JP2003112391A - Ultraviolet absorbing film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film to be applied to a window pane for cutting harmful ultraviolet rays. SOLUTION: The ultraviolet absorbing film is a film, to be applied to a window pane, for cutting ultraviolet rays, which is composed of a film containing a fluorescent brightener or an ultraviolet-absorbing film which cuts the ultraviolet rays originating from solar beams or fluorescent lighting and thereby, prevents a photograph from being faded, as an ultraviolet-absorbing film which contains a fluorescent brightener represented by formula (1) and is characterized in that its ultraviolet permeability for the wavelength range of 410 nm or less is 90% or lower. (In the formula, R1 and R4 are a hydrogen atom, an alkyl group or an alkoxy group; R2 and R3 are an alkyl group. [A] is a substituted aryl group or a substituted ethenyl group). The ultraviolet absorbing film may contain a fluorescent brightener in a support or may have a binder layer containing a fluorescent brightener and a binder on the support. Further, the film may have a tacky layer on the binder layer and a release paper on the tacky layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet-absorbing adhesive film for windowing and sunlight, which cuts off harmful ultraviolet rays from sunlight and ultraviolet rays emitted from lighting equipment such as fluorescent lamps which attracts flying insects. The present invention relates to an ultraviolet absorbing film that blocks ultraviolet rays from fluorescent lamps to prevent fading of photographs and liquid crystal displays.

[0002]

2. Description of the Related Art A UV absorber is used for the purpose of blocking UV rays from sunlight, which is harmful to the human body, and UV rays emitted from lighting equipment such as fluorescent lamps, incandescent lamps, halogen bulbs, and mercury lamps that attract flying insects. The film for window covering including is put on the market. However, the absorption edge is 3 to suppress the yellow color.
Although it is possible to absorb up to 410 nm, which has a shorter wavelength than 80 nm or a long wavelength, it is dealt with by adding a dye / pigment for color tone adjustment in order to have a strong yellow tint or suppress yellow tint. Since the absorption edge is short-wave, it has a low UV-shielding ability. In particular, three-wavelength fluorescent lamps, which are expected to become more widespread in the future, have no absorption at 380 nm or less, or even if there is a small amount, they prevent flying insects. There is no need because the ability can be expected from the three-wavelength fluorescent lamp itself. However, even if it is a three-wavelength fluorescent lamp, since the light emission around 405 nm remains, the insect light curve disclosed in JP-A-7-3189 (In general, insects strongly react to wavelengths close to the ultraviolet region, As is clear from this graph showing the wavelength dependence), it is necessary to shield the bright line near 405 nm in order to effectively prevent flying insects, and in order to do so, cut the light up to 410 nm. Is desired. When light up to 410 nm is cut off, it becomes yellowish, and the problem can be solved by adding a dye / pigment for color tone adjustment in order to improve this, but there is a disadvantage that the light transmittance in the visible region is sacrificed. Further, a whitening polyester film which is excellent in weather resistance, whiteness and adhesiveness in which a yellowing degree due to ultraviolet irradiation is suppressed by blending a fluorescent whitening agent together with an ultraviolet absorber (JP-A-11-291432, JP-A-11- 2682
No. 14 publication) has been proposed, but similar disadvantages have not been solved. In addition, a composition made of a transparent resin containing a fluorescent whitening agent has been proposed as a cover for blocking fluorescent lamp ultraviolet rays (Japanese Patent Publication No. 6-3682).

[0003]

SUMMARY OF THE INVENTION The present invention was developed in order to solve the above-mentioned problems of the prior art, and its object is to provide a fluorescent whitening agent which emits blue fluorescence which is a complementary color of yellow. By containing, the wavelength side longer than 405 nm,
In particular, a film for window covering that has a high transparency without yellowing even when cutting up to 410 nm, which is a wavelength longer than 380 nm,
It is to provide a film that blocks the fading of photos, liquid crystal displays, etc. by blocking the sunlight and ultraviolet rays from fluorescent lamps.

[0004]

DISCLOSURE OF THE INVENTION The present invention is directed to a window covering film for UV protection comprising a film containing a fluorescent whitening agent or UV absorption to prevent fading of photographs by cutting UV rays from sunlight and fluorescent lamps. The film is characterized in that (1) it is an ultraviolet absorbing film having the following general formula (I):
An ultraviolet-absorbing film containing a fluorescent brightening agent represented by and having a transmittance of 90% or less at 410 nm or less.

[Chemical 2] (In the formula, R₁And R_FourIs a hydrogen atom, an alkyl group or
Represents an alkoxy group, R ₂And R₃Represents an alkyl group
You [A] represents a substituted aryl or substituted ethenyl group.
You )

The preferred embodiments of the present invention are shown below: (2) The ultraviolet absorbing film has a fluorescent whitening agent layer containing the above-mentioned optical brightening agent and a binder on a transparent support. The ultraviolet absorbing film described in 1). (3) The ultraviolet absorbing film has a constituent layer having at least an adhesive layer on a transparent support and a release paper on the constituent layer,
The ultraviolet absorbing film as described in (2) above, wherein the constituent brightening agent is contained in the constituent layer.

(4) An ultraviolet absorbing film, wherein the fluorescent whitening agent layer described in (2) above or the constituent layer described in (3) above has a glass scattering preventing function. (5) An ultraviolet absorbing film, wherein the fluorescent whitening agent layer described in (2) above or the constituent layer described in (3) above further contains an ultraviolet absorber.

Generally, optical brighteners range from about 320 to about 410.
The compound has a property of absorbing light having a wavelength of nm and emitting light having a wavelength of about 410 to about 500 nm. Textiles dyed with these optical brighteners have about 410 newly emitted optical brighteners in addition to the original yellow reflected light.
Since the blue light having a wavelength of about 500 nm is added, the reflected light becomes white, and the energy of visible light increases due to the fluorescence effect, resulting in whitening. When a transparent support is coated with an adhesive containing an ultraviolet absorber and the amount of ultraviolet absorber added is adjusted so as to block ultraviolet rays of 410 nm or less, especially 405 nm or less, the reflected light feels strongly yellowish. However, they have found that when a fluorescent whitening agent is added to the adhesive layer or the hard coat layer instead of or in addition to the ultraviolet absorber, the reflected light is whitened, and the present invention has been accomplished.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be described in detail below. The support may be, for example, polyethylene terephthalate having a molecular weight of 30,000 to 50,000 or a copolymer film containing polyethylene terephthalate as a main component, and is highly transparent, for example, Lumirror and Unitika manