JP2003213230A - Protective film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prepare a protective film having a hard coat layer excellent in scratching resistance, weather resistance and transparency, and capable of being used by pasting it on the side of outdoors for a long period. <P>SOLUTION: This protective film has a hard coat layer containing an ultraviolet light-absorbing agent on one side of a resin film and an adhesive layer containing the ultraviolet light-absorbing agent on the another side surface. The adhesive layer and/or hard coat layer preferably contain a heat rays- insulating agent, or are further installed with a layer containing the heat rays- insulating agent. The hard coat layer consists preferably of a cured material of a covering composition (a) containing a compound having ≥1 polymerizable functional group having an active energy beam-curing property as a curing component. The covering composition (a) contains preferably colloidal silica. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a protective film having an effect of blocking ultraviolet rays and / or heat rays, which is used by being adhered to automobile glass, window glass of buildings and the like. More specifically, it relates to a protective film having a hard coat layer having excellent scratch resistance, weather resistance and transparency, which can be attached to the outdoor side and used for a long time.

[0002]

2. Description of the Related Art Sunlight contains ultraviolet rays that cause deterioration of substances and infrared rays that serves as a heat source, and often causes disadvantages in daily life and industry.

Therefore, a resin film such as an ultraviolet blocking film may be attached to glass (particularly window glass) for the purpose of blocking ultraviolet rays and / or heat rays and preventing scattering of the glass.

For example, in a convenience store or the like where large glass is used in a part of the store, in order to protect the products in the store from sunlight, insects are also exposed to near-ultraviolet rays contained in a fluorescent lamp. Therefore, an ultraviolet ray blocking film may be attached to the glass from the viewpoint of insect repellent.

Conventionally, as such a resin film,
A plastic film base material coated with a polymer resin with a UV absorber added as the main component or an adhesive with a UV absorber added, or a plastic film base with the UV absorber kneaded Things are known.

[0006]

The conventional resin film as described above is usually used by sticking it from the indoor side. For example, when it is applied to a convenience store that is open 24 hours a day, In some cases, it was difficult to attach the product from the indoor side due to work reasons such as the need to move the product.

However, when the conventional resin film is used by being stuck on the outdoor side, the scratch resistance and weather resistance are insufficient, so
It is easily scratched and its transparency deteriorates, and since it is exposed to sunlight directly, the plastic film substrate is easily colored,
There was a problem that they had to be replaced in a short period of time.

An object of the present invention is to provide a protective film having a hard coat layer which is excellent in scratch resistance, weather resistance and transparency and which can be used by being stuck on the outdoor side for a long time.

[0009]

In order to achieve the above object, the protective film of the present invention is a protective film to be adhered to the glass surface on the outdoor side, and an adhesive layer for adhering to the glass surface, A resin film attached via an adhesive layer, and a hard coat layer provided on the surface of the resin film, wherein the adhesive layer and the hard coat layer contain an ultraviolet absorber. .

Since the protective film of the present invention has a hard coat layer containing an ultraviolet absorber on the surface of the resin film, it is excellent in scratch resistance, weather resistance and transparency and can be used on the outdoor side for a long time. . Further, since the pressure-sensitive adhesive layer also contains a UV absorber, it has a sufficient UV blocking effect.

In the protective film of the present invention, it is preferable that the pressure-sensitive adhesive layer and / or the hard coat layer contains a heat ray blocking agent, or a layer containing a heat ray blocking agent is further provided. According to this aspect, not only the ultraviolet rays but also the infrared rays serving as the heat source can be blocked.

The hard coat layer preferably comprises a cured product of the coating composition (a) containing as a curable component a compound having at least one active energy ray-curable polymerizable functional group. According to this aspect, a hard coat layer having excellent scratch resistance, weather resistance and transparency can be formed.

Further, it is preferable that the coating composition (a) contains colloidal silica. According to this aspect, the scratch resistance of the hard coat layer can be further improved.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The protective film of the present invention comprises a pressure-sensitive adhesive layer for sticking to a glass surface, a resin film stuck via the pressure-sensitive adhesive layer, and a hard coat provided on the surface of the resin film. A layer, and the adhesive layer and the hard coat layer contain an ultraviolet absorber. Further, the protective film of the present invention may further have a heat ray blocking layer.

The resin film and each layer will be described in detail below. As the resin film used in the present invention, polycarbonate is preferably used from the viewpoint of weather resistance, but aromatic polyester resins such as polyethylene terephthalate, polybutylene terebutarate and polyethylene naphthalate can also be used. Further, the resin may have a single composition or a blend of a plurality of resins. Although the thickness of the resin film can be appropriately selected, it is usually preferably 25 to 200 μm.

In order to improve the adhesion between the resin film and the hard coat layer (and the heat ray blocking layer), it is preferable to perform surface treatment or undercoat treatment of the resin film.
As the surface treatment, for example, corona discharge treatment, plasma (glow discharge) treatment, high frequency sputter etching treatment,
A known method such as alkaline solution treatment can be adopted. As the undercoating treatment, an easily adhesive agent such as urethane emulsion or polyester emulsion may be applied.

Next, the hard coat layer formed on the surface of the resin film will be described. The hard coat layer may be composed of one cured product layer or may be composed of two or more cured product layers.

In the present invention, the coating composition for forming the hard coat layer contains a compound containing an ultraviolet absorber and having at least one active energy ray-curable polymerizable functional group as a curable component (hereinafter, referred to as active compound). It is preferable to use a coating composition (a) containing an energy ray-curable component). In the following description, the acryloyl group and the methacryloyl group are collectively referred to as a (meth) acryloyl group, and the expressions (meth) acryloyloxy group, (meth) acrylic acid, (meth) acrylate and the like are also the same.

Among the active energy ray-curable components, the compound having one polymerizable functional group capable of being polymerized by active energy rays (hereinafter, simply referred to as a monofunctional compound) has a (meth) acryloyl group. A compound is preferable, and a compound having an acryloyl group is particularly preferable. In addition, it may have a functional group such as a hydroxyl group and an epoxy group. Examples of the monofunctional compound include the following.

Alkyl (meth) acrylate (wherein the alkyl group has 1 to 13 carbon atoms), allyl (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, butanediol (meth) acrylate, butoxytriethylene glycol. Mono (Meta)
Acrylate, tert-butylaminoethyl (meth)
Acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, di Cyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate,

N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate,
Glycerol (meth) acrylate, glycidyl (meth) acrylate, heptadecafluorodecyl (meth)
Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride, 2-hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, 3- (meth) acryloyloxypropyl Trimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxylated cyclo Decatriene (meth) acrylate,

Morpholine (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, octafluoropentyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate,
Phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxy (meth) acrylate,
Polypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, trifluoroethyl (meth) acrylate, vinyl acetate, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylformamide, morpholino (Meth) acrylate, 2-
Morpholinoethyl (meth) acrylate.

Of the active energy ray-curable components,
Examples of the compound having two or more active energy ray-curable polymerizable functional groups (hereinafter, simply referred to as a polyfunctional compound) are, for example, JP-A No. 11-240103, paragraphs 0016 to 0020 and paragraphs 0023 to. 00
And the compounds described in 47. Preferred polyfunctional compounds include compounds having two or more (2 to 50 are preferable, and 3 to 30 are preferable) one or more kinds of polymerizable functional groups selected from (meth) acryloyl groups. Among them, a compound having two or more (meth) acryloyloxy groups, that is, a polyester of (meth) acrylic acid and a compound having two or more hydroxyl groups such as polyhydric alcohol is preferable. Further, it may be a compound having various functional groups or bonds other than the above-mentioned polymerizable functional groups. In particular, a (meth) acryloyl group-containing compound having a urethane bond (hereinafter referred to as acrylic urethane),
A (meth) acrylic acid ester compound having no urethane bond is preferable.

The above-mentioned acrylic urethane is an acrylic urethane which is a reaction product of pentaerythritol or polypentaerythritol which is a multimer thereof, polyisocyanate and hydroxyalkyl (meth) acrylate, and is active energy ray-curable polymerizable. 3 functional groups
A polyfunctional compound having one or more (more preferably 4 to 20) or a hydroxyl group-containing poly (meth) acrylate of pentaerythritol or polypentaerythritol,
A polyfunctional compound which is an acrylic urethane which is a reaction product with a polyisocyanate and which has 3 or more (more preferably 4 to 20) active energy ray-curable polymerizable functional groups can be mentioned.

Examples of the (meth) acrylic acid ester compound having no urethane bond include pentaerythritol type poly (meth) acrylate and isocyanurate type poly (meth) acrylate. The pentaerythritol-based poly (meth) acrylate is a polyester of pentaerythritol or polypentaerythritol and (meth) acrylic acid (preferably having 4 to 20 active energy ray-curable polymerizable functional groups).
Say. The isocyanurate-based poly (meth) acrylate is a compound obtained by adding 1 to 6 mol of caprolactone or alkylene oxide to 1 mol of tris (hydroxyalkyl) isocyanurate or tris (hydroxyalkyl) isocyanurate. , (Meth) acrylic acid polyester (preferably having 2 to 3 active energy ray-curable polymerizable functional groups).

In the present invention, the above-mentioned preferred polyfunctional compound and a polyfunctional compound having two or more other active energy ray-curable polymerizable functional groups (particularly poly (meth) acrylate of polyhydric alcohol). You may use together with.

The ratio of the monofunctional compound or the polyfunctional compound in the active energy ray-curable component is not particularly limited.

Further, examples of the ultraviolet absorber include the following compounds. 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
2,2'-dihydroxy-4-methoxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (5-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5
-Di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-tert-butyl-2-
Hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-butyl-
2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-pentyl-2-hydroxyphenyl) benzotriazole, octyl-3
-{3- (2H-benzotriazol-2-yl) -5
-Tert-butyl-4-hydroxyphenyl} propionate, phenyl salicylate, p-tert-butylphenyl salicylate.

The amount of the ultraviolet absorber used in the coating composition (a) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the active energy ray-curable component. If the amount of the ultraviolet absorber used is too small, sufficient weather resistance cannot be exhibited and the resin film is likely to be colored. On the other hand, if the amount of the ultraviolet absorber used is too large, the ultraviolet absorber tends to bleed out, and the coating composition (a) may not be sufficiently cured.

The coating composition (a) can also contain colloidal silica or polysilazane. By including these, the hardness of the cured product of the coating composition (a) can be increased, and the scratch resistance of the hard coat layer can be improved. In the present invention, it is preferable to contain colloidal silica from the viewpoint of cost.

As the colloidal silica, JP-A-11-
No. 240103, paragraphs 0050 to 0078, unmodified surface-modified colloidal silica, or
Colloidal silica surface-modified with a compound (modifying agent) having a hydrolyzable silicon group or a silicon group to which a hydroxyl group is bonded (hereinafter simply referred to as modified colloidal silica).
Can be used. Further, for example, a commercially available product such as a trade name "Snowtex ITA-ST" (manufactured by Nissan Chemical Co., Ltd.) can be used. In the present invention, modified colloidal silica is preferably used from the viewpoint of dispersion stability in the coating composition (a). The average particle size of the colloidal silica is preferably 200 nm or less, and 1 to 10
0 nm is more preferable, and 1 to 50 nm is particularly preferable.

The amount of colloidal silica used in the coating composition (a) is preferably 5 to 300 parts by mass, more preferably 10 to 250 parts by mass, based on 100 parts by mass of the active energy ray-curable component. If the amount used is too small, it is difficult to obtain sufficient scratch resistance, and if the amount used is too large, clouding (haze) tends to occur, and cracks are likely to occur in the formed cured product layer.

Further, as polysilazane, Japanese Patent Laid-Open No.
Preferable examples thereof include the polysilazanes described in paragraph numbers 0097 to 0104 of JP-A-240103. In the present invention, perhydropolysilazane is preferable, and its molecular weight is preferably 200 to 50,000 in terms of number average molecular weight. If the number average molecular weight is less than 200, it is difficult to obtain a uniform cured product, and if it exceeds 50,000, it is difficult to dissolve in a solvent, which is not preferable.

The amount of polysilazane used in the coating composition (a) is preferably 5 to 300 parts by mass, more preferably 10 to 100 parts by mass, based on 100 parts by mass of the active energy ray-curable component.

The coating composition (a) may contain a solvent and various functional compounding agents in addition to the above basic components.

Examples of the solvent include hydrocarbons, halogenated hydrocarbons, ethers, esters, ketones and the like, and xylene or dibutyl ether is particularly preferable. As the solvent, a plurality of kinds of solvents may be mixed and used in order to adjust the solubility of polysilazane and the evaporation rate of the solvent. The amount of the solvent used varies depending on the coating method used and the like, but it is preferable to prepare the solvent so that the solid content concentration is 0.5 to 80% by mass.

As the functional compounding agent, a photopolymerization initiator, a light stabilizer, an antioxidant, a thermal polymerization inhibitor, a polymethylmethacrylate resin (PMMA), a heat ray blocking agent, an antistatic agent, a leveling agent. , Antifoaming agents, thickening agents, anti-settling agents, pigments, dyes, optical brighteners, silane coupling agents, dispersants, curing catalysts (acids, alkalis or salts) and the like.

In the present invention, a photopolymerization initiator is preferably contained in order to efficiently cure the active energy ray-curable component. As the photopolymerization initiator, an aryl ketone photopolymerization initiator (for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyl dimethyl ketals, benzoyl benzoates,
α-acyloxime esters, etc.), sulfur-containing photopolymerization initiators (for example, sulfides, thioxanthones, etc.), acylphosphine oxide photopolymerization initiators, diacylphosphine oxide photopolymerization initiators, other photopolymerization initiators Is mentioned. Specifically, JP-A-11-24
Examples thereof include the compounds described in paragraph Nos. 0081 to 0085 of JP-A No. 0103. In the present invention, an acylphosphine oxide photopolymerization initiator is particularly preferable. A plurality of types of photopolymerization initiators may be used in combination, and a photosensitizer such as amines may be used in combination.

The amount of the photopolymerization initiator used is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the active energy ray-curable component (when polysilazane is included, the total of polysilazane and the active energy ray-curable component). , Especially 0.1-10
Parts by mass are preferred.

The light stabilizer is preferably a hindered amine light stabilizer which is used as a light stabilizer for synthetic resins. Specific examples thereof include the compounds described in paragraph No. 0094 of JP-A No. 11-240103. In the present invention, 1,2,2,6,6-pentamethyl-
A compound having a polymerizable functional group in the molecule, such as 4-piperidyl methacrylate, is particularly preferable.

As the antioxidant, 2,6-di-ter is used.
Examples thereof include hindered phenolic antioxidants such as t-butyl-p-cresol and phosphorus antioxidants such as triphenylphosphite. Examples of the leveling agent include silicone resin-based leveling agents and acrylic resin-based leveling agents.

