JPH10128899A - Film for preventing glass scattering having light diffusing function - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppers the reflection of an outdoor light and a fluorescent light and reduce the mirroring of the outdoor light by a method wherein a light diffusing layer is provided on the surface of a film under the condition that the visibility of a transmitted image is specified. SOLUTION: This glass scatting-preventive film consists of a film serving as a board, a light diffusing layer, the visibility of a transmitted image of which is 10% or more when an optical comb width of 0.5mm is employed, and a self-adhesive layer under the condition that the light diffusing layer is provided on one side of the film while the self-adhesive layer is provided on the other side of the film. In the case that the light diffusing layer is provded by utilizing a fine particle-dispersed ultraviolet curing type resin composition, as the ultraviolet curing type resin composition, one prepared by compounding an acrylic urethane-based reactive compound of the like with a photopolymerization initiator and having the excellent adhesion between the skin hardened by ultraviolet rays and a support and a hard coating properties is preferable. In addition, the size of the fine particle, its loadings and the like must be properly adjusted so as to set the visibility of the transmitted image to be 10% or more, more preferably 15% or more when the optical comb width of 0.5mm is employed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used for glass and window glass of showcases and buildings, etc., and suppresses reflection by external light or fluorescent lamps to reduce the reflection of external light, thereby transmitting the outside light. The present invention relates to a film that can clearly see the image on the side and prevents scattering of glass destroyed by a shock caused by a natural disaster such as an earthquake or a shock caused by a man-made disaster.

[0002]

2. Description of the Related Art Glass shatterproof films use, for example, a film support such as polyester as a base material having a certain tensile strength or more, and an acrylic pressure-sensitive adhesive having a certain range of adhesive strength on the side to be attached to glass. Is coated with 10 to 20 μm, and the other side is coated with a 3 to 5 μm hard coating agent such as a UV resin for the purpose of protecting abrasion caused by a rubber spatula used when attaching a film to glass.

In recent years, in showcases and buildings,
There is a demand for reduction of glare and reflection due to external light entering the room in order to make the exhibits more visible.
However, the conventional anti-scattering film provided with a hard coat layer is very dazzling where external light directly enters, and the external scenery is reflected, for example, when used for glass of a showcase, etc. Then, although the scattering of the glass due to the impact of a disaster or the like can be prevented, there is a problem that the exhibits are difficult to see.

To cope with such a problem, there has been proposed a method of forming an anti-reflection film utilizing the light interference effect on the surface of the hard coat layer. Although it is effective, outside light is not reflected due to insufficient anti-reflection effect at other angles, and it is necessary to form a thin film with high accuracy, so processing requires considerable labor .

[0005]

SUMMARY OF THE INVENTION The present invention suppresses the reflection of external light or fluorescent light and reduces the reflection of external light when a glass shatterproof film is attached, thereby reducing the reflection of external light. An object of the present invention is to provide a glass shatterproof film capable of clearly seeing an image.

[0006]

As a result of intensive studies on the above problems, a light diffusion layer is provided on the surface of the anti-scattering film, and the transmitted image clarity is increased to 10% or more when the optical width is 0.5 mm. By doing so, when affixed to window glass or door glass, glare due to reflection of external light or fluorescent light is suppressed (anti-glare), not only the reflection of external light is reduced, but also the transmitted image on the other side And found that they can be clearly seen, leading to the present invention. That is, the present invention
(1) a glass shatterproof film having a light diffusion layer on the surface of the film and having a transmitted image definition of more than 10% at an optical comb width of 0.5 mm; (2)
The glass scattering prevention film according to (1), wherein the light diffusion layer has a number of fine irregularities on the surface.
(3) The glass scattering prevention film according to any one of (1) and (2), wherein the light diffusion layer is a cured film of at least a mixture of an ultraviolet curable resin composition and fine particles, (4)
(3) The glass shatterproof film according to (3), wherein the fine particles have an average particle size of 0.5 to 2 μm according to the Coulter counter method, and (5) the fine particles are a silicon compound, a metal compound, a polymer compound, or a mixture thereof. The glass shatterproof film according to any one of (3) and (4), wherein (6) a plurality of fine particles having different average particle diameters are used (3) to (5). (7) 30 or more acrylate monomers having 4 or more functions in the ultraviolet-curable resin composition.
The glass shatterproof film according to (3), wherein the film is contained in an amount of from 90 to 90 parts by weight. (8) The thickness of the light diffusion layer is 0.
The glass shatterproof film according to any one of (1) to (7), which has a thickness of 5 to 10 μm, and (9) a fluororesin layer or a multilayer antireflection film formed on the light diffusion layer. (8) The glass shatterproof film according to any one of (1) to (9), wherein the light diffusion layer is colored. Film.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The glass scattering prevention film having a light diffusion function of the present invention is a film serving as a substrate, a light diffusion layer having a transmitted image definition of 10% or more at an optical comb width of 0.5 mm, and an adhesive layer. The light diffusion layer is provided on one side of the film, and the adhesive layer is provided on the other side.
The light-diffusing layer used in the present invention diffuses or scatters incoming light, so that the amount of light directly entering the eye is reduced. Reflection is reduced, and the transmitted image can be clearly seen. As a method for forming a fine uneven light diffusion layer on this surface, there are a sand blast method in which fine powder solids are sprayed on the surface of a transparent synthetic resin sheet to form extremely fine irregularities, and a fine particle such as silica is cured by an ultraviolet curable resin composition. And then apply it on a film, and then irradiate it with ultraviolet light to form a cured film having extremely fine irregularities. Easiness of processing, productivity, and easy adjustment of light diffusion Therefore, it is preferable to apply a mixed dispersion in which fine particles are dispersed in an ultraviolet-curable resin composition to a film, and then irradiate ultraviolet rays to form a cured film having extremely fine irregularities.

When a light diffusion layer is provided using an ultraviolet-curable resin composition in which fine particles are dispersed, examples of the ultraviolet-curable resin composition include acrylic, urethane, acrylic urethane, epoxy, and silicone-based resins. A compound in which a photopolymerization initiator is blended with the reactive compound (1) is preferably used. In particular, a film cured by ultraviolet rays having excellent adhesion to a support and having a hard coat property is preferable.
In particular, in order to have a hard coat property, it is preferable to use a monomer having four or more functional groups as a reactive compound, and further blend a reactive compound other than the monomer with a photopolymerization initiator. Examples of the monomer having four or more functional groups include dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexa (meth) acrylate, and hexa (meth) acrylate obtained by reacting dipentaerythritol with epsilon-caprolactone. Is raised.

Examples of the reactive compound other than the monomer having four or more functional groups include a reactive monomer other than the monomer and a reactive oligomer. As the reactive monomer, for example, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl acrylate, glycidyl (meth) acrylate, acryloyl morpholine,
t-butylaminoethyl (meth) acrylate, 2-cyano (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylacrylamide, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, Phenoxydiethylene glycol (meta)
Acrylate, ethylene glycol di (meth) acrylate, and the like. As the reactive oligomer, for example, a polyester (meth) acrylate obtained by reacting a polyester polyol with (meth) acrylic acid, or a reaction obtained by reacting a bisphenol-type epoxy resin with (meth) acrylate or hydroxy (meth) acrylate is used. Epoxy (meth) acrylate,
Urethane (meth) acrylate obtained by a reaction between an organic polyisocyanate and a hydroxy (meth) acrylate compound, or a reaction between a polyol, an organic polyisocyanate and a hydroxy (meth) acrylate compound, and the like.

Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, (1-6-η-cumene) (η-cyclopentadienyl) iron (1+) hexafluorophosphate (1-), , 2-Dimethoxy-2-phenylacetophenone, Michler's ketone, 2-methyl- [4
-(Methylthio) phenyl] -2-morpholino-1-
Propanone, 2-benzyl-2-dimethylamino-1-
(4-morpholinophenyl) -butanone-1,2-chlorothioxanthone, 2,4-dimethylthioxanthone,
Examples thereof include 2,4-diisopropylthioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide. These photopolymerization initiators can be used alone or in combination of two or more at an arbitrary ratio.

The compounding amount is preferably 30 to 95 parts by weight, more preferably 3 to 95 parts by weight, of a monomer having four or more functional groups in 100 parts by weight of the ultraviolet curable resin composition.
5 to 90 parts by weight, preferably 5 to 6 other reactive compounds
5 parts by weight, more preferably 10 to 60 parts by weight, the photopolymerization initiator is preferably 0.01 to 15 parts by weight, and preferably about 0.1 to 10 parts by weight.

The fine particles differ depending on the desired light diffusivity and transmitted image sharpness, but if they are too fine, the light diffusivity will be poor, and if they are too large, the transmitted image sharpness will be reduced. Average particle size is preferably 0.5 to 2 μm, more preferably 1 to 2 μm.
Those having a thickness of about 1.5 μm are preferable. It is also possible to use a mixture of a plurality of fine particles having different average particle sizes. The material is preferably transparent, and silica, a metal compound or a polymer compound is suitably used. Examples of silica include synthetic particles of silicon dioxide. Examples of the metal compound include alumina, titania, and zirconia. Examples of the polymer compound include polymethyl (meth) acrylate resin.

The compounding amount varies depending on the desired antiglare property, clearness of the transmitted image, the particle diameter of the fine particles used, the thickness of the light diffusing layer, and the like. Diffusivity (haze value) is preferably 3 to 40%,
More preferably, the content is about 5 to 30%, and those having this haze value are, for example, preferably 0.1 to 90 parts by weight based on 100 parts by weight of the ultraviolet-curable resin composition.
It is more preferably obtained by adding about 0.5 to 80 parts by weight, and still more preferably about 1 to 70 parts by weight. At this time, the particle size of the fine particles is adjusted so that the transmitted image clarity, which is one of the indices of the visibility of the transmitted image, is more than 10%, more preferably 15% or more at an optical comb width of 0.5 mm. , Its blending amount and the like must be appropriately adjusted. If the transmitted image definition is 10% or less, the transmitted image may be unclear and the effect of the present invention may not be sufficiently exhibited.

Further, various leveling agents can be used to impart uniformity to the coated surface when coated on the film and to provide abrasion resistance of the formed light diffusion layer. Examples of such a material include a silicone-based or fluorine-based varnish, a surfactant, and a coupling agent.

The thickness of the light diffusing layer in the present invention is, for example, when the light diffusing layer of the present invention is made of a UV-curable resin composition and fine particles, the cured resin layer becomes too thick, so that all of the fine particles are removed. The light diffusing property is lost by being buried in the resin, or the curling of the light diffusing layer is not particularly limited as long as there is no problem in production and use such as extreme curling of the film due to curing shrinkage. 1
0 μm, more preferably about 1 to 5 μm.

When the light diffusing layer in the present invention is formed on a film, a mixture dispersion prepared by uniformly dissolving and dispersing the ultraviolet-curable resin composition and the fine particles in a solvent and adjusting the concentration to a desired concentration is prepared by: It can be obtained by applying the composition on a film so as to have a uniform thickness, removing the solvent preferably by heating, and then irradiating ultraviolet rays to cure the mixture. The solvent is preferably a solvent that dissolves an ultraviolet-curable resin, for example, toluene, methanol, ethanol, alcohols such as isopropyl alcohol,
Examples include ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate and butyl acetate. These solvents may be used alone or in a mixture at an arbitrary ratio. The method of applying the mixture dispersion is not particularly limited, but is preferably a uniform film thickness in order to keep the characteristics of the light diffusion layer constant. For example, a wire bar method, a dip coating method, a spin coating method, a gravure method Various coating methods such as a method, a microgravure method, and a doctor blade method can be used.

Further, the light diffusion layer of the present invention can be colored by adding a dye to these mixed dispersions. By coloring the light diffusion layer, the light transmittance can be arbitrarily adjusted. As the dye, disperse dyes and water-insoluble organic dyes are preferable from the viewpoint of solubility in organic solvents. For example, Kayalon Polyester Co.
lours and Kayaset Colors (all manufactured by Nippon Kayaku Co., Ltd.). In addition, the compounding amount is appropriately determined depending on the desired transmittance and the thickness of the light diffusion layer.

In the anti-scattering film of the present invention, for example, a low-refractive-index fluorine-based resin layer can be further formed as an anti-reflection film layer on the light diffusion layer, and a thin film of silicon dioxide or a metal compound can be formed. It is also possible to form a multilayer anti-reflection film in which a large number of are laminated. By providing the above-mentioned layer optically designed to reduce the reflected light by the light interference effect on the light diffusion layer, not only the light transmittance is improved, but also the surface of the light diffusion layer becomes whitish due to the reflected light. Can be prevented, and can be made easier to see. The thickness of the antireflection film layer and the number of layers of the multilayer antireflection film are appropriately determined depending on the refractive index of the material used.

After the light diffusion layer is formed, an adhesive such as an acrylic resin is applied to the opposite side of the film by a known coating method and dried, and a 10 to 20 μm adhesive layer is formed to form a low reflection glass. Can make shatterproof film. In this case, the adhesive strength needs to be designed in the range of 160 to 1000 g / cm, preferably in the range of 500 to 800 g / cm. Below the range, sufficient scattering prevention performance cannot be exhibited, and above the above, glue remains at the time of peeling, and a large defect occurs as a scattering prevention film.

Further, as the film of the anti-scattering film having a light diffusion function used in the present invention, if the film has a tensile strength of 4 kgf / 10 mm or more,
Anything may be used. As a film having such properties, for example, polyethylene, polypropylene, polyester, nylon, polystyrene, polyvinyl chloride, ethylene vinyl alcohol, polyvinylidene chloride, polycarbonate, acrylic, fluororesin, polyacrylonitrile, polyimide and other resins Film. More preferred are polyester and polycarbonate films.

The glass shatterproof film of the present invention preferably has a transmitted image definition of more than 10%, more preferably at least 15% at an optical comb width of 0.5 mm.
When affixing the glass shatterproof film of the present invention to glass, the glass shatterproof film of the present invention having the same area as the glass on the surface of a glass or window glass of a showcase or a building for preventing shattering using an adhesive layer. Just stick them together. At this time, it is preferable that dust and dirt on the glass surface be removed as much as possible, and furthermore, looseness and wrinkles are eliminated by a rubber spatula or the like, and the glass is uniformly bonded.

[0022]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples, but it goes without saying that these Examples do not limit the present invention.

Example 1 5 parts by weight of silica fine particles having an average particle size of 1 μm and a photopolymerization initiator (Irgacure 184: Ciba-Geigy) 5
Parts by weight, and 100 parts by weight of an ultraviolet curable acrylic resin containing 90 parts by weight of dipentaerythritol hexaacrylate are stirred at high speed in a mixed solvent of toluene and isopropyl alcohol to prepare a dispersion having a solid content of 25% by weight. One side of a 50 μm-thick easily-adhesive polyester film (A-4300 manufactured by Toyobo Co., Ltd.) is applied by a microgravure method so that the film thickness after curing by ultraviolet irradiation becomes 2.5 μm, and then cured by ultraviolet irradiation. Thus, a light diffusion layer was formed. Next, an acrylic adhesive SK Dyne 906 (acrylic adhesive manufactured by Soken Chemical Co., Ltd.) was dried on the surface of the film opposite to the light diffusion layer to a thickness of 15 μm.
The film was coated with a comma coater, dried, and then wound up, and a polyester separator of 25 μm was stuck to the adhesive layer to obtain a glass shatterproof film of the present invention.
Table 1 shows the light diffusion property, transmitted image definition, and scattering prevention performance of the obtained scattering prevention film.

Example 2 10 parts by weight of silica fine particles having an average particle diameter of 1 μm and a photopolymerization initiator (Irgacure 184: manufactured by Ciba Geigy)
5 parts by weight and 100 parts by weight of Kayanova FOP-1200 (UV hard coating agent manufactured by Nippon Kayaku Co., Ltd.) are stirred at high speed in a mixed solvent of toluene and isopropyl alcohol to prepare a dispersion having a solid content of 35% by weight, and after curing. Has a thickness of 3.5
A light diffusing layer of the present invention was formed by the same operation as in Example 1 except that the thickness was adjusted to μm. Next, an adhesive layer was formed on the surface of the sheet opposite to the light diffusion layer by the same operation as in Example 1 to obtain a glass shatterproof film of the present invention. Table 1 shows the light diffusion property, transmitted image definition, and scattering prevention performance of the obtained scattering prevention film.

Comparative Example 1 A glass shatterproof film was obtained in the same manner as in Example 2 except that 5 parts by weight of silica fine particles having an average particle size of 4.2 μm was used. Table 1 shows the light diffusion property, transmitted image definition, and scattering prevention performance of the obtained scattering prevention film.

[0026]

Table 1 Haze value Pencil hardness Adhesiveness Transmission image sharpness Anti-scattering performance Example 119% 3H 100/100 30% 99% or more Example 210% 3H 100/100 41% 99% or more Comparative example 119% 3H 100/100 3% 99% or more

(1) Pencil hardness: according to JIS K5400 (2) Adhesion test: according to JIS K5400 cross-cut tape method (gap 1 mm). (3) Light diffusivity: the haze value was measured using a haze meter (manufactured by Tokyo Denshoku Co., Ltd.). (4) Transmission image clarity: The transmission image clarity at an optical comb width of 0.5 mm was measured using an image clarity measuring device (manufactured by Suga Test Instruments Co., Ltd.) according to JIS K7105 image clarity measuring method. (5) Scattering prevention performance: According to JIS A5759 scattering prevention performance test B method.

From the results shown in Table 1, it can be seen that the film of the present invention has a higher transmitted image definition than the comparative example, and is excellent in antiglare properties from the comparison between Example 2 and Comparative Example 1.

[0029]

According to the present invention, there is provided a film for preventing scattering of glass having a light diffusing layer. The film is used for glass such as showcases and buildings, window glass, and the like.
In addition to preventing scattering of glass at the time of destruction, suppressing glare caused by reflection of external light and fluorescent light, not only the reflection of external light is reduced, but also the transmitted image on the other side can be seen clearly.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI B32B 27/30 B32B 27/30 D C09D 4/02 C09D 4/02 7/12 7/12

Claims (10)

[Claims] 1. A film having a light diffusion layer on the surface of the film, and
A glass shatterproof film having a transmitted image definition of more than 10% at an optical comb width of 0.5 mm. 2. The glass scattering prevention film according to claim 1, wherein the light diffusion layer has a large number of fine irregularities on the surface. 3. The glass shatterproof film according to claim 1, wherein the light diffusion layer is a cured film of at least a mixture of an ultraviolet curable resin composition and fine particles. 4. The glass shatterproof film according to claim 3, wherein the fine particles have an average particle diameter of 0.5 to 2 μm as measured by a Coulter counter method. 5. The glass shatterproof film according to claim 3, wherein the fine particles are a silicon compound, a metal compound, a polymer compound or a mixture thereof. 6. The glass shatterproof film according to claim 3, wherein a plurality of fine particles having different average particle diameters are used. 7. The glass shatterproof film according to claim 3, wherein the ultraviolet curable resin composition contains 30 to 90 parts by weight of an acrylate monomer having four or more functional groups. 8. The glass scattering prevention film according to claim 1, wherein the thickness of the light diffusion layer is 0.5 to 10 μm. 9. The glass shatterproof film according to claim 1, wherein a fluorine resin layer or a multilayer antireflection film is formed on the light diffusion layer. 10. The glass shatterproof film according to claim 1, wherein the light diffusion layer is colored.