistance is not impaired. This hard coat layer, a hard coat material-containing coating solution, using a known method, for example, bar coating method, knife coating method, roll coating method, blade coating method, die coating method, gravure coating method, etc.
It can be formed by coating on an ultraviolet light shielding layer, heating and curing. When a hard coat layer made of an inorganic silica-based compound is formed, a physical vapor deposition method (PVD method) such as a vacuum deposition method, a sputtering method, or an ion plating method can be employed.

[0010] The thickness of the hard coat layer thus formed is usually 0.05 to 30 µm, preferably 0.05.
２０20 μm. In the hard coat film of the present invention, if necessary, a release sheet can be provided via an adhesive layer on the surface opposite to the side on which the ultraviolet ray shielding layer and the hard coat layer are provided on the base film in this manner. . The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited and may be appropriately selected from conventionally known various pressure-sensitive adhesives depending on the situation. , Urethane-based and silicone-based pressure-sensitive adhesives are preferred. The thickness of this adhesive layer is usually 5 to
It is in the range of 100 μm, preferably 10 to 60 μm.
The release sheet provided on the pressure-sensitive adhesive layer includes, for example, paper such as glassine paper, coated paper, laminated paper, and various plastic films coated with a release agent such as a silicone resin. The thickness of the release sheet is not particularly limited, but is usually 20 to
It is about 150 μm. The pressure-sensitive adhesive layer may contain an ultraviolet absorber or a light stabilizer, if necessary. The hard coat film of the present invention is suitably used particularly for attaching an outer surface of a window glass or a plastic board for windows. When used, the release sheet may be peeled off and attached so that the surface of the pressure-sensitive adhesive layer is in contact with the object. If necessary, printing can be performed on any layer other than the hard coat layer of the hard coat film of the present invention.

[0011]

EXAMPLES 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 physical properties of the hard coat films produced in the respective examples were determined according to the following procedures. (1) Pencil hardness The pencil hardness was measured by a hand drawing method according to JIS K 5400. (2) Weather resistance Weatherometer [WEL-SU, manufactured by Suga Test Machine Co., Ltd.]
N-DC type], an accelerated weathering test for 1000 hours was performed, and the appearance was visually observed and evaluated according to the following criteria. ：: No deterioration ×: Deterioration (3) Scratch resistance The surface of the hard coat layer was rubbed with steel wool # 0000, and the appearance was visually observed and evaluated according to the following criteria. ：: No scratches ×: Scratches (4) Antibacterial properties Inoculated on the film with MRSA bacteria solution (10 ⁴ cells / ml) (1
0 μl / cm ² ) and left at 23 ° C. and 65% RH for 3 hours.
The bacteria were washed away, and the number of viable bacteria was measured using a medium for measuring the number of bacteria. (5) Antifouling property Dirt after 500 hours of outdoor exposure was visually observed and evaluated according to the following criteria. ：: No stain ×: Stained Example 1 As a substrate film, a polyethylene terephthalate film having a thickness of 50 μm [hereinafter abbreviated as PET film. Using "4100" manufactured by Toyobo Co., Ltd.], 2% by weight of cerium oxide powder [Serigard S3018-02 manufactured by Nippon Inorganic Chemical Industry Co., Ltd .; Silicon binder [Colcoat
"N-103X" manufactured by Co., Ltd.] A coating agent consisting of 98% by weight was applied with a Meyer bar so that the dry film thickness became 2 μm, and then dried at 100 ° C. for 1 minute to provide an ultraviolet shielding layer. . Then, a coating agent containing an inorganic silica-based compound on the coated surface [GO-100 manufactured by Nikko Corporation]
SX "] was applied using a Meyer bar to a dry film thickness of 3 μm, and then dried at 100 ° C. for 2 minutes to provide a hard coat layer. Table 1 shows the physical properties of this hard coat film. Example 2 As a base film, a PET film having a thickness of 25 μm [“Lumirror Q37 # 25” manufactured by Toray Industries Inc., containing an ultraviolet absorber] was subjected to corona discharge treatment on both surfaces, and then one surface thereof was coated with an inorganic material. A coating agent comprising a silica-based binder as a main component and a small amount of cerium oxide powder, which is an ultraviolet scattering agent, [Cerastertz 2 manufactured by Parker Processing Co., Ltd.
7 "] was applied using a Meyer bar so that the dry film thickness became 3 μm, and then dried at 120 ° C. for 2 minutes to provide an ultraviolet shielding layer. Next, a coating agent containing a polyorganosiloxane compound [“Organosilica Sol CX-SZ” manufactured by Nippon Shokubai Co., Ltd.] was applied to the coated surface with a Meyer bar so that the dry film thickness became 5 μm.
After drying at 0 ° C. for 2 minutes, a hard coat layer was provided. Table 1 shows the physical properties of this hard coat film. Example 3 A 25 μm-thick polyethersulfone film [“TALPA-” manufactured by Mitsui Toatsu Chemicals, Inc.]
1000 "], two surfaces of which were subjected to a corona discharge treatment, and one surface of which was coated with 2% by weight of titanium dioxide powder [manufactured by Ishihara Techno Co., Ltd., average particle size 20 nm] and a silicon-based binder [colcoat] "N-103X" manufactured by Co., Ltd.]
98% by weight of coating agent is dried to a thickness of 2μ
m after coating with a Meyer bar to 100 m
For 1 minute to provide an ultraviolet shielding layer. Then, a coating agent containing an inorganic silica-based compound [“Frescella” manufactured by Matsushita Electric Works, Ltd.]
m after coating with a Meyer bar to 100 m
For 5 minutes to provide a hard coat layer. Table 1 shows the physical properties of this hard coat film. Example 4 A PET film having a thickness of 50 μm [“4100” manufactured by Toyobo Co., Ltd.] was used as a base film.
From 0.1% by weight of Tinuvin 1130 [manufactured by Ciba Specialty Chemicals Co., Ltd.] which is an ultraviolet absorber and 99.9% by weight of an organic urethane-based binder [“Superflex 410” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] The coating agent was applied with a Meyer bar so that the dry film thickness became 2 μm, and dried at 120 ° C. for 2 minutes to provide an ultraviolet shielding layer. Next, a coating agent containing inorganic silica-based compound [Cerastars 17 (manufactured by Parker Processing Co., Ltd.)] was applied to the coated surface with a Mayer bar so that the dry film thickness became 3 μm, and then the coating was performed at 120 ° C. for 2 minutes After drying, a hard coat layer was formed. Table 1 shows the physical properties of this hard coat film. Example 5 As a base film, a PET film having a thickness of 50 μm [“4100” manufactured by Toyobo Co., Ltd.] was used.
From 0.1% by weight of Tinuvin 1130 [manufactured by Ciba Specialty Chemicals Co., Ltd.] which is an ultraviolet absorber and 99.9% by weight of an organic urethane-based binder [“Superflex 410” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] The coating agent was applied with a Meyer bar so that the dry film thickness became 2 μm, and dried at 120 ° C. for 2 minutes to provide an ultraviolet shielding layer. Next, silica gel (SiO
_X · nH ₂ O) at a temperature of 1000 ° C. and a pressure of 5 × 10 ⁻³ Torr
Vacuum evaporation was performed under the conditions of r to form a hard coat layer made of a silicon oxide film having a thickness of 0.1 μm. Next, this P
97% by weight of butyl acrylate on the opposite side of the ET film
And a toluene solution containing 40% by weight of a copolymer of acrylic acid and 0.5% by weight of an aluminum chelate,
After coating with a comma coater, the coating was dried at 100 ° C. for 2 minutes to form an adhesive layer having a thickness of 20 μm. Further, a release film [SP- manufactured by Lintec Co., Ltd.] having a thickness of 38 μm.
PET3811 "] was laminated to produce a hard-coated pressure-sensitive adhesive film. Table 1 shows the physical properties of this hard coat film. Example 6 As a base film, a PET film having a thickness of 50 μm [“Lumirror # 50” manufactured by Toray Industries, Inc.] was subjected to corona discharge treatment, and one surface thereof was provided with Tinuvin 1130, an ultraviolet absorber, on one surface thereof. 2% by weight of Ciba Specialty Chemicals Co., Ltd.] and 4% by weight of Irgacure, a photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd.], and a UV-curable polyfunctional acrylate binder [TOA GOsei Co., Ltd.] "Aronix M305" manufactured by Co., Ltd.] is coated with a coating agent consisting of 94% by weight with a Meyer bar so that the film thickness after curing becomes 1 μm, and then 200 mJ / cm ^2.
Irradiation and curing were performed to provide a first ultraviolet shielding layer. Further, on this, cerium oxide powder as an ultraviolet scattering agent [Nippon Inorganic Chemical Industry Co., Ltd. “Serigard S301”
8-02 ", an average particle size of 1 μm] 2% by weight, and a coating agent comprising 98% by weight of a silicon-based binder [“ N-103X ”manufactured by Colcoat Co., Ltd.] and a Meyer bar having a dry film thickness of 2 μm. And dried at 100 ° C. for 1 minute to provide a second ultraviolet shielding layer. Next, a coating agent containing an inorganic silica compound [“GO-100SX” manufactured by Nikko Co., Ltd.]
After coating with a Meyer bar so that the
After drying at a temperature of 2 ° C for 2 minutes, a hard coat layer was provided. next,
A urethane-based pressure-sensitive adhesive was applied on the opposite surface of the PET film using a comma coater, and then dried at 140 ° C. for 3 minutes to form a pressure-sensitive adhesive layer having a thickness of 50 μm. Furthermore, a release film [SP-P manufactured by Lintec Co., Ltd.] having a thickness of 38 μm.
ET3811 "] was laminated to produce a hard-coated pressure-sensitive adhesive film. The urethane-based pressure-sensitive adhesive was 97% by weight of a polyurethane elastomer ["Chrisbon 5150S" manufactured by Dainippon Ink and Chemicals, Inc., concentration: 50% by weight].
Cross-linking agent [Crisbon NX, manufactured by Dainippon Ink and Chemicals, Inc.
75% by weight] and 3% by weight. Table 1 shows the physical properties of this hard coat film. Example 7 As a base film, a PET film having a thickness of 50 μm [“Lumirror # 50” manufactured by Toray Industries, Inc.] was subjected to corona discharge treatment on both surfaces, and then a polyester-based primer [Nihon Gosei Chemical Industry Co., Ltd. "Polyester W"
R-901 ”] was applied using a Meyer bar so that the dry film thickness became 1 μm, and then heated at 100 ° C. for 2 minutes to form a primer layer. On this primer layer, cerium oxide powder as an ultraviolet scattering agent [Nippon Inorganic Chemical Industry Co., Ltd.
“Serigard S3018-02”, average particle size 1 μm]
2% by weight and silicon-based binder [Colcoat Co., Ltd. "N
-103X "] 98% by weight of a coating agent,
After coating with a Meyer bar so as to have a dry film thickness of 2 μm, the coating was dried at 100 ° C. for 1 minute to provide an ultraviolet shielding layer. Next, a coating agent containing an inorganic silica-based compound on the coated surface [“GO-100SX” manufactured by Nikko Corporation]
Was coated with a Meyer bar so that the dry film thickness became 3 μm, and then dried at 100 ° C. for 2 minutes to provide a hard coat layer. Next, on the opposite surface of the PET film, a 20 μm-thick pressure-sensitive adhesive layer [however,
2% by weight of UV absorber "Sumisorb 90" (manufactured by Sumitomo Chemical Co., Ltd.)], and a release film was laminated thereon to prepare a hard coat adhesive film. Table 1 shows the physical properties of this hard coat film. Example 8 On the hard coat layer of Example 2, 99.5% by weight of a polyester resin [Vylon 20SS, manufactured by Toyobo Co., Ltd.] was added to a zirconium phosphate antibacterial agent carrying silver ions [Novalon AG300, Toagosei Co., Ltd.]. Chemical Co., Ltd., average particle size
5 .mu.m] was added using a mixed solvent of toluene and methyl ethyl ketone with a gravure coater so that the thickness after drying was 0.2 .mu.m.
Drying treatment was performed at 100 ° C. for 30 seconds. Table 1 shows the physical properties of this hard coat film. Example 9 On the hard coat layer of Example 2, furthermore, Ishihara Techno Co., Ltd.
Made, titanium oxide ST-K03 with a gravure coater,
Coating so that the thickness after drying becomes 0.5 μm,
Drying was performed at 20 ° C. for 20 minutes. Table 1 shows the physical properties of this hard coat film. Comparative Example 1 A hard coat film was produced in the same manner as in Example 1 except that cerium oxide powder as an ultraviolet scattering agent was not used. The physical properties are shown in Table 1. Comparative Example 2 A 50 μm thick PET film [“4100” manufactured by Toyobo Co., Ltd.] was used as a base film, and on one side thereof,
Cerium oxide powder as an ultraviolet scattering agent [Nippon Inorganic Chemical Industry Co., Ltd. “Serigard S3018-02”, average particle size 1
μm] and a binder containing 98% by weight of a binder [“GO-100SX” manufactured by Nikko Co., Ltd.] containing 2% by weight of an inorganic silica-based compound. And dried at 100 ° C. for 1 minute. Table 1 shows the physical properties of this hard coat film.

[0012]

[Table 1]

[0013]

The hard coat film of the present invention has excellent abrasion resistance and weather resistance, and furthermore, even if a photocatalyst layer is provided, there is little deterioration due to the photocatalyst layer, and a layer having antibacterial properties can be provided. Yes, it is particularly suitable for attaching to the outer surface of a window glass or a plastic board for windows.

Claims (9)

[Claims] 1. A hard coat film comprising: a transparent substrate film; and an ultraviolet shielding layer and a hard coat layer containing a silicon compound having a siloxane bond are sequentially provided on one surface of the transparent base film. 2. The hard coat film according to claim 1, wherein the ultraviolet shielding layer is a layer comprising one or more layers containing at least one selected from an ultraviolet scattering agent and an ultraviolet absorber. 3. The hard coat film according to claim 2, wherein the ultraviolet shielding layer is a layer containing an inorganic ultraviolet scattering agent in a silicon binder. 4. The hard coat film according to claim 2, wherein the ultraviolet shielding layer is a layer containing an ultraviolet absorbent in an organic binder. 5. The ultraviolet shielding layer is formed by sequentially laminating a layer containing an ultraviolet absorber in an organic binder and a layer containing an inorganic ultraviolet scattering agent in a silicon binder from the substrate film side. The hard coat film according to claim 2, which has a two-layer structure. 6. The hard coat film according to claim 1, wherein a primer layer is provided between the ultraviolet shielding layer and the substrate film. 7. The hard coat layer containing a silicon compound having a siloxane bond is a layer containing an inorganic silica compound and / or a polyorganosiloxane compound as a main component. Hard coat film. 8. The hard coat film according to claim 1, wherein a release sheet is provided via an adhesive layer on a surface of the transparent substrate film opposite to the surface on which the hard coat layer is provided. . 9. The hard coat film according to claim 1, which is used for attaching an outer surface of a window glass or a window plastic board.