Examples of the heat ray blocking agent include fine particles of a conductive inorganic compound such as ATO (antimony oxide-added tin oxide) and ITO (tin oxide-added indium oxide). The heat ray blocking agent is preferably used in an amount of 0.1 to 50 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the active energy ray curable component (the total of polysilazane and the active energy ray curable component when polysilazane is included). The mass part is more preferable.

Examples of the defoaming agent include silicone resin defoaming agents such as polydimethylsiloxane. Examples of the thickener include polymethylmethacrylate-based polymers, hydrogenated castor oil-based compounds, and fatty acid amide-based compounds.

The thickness of the hard coat layer formed of the cured product of the coating composition (a) is preferably 1 to 20 μm, and particularly 1 to 1
0 μm is preferable. If the thickness of the cured product layer is too small, sufficient scratch resistance cannot be obtained, and if it is too large, curing with active energy rays may be insufficient and the adhesion to the resin film may be impaired.

The method for applying the coating composition (a) onto the resin film is not particularly limited and a known method can be adopted. For example, dip coating method, spin coating method, float coating method, gravure coating method, die coating method, shower coating method, ring coating method, bar coating method, micro gravure coating method, roll coating method, blade coating method, air knife coating method. Various methods such as In the present invention, a gravure coating method, a die coating method or a micro gravure coating method is preferably adopted from the viewpoint of productivity (continuous coating is possible) and surface appearance.

The active energy ray for curing the active energy ray-curable component contained in the coating composition (a) is not particularly limited, and ultraviolet rays, electron beams and other active energy rays can be used. In the present invention, ultraviolet rays are preferred. As the ultraviolet ray source, a xenon lamp, a pulse xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, etc. can be used. When the coating composition (a) contains a solvent, it is preferable to cure the coating composition after removing the solvent.

When the coating composition (a) contains polysilazane, paragraph 0 of JP-A No. 11-240103.
The polysilazane can be cured by the method described in 109-0112. In the present invention, from the viewpoint of the heat resistance of the resin film, for example, fine particles of a metal such as gold, silver, palladium, platinum and nickel described in JP-A-7-196986, JP-A-9-31333. It is preferable to cure at a low temperature using a catalyst such as amines and acids described in 1.

When the hard coat layer is composed of two or more cured product layers, the inner layer in contact with the outermost layer is the cured product of the coating composition (a) and the outermost layer contains polysilazane. It is preferably a cured product of the coating composition, that is, a silica layer. The polysilazane is preferably the above-mentioned perhydropolysilazane.

Next, the adhesive layer will be described. The adhesive layer of the protective film of the present invention contains an ultraviolet absorber.
As a result, most of the ultraviolet rays that cannot be sufficiently blocked by the ultraviolet absorber contained in the hard coat layer can be blocked.

As the ultraviolet absorber, the same one as described in the above hard coat layer can be used. The amount of the ultraviolet absorber used is preferably 0.1 to 20 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the adhesive component.

There are no particular restrictions on the components of the pressure-sensitive adhesive, and the pressure-sensitive adhesives that are commonly used for ultraviolet blocking films and the like can be used. Examples of preferable components of the pressure-sensitive adhesive used in the present invention include compositions containing an unsaturated carboxylic acid ester copolymer as a main component. In particular, 100 parts by mass of a copolymer having a glass transition temperature of -20 ° C or less, which is derived from 99.9 to 85 parts by mass of an unsaturated carboxylic acid ester monomer and 0.1 to 15 parts by mass of a vinyl monomer having a crosslinkable functional group. Parts, 70 to 400 parts by weight of solvent, and 0.01 to 20 parts by weight of a cross-linking agent capable of reacting with the cross-linkable functional group are preferred.

Examples of the unsaturated carboxylic acid ester monomers include alkyl (meth) acrylate (wherein the alkyl group has 1 to 13 carbon atoms) monomers, vinyl ester monomers such as vinyl acetate and vinyl propionate, and the like. .

Examples of the vinyl monomer having a crosslinkable functional group include vinyl monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid,
In addition to vinyl monomers having a hydroxyl group such as and hydroxyalkyl ester of (meth) acrylic acid (the number of carbon atoms of the hydroxyalkyl group is 1 to 9), vinyl monomers having an epoxy group and an amino group are included.

As the cross-linking agent, a metal cross-linking agent and an organic polyvalent isocyanate compound are mainly used.
Examples of the metal crosslinking agent include aluminum trisacetylacetonate, aluminum isopropionate, aluminum secondary butyrate, titanium tetraisopropionate, titanium tetranormal butyrate, titanium tetra-2-ethylhexylate, antimony butyrate. , Zirconium secondary butyrate and the like.

Examples of the organic polyvalent isocyanate compound include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate,
Examples thereof include 4,4-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dimer acid diisocyanate, norbornene diisocyanate, and adduct compounds thereof.

Further, the pressure-sensitive adhesive layer can contain the same heat ray blocking agent as described in the above hard coat layer. The amount of the heat ray blocking agent used is preferably 0.1 to 50 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the pressure-sensitive adhesive component.

The thickness of the pressure-sensitive adhesive layer is preferably 10 to 40 μm. If the thickness of the pressure-sensitive adhesive layer is too small, it may not be possible to obtain sufficient adhesive strength, and if it is too large, it becomes difficult to carry out the work of laminating the film, or when the film is peeled off, the pressure-sensitive adhesive layer is formed on the glass surface. It becomes easy to remain in.

The method for forming the pressure-sensitive adhesive layer is not particularly limited. For example, the resin film may be directly coated with the pressure-sensitive adhesive solution, or the resin film subjected to silicone release treatment may be coated with the pressure-sensitive adhesive solution. Then, a pressure-sensitive adhesive sheet having a predetermined thickness may be separately manufactured and then adhered.

Next, the heat ray blocking layer will be described. The heat ray-shielding layer can be formed by applying a coating composition containing the heat ray-shielding agent, or depositing the heat ray-shielding agent by a vacuum vapor deposition method, a sputtering method, an ion plating method, or a CVD method.

The resin component contained in the coating composition containing the heat ray-shielding agent can stably disperse and retain the heat ray-shielding agent, which is a fine particle metal oxide such as ATO or ITO, and is in contact with the heat ray-shielding layer ( Any resin can be used without particular limitation as long as it is a resin having good adhesion to the resin film, the pressure-sensitive adhesive layer or the hard coat layer). In the present invention, for example, a compound having a (meth) acroyl group is preferably used. More specifically, acrylic urethane and a (meth) acrylic acid ester compound are preferable, and further, they have thermosetting property when used in combination with active energy ray curable or a crosslinking agent such as isocyanate type or a curing component such as polysilazane. Is more preferable.

For example, a heat ray blocking agent was added (meta).
A coating composition in which a light stabilizer, a cross-linking agent, and the like are added to an acrylic resin solution as needed may be applied by a gravure coating method, a die coating method, a micro gravure coating method, or the like.

The thickness of the heat ray blocking layer is preferably 1 to 10 μm. If it is out of this range, the desired effect may not be exhibited or the appearance may be uneven.

The heat ray blocking layer is preferably formed between the resin film and the hard coat layer or between the resin film and the adhesive layer.

FIG. 1 shows a schematic diagram of a cross section of a state in which a protective film, which is an embodiment of the present invention, is attached to a glass surface. This protective film 1 is a resin film 1
Hard coat layer 1b containing an ultraviolet absorber on one side of a
Is formed, and an adhesive layer 1c containing an ultraviolet absorber is formed on the other surface. Then, it is adhered to the glass surface (outdoor side) via the pressure-sensitive adhesive layer 1c.

In the protective film 1, for example, the coating composition (a) is applied to one surface of the resin film 1a and the coating composition (a) is cured to form the hard coat layer 1b. It can be manufactured by forming the pressure-sensitive adhesive layer 1c on the surface opposite to.

Further, FIG. 2 shows a schematic diagram of a cross section of a state in which a protective film according to another embodiment of the present invention is attached to the glass surface. In this protective film 3, a heat ray blocking layer 3d is formed on one surface of a resin film 3a,
Hard coat layer 3b containing an ultraviolet absorber on its surface
Are stacked. Further, an adhesive layer 3c containing an ultraviolet absorber is formed on the other surface. Then, it is attached to the glass surface (outdoor side) via the pressure-sensitive adhesive layer 3c.

In the protective film 3, for example, after forming the heat ray blocking layer 3d on one surface of the resin film, the coating composition (a) is applied to the surface of the heat ray blocking layer to form the coating composition (a). It can be produced by curing to form the hard coat layer 3b and forming the pressure-sensitive adhesive layer 3c on the opposite surface of the hard coat layer.

[0068]

EXAMPLES The present invention will be described below based on Examples (Examples 1 to 8) and Comparative Examples (Examples 9 and 10), but the present invention is not limited thereto. In each example, the following adhesive solution and infrared blocking agent solution were used.

[Preparation of pressure-sensitive adhesive solution and pressure-sensitive adhesive sheet] Solid content of butyl acrylate / acrylic acid = 96/4 (molar ratio), solid content of acrylic acid resin having a mass average molecular weight of 500,000 as a solid component 25 29.7 parts by mass of a benzotriazole-based ultraviolet absorber (trade name "Tinuvin 328", manufactured by Ciba Specialty Chemicals) in 99.7 parts by mass of a toluene solution of mass%, and a hindered amine light stabilizer (trade name "Mark LA- 63 ", manufactured by Asahi Denka Co., Ltd.)
1.5 parts by mass and 30 parts by mass of tert-butanol were added and thoroughly mixed with stirring to completely dissolve them. Further, 0.3 parts by mass of a trimer of hexamethylene diisocyanate was dissolved in 3 parts by mass of tert-butanol as a cross-linking component, added, and sufficiently stirred and mixed to prepare an adhesive solution. This adhesive solution was applied to a 38 μm-thick polyester film that had been subjected to a silicone peeling treatment using a blade coater, followed by oven-drying at 100 ° C. for 3 minutes to give a thickness of 20.
A pressure-sensitive adhesive sheet of μm was obtained (hereinafter referred to as a pressure-sensitive adhesive sheet).

In the above-mentioned pressure-sensitive adhesive solution, an ultraviolet absorber and a tert-solution for dissolving the ultraviolet absorber are used.
A pressure-sensitive adhesive solution was prepared without using butanol, and a pressure-sensitive adhesive sheet having a thickness of 20 μm was prepared in the same manner as described above (hereinafter referred to as a pressure-sensitive adhesive sheet).

A pressure-sensitive adhesive solution was prepared in the same manner as above except that 4 parts by mass of "Tinuvin 328" was used, and a pressure-sensitive adhesive sheet having a thickness of 20 μm was prepared in the same manner as described above (hereinafter, It is called an adhesive sheet.)

[Preparation of Infrared Blocker Solution] In a 1000 mL four-necked flask equipped with a stirrer and a cooling tube, an acrylic resin solution having a solid content of 30% by mass (isobutyl methacrylate, ethyl acrylate, 2-hydroxyethyl methacrylate, Mass average molecular weight 170,000 consisting of diethylaminoethyl methacrylate, Tg 20 ° C) 300
Parts by weight, 180 parts by weight of fine particle ATO, 2 parts by weight of hindered amine light stabilizer (trade name "Tinuvin 622L
D ", manufactured by Ciba Specialty Chemicals), n-
After adding 200 parts by mass of butanol and stirring, the diameter was 0.
Dispersion was performed with a media disperser using 5 mm zirconia beads to obtain a main agent of an infrared ray blocking agent. Furthermore, as a cross-linking component, a hexamer diisocyanate trimer of 25
A mass% tert-butanol solution (40 parts by mass) was added, and sufficiently mixed by stirring to prepare an infrared blocking agent solution.

The active energy ray-curable component, ultraviolet absorber, photopolymerization initiator, light stabilizer, and colloidal silica shown below were used.

Active energy ray curable component A-1: Acrylic urethane having a molecular weight of 23,000 obtained by reacting hydroxyl group-containing dipentaerythritol polyacrylate with hexamethylene diisocyanate (average number of acryloyl groups per molecule is 15). A-2: Bifunctional acrylic urethane having a molecular weight of 1000, which is a reaction product of 1 mol of a bimolecular adduct of bisphenol A-ethylene oxide, 2 mol of hexamethylene diisocyanate, and 2 mol of 2-hydroxyethyl acrylate. A-3: Dipentaerythritol hexaacrylate.

Ultraviolet absorber B-1: Benzotriazole type ultraviolet absorber (trade name "Tinuvin 328") B-2: Benzophenone type ultraviolet absorber (trade name "Ubinal 3049" manufactured by BASF) Photopolymerization initiator C -1: 1-hydroxycyclohexyl phenyl ketone. C-2: 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Light stabilizer Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate colloidal silica Ethyl cellosolve dispersion type colloidal silica (silica content 30% by mass, average particle size 11 nm) 50 parts by mass In addition, 5 parts by weight of 3-mercaptopropyltrimethoxysilane and 0.
Colloidal silica having a hydrolyzed condensate of mercaptosilane on its surface, obtained by adding 1.5 parts by mass of 01N hydrochloric acid, heating and stirring at 40 ° C. for 4 hours, and then aging at room temperature for 12 hours.

[Example 1] 3 equipped with a stirrer and a cooling pipe
In a 00 mL four-necked flask, 60 parts by mass of isopropyl alcohol, 60 parts by mass of butyl acetate, 30 parts by mass of ethyl cellosolve, 3 parts by mass of an ultraviolet absorber (B-1), 5 parts by mass of a photopolymerization initiator (C-1). , And 1 part by weight of a light stabilizer were added and dissolved. Subsequently, 100 parts by mass of the active energy ray-curable component (A-1: A-2 = 60: 40) was added to prepare coating composition 1.

Then, a polycarbonate film (100 mm square, 100 μm thick) which has been subjected to double-sided corona discharge treatment
m, trade name “Lexan film (8010)”, manufactured by SP Pacific Co., Ltd. ) Coating composition 1 on one side
Was coated using a spin coater, and then held in a hot air circulation oven at 80 ° C. for 5 minutes. Next, this film was exposed to 3000 mJ / cm in an air atmosphere using a high pressure mercury lamp.
² (ultraviolet ray integrated energy amount in the wavelength range of 300 to 390 nm) was irradiated to form a hard coat layer having a film thickness of 7 μm.

Then, the other surface of the film (the surface on which the hard coat layer is not formed) is coated with an infrared blocking agent solution using a blade coater, and then 80
Film thickness 5μm by holding in a hot air circulation oven at ℃ for 20 minutes
The infrared blocking layer was formed, and the pressure-sensitive adhesive sheet was further attached to the surface of the infrared-ray blocking layer to form a pressure-sensitive adhesive layer, to prepare a protective film.

[Example 2] A coating composition 2 was prepared in the same manner as in Example 1 except that the ultraviolet absorber was changed to B-2. Then, the coating composition 2 was applied to one side of a polycarbonate film (100 mm square, thickness 100 μm) that had been subjected to double-sided corona discharge treatment in the same manner as in Example 1 to form a hard coat layer. Then, an infrared ray blocking layer and a pressure-sensitive adhesive layer were formed on the other surface in the same manner as in Example 1 to prepare a protective film.

Example 3 A coating composition 3 was prepared in the same manner as in Example 1 except that 30 parts by mass of colloidal silica was added.
Then, on one side of the polycarbonate film (100 mm square, thickness 100 μm) that has been subjected to double-sided corona discharge treatment,
The coating composition 3 was applied in the same manner as in Example 1 to form a hard coat layer. Then, an infrared ray blocking layer and a pressure-sensitive adhesive layer were formed on the other surface in the same manner as in Example 1 to prepare a protective film.

[Example 4] A coating composition 4 was prepared in the same manner as in Example 3 except that the ultraviolet absorber was changed to B-2. Then, the coating composition 4 was applied to one side of a polycarbonate film (100 mm square, thickness 100 μm) subjected to double-sided corona discharge treatment in the same manner as in Example 1 to form a hard coat layer. Then, an infrared ray blocking layer and a pressure-sensitive adhesive layer were formed on the other surface in the same manner as in Example 1 to prepare a protective film.

[Example 5] 3 equipped with a stirrer and a cooling pipe
In a 00 mL four-necked flask, 60 parts by mass of isopropyl alcohol, 60 parts by mass of butyl acetate, 30 parts by mass of ethyl cellosolve, 3 parts by mass of an ultraviolet absorber (B-1), 5 parts by mass of a photopolymerization initiator (C-1). , And 1 part by weight of a light stabilizer were added and dissolved. Subsequently, 100 parts by mass of the active energy ray-curable component (A-3) was added to prepare coating composition 5.

A polycarbonate film (100 mm square, thickness 100 μm) that has been subjected to double-sided corona discharge treatment
The coating composition 5 was applied to one surface of m) in the same manner as in Example 1 to form a hard coat layer. Then, an infrared ray blocking layer and a pressure-sensitive adhesive layer were formed on the other surface in the same manner as in Example 1 to prepare a protective film.

[Example 6] As a resin film, a PET film (1
A protective film was produced in the same manner as in Example 1 except that a 100 mm square and a thickness of 100 μm) were used.

[Example 7] As a resin film, a PET film (1
A protective film was produced in the same manner as in Example 2 except that a 100 mm square and a thickness of 100 μm) were used.

[Example 8] A coating composition 6 was prepared in the same manner as in Example 5 except that the photopolymerization initiator was changed to C-2. PE that has been subjected to an easy adhesion treatment of urethane emulsion
The coating composition 6 was applied to one side of a T film (100 mm square, thickness 100 μm) in the same manner as in Example 1 to form a hard coat layer. Then, an infrared ray blocking layer and a pressure-sensitive adhesive layer were formed on the other surface in the same manner as in Example 1 to prepare a protective film.

[Example 9] A coating composition 7 was prepared in the same manner as in Example 1 except that 5 parts by mass of the ultraviolet absorber (B-1) was used. Then, the coating composition 7 was applied to one side of a polycarbonate film (100 mm square, thickness 100 μm) that had been subjected to double-sided corona discharge treatment in the same manner as in Example 1 to form a hard coat layer. Then, an infrared ray blocking layer was formed on the other surface in the same manner as in Example 1, and the pressure sensitive adhesive sheet was further bonded to this surface to form a pressure sensitive adhesive layer to prepare a protective film.

Example 10 In a 300 mL four-necked flask equipped with a stirrer and a cooling tube, 60 parts by mass of isopropyl alcohol, 60 parts by mass of butyl acetate, 30 parts by mass of ethyl cellosolve, and a photopolymerization initiator (C-1). 5 parts by mass and 1 part by mass of the light stabilizer were added and dissolved. Subsequently, the active energy ray-curable component (A-1: A-2 = 60: 40)
Coating Composition 8 was prepared by adding 100 parts by mass.

Then, a polycarbonate film (100 mm square, 100 μm thick) that has been subjected to double-sided corona discharge treatment
The coating composition 8 was applied to one surface of m) in the same manner as in Example 1 to form a hard coat layer. Then, an infrared ray blocking layer was formed on the other surface in the same manner as in Example 1, and the pressure sensitive adhesive sheet was further bonded to this surface to form a pressure sensitive adhesive layer to prepare a protective film.

[Preparation of Test Sample] The release-treated polyester film was peeled off from the pressure-sensitive adhesive layer of the protective film obtained in each of the above examples, and the pressure-sensitive adhesive layer was soda lime glass (1
00mm square, thickness 6mm) and then 1k
A test sample was prepared by pressing the whole body with a pressure of g / cm ² . Then, using this test sample, various physical properties were measured and evaluated by the methods described below. The results are shown in Table 1.

[Initial Haze Value] Regarding the sample before the abrasion test, the haze value (%) at four locations was measured with a haze meter, and the average value was calculated.

[Surface Scratch Resistance] The taper abrasion test method was used to combine two CS-10F wear wheels with 500 g weights each and measure the haze value after 100 rotations with a haze meter. The haze value was measured at four points on the wear cycle orbit, and the average value was calculated. The surface abrasion resistance (ΔH) is represented by the value (%) of (haze value after abrasion test)-(initial haze value).

[Ultraviolet transmittance] Using a spectrophotometer (model "U-4000", manufactured by Hitachi, Ltd.) according to JIS R3106, ultraviolet rays (280 to 380 nm) are transmitted from the soda lime glass side of each test sample. The rate was measured.

[Weather resistance] Using a sunshine weather meter, the black panel temperature was 63 ° C., the rainfall was 12 minutes,
After a cycle of 48 minutes of drying, each test sample was exposed for 1000 hours from the protective film side, and then the change in appearance and the peelability when peeling the protective film from the glass were visually evaluated. The appearance was evaluated by evaluating the change in color tone and the state of adhesion of the protective film to the glass surface, and the peelability of the protective film was classified according to the following categories. 1: The adhesive layer could be peeled off without remaining on the glass surface. 2: Peeled at the interface between the resin film and the infrared blocking layer. 3: The adhesive layer was cohesively broken and remained on the glass surface. 4: Peeled at the interface between the infrared ray blocking layer and the pressure-sensitive adhesive layer.

[0096]

[Table 1]

From Table 1, it can be seen that the protective films of Examples 1 to 8 containing the ultraviolet absorber in both the hard coat layer and the pressure-sensitive adhesive layer are excellent in scratch resistance, weather resistance and transparency. On the other hand, the protective films of Examples 9 and 10 containing the ultraviolet absorber only in the hard coat layer or the adhesive layer,
It can be seen that the weather resistance is inferior such that the transparency is lowered due to the bleed-out of the ultraviolet absorber, the adhesive is coagulated and peeled off (Example 9), and the resin film is significantly yellowed (Example 10).

Although no clear difference was observed in the UV blocking effect, the reason for this was that the total amount of the UV absorbers contained in the protective film of each example was about the same, and the infrared blocking layer was It is considered that it has a certain degree of ultraviolet blocking effect and that the ultraviolet transmittance was measured through the glass of the test sample.

[0099]

As described above, the protective film of the present invention has a hard coat layer containing an ultraviolet absorber on one surface of the organic resin film, and therefore has excellent scratch resistance, weather resistance and transparency. Since it has an adhesive layer containing an ultraviolet absorber on one surface, it has a sufficient ultraviolet blocking effect. Therefore, even when it is attached to a window glass or the like from the outdoor side and used for a long period of time, deterioration of transparency and coloring of the resin film are less likely to occur.

[Brief description of drawings]

FIG. 1 is a schematic view showing a cross section of a state in which a protective film according to an embodiment of the present invention is attached to glass.

FIG. 2 is a schematic view showing a cross section of a state in which a protective film according to another embodiment of the present invention is attached to glass.

[Explanation of symbols]

1,3. Protective film 1a, 3a. Resin film 1b, 3b. Hard coat layer 1c, 3c. Adhesive layer 2. Glass 3d. Heat ray blocking layer

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 5/00 C09D 5/00 Z C09J 11/00 C09J 11/00 201/00 201/00 (72) Invention Person Hiroshi Yamamoto 1150, Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Asahi Glass Co., Ltd. (72) Inventor Satoshi Tanaka 530, Oshima, Namerikawa City, Toyama Prefecture F Term (reference) 4F100 AA20C AK01A AT00A BA03 BA07 BA10C CA23C CC02C DE04C GB07 GB32 JB14C JD10B JD10C JK09 JK12C JL09 JL13B JN01 4J004 AA10 AB01 CA06 CA07 CC02 CC03 FA04 4J038 DL172 FA011 FA121 FA131 FA141 FA151 FA161 FA281 GA12 HA446 KA08 KA12 MA11 NA03 NA19 PA17 PB07 PB08 PC08 4J040 DF041 DF051 EF181 EF291 EF301 GA07 HA136 HD41 JA09 JB09 KA29 KA32 KA42 MA05 MB03 NA12 NA16 PA23

Claims (4)

[Claims] 1. A protective film to be adhered to a glass surface on the outdoor side, which comprises an adhesive layer for adhering to the glass surface, a resin film adhered via the adhesive layer, and a resin film of the resin film. A protective film comprising a hard coat layer provided on the surface, wherein the pressure-sensitive adhesive layer and the hard coat layer contain an ultraviolet absorber. 2. The protective film according to claim 1, wherein the pressure-sensitive adhesive layer and / or the hard coat layer contains a heat ray blocking agent, or is further provided with a layer containing a heat ray blocking agent. 3. The cured product of the coating composition (a), wherein the hard coat layer comprises a compound having at least one active energy ray-curable polymerizable functional group as a curable component. The protective film described in. 4. The protective film according to claim 3, wherein the coating composition (a) contains colloidal silica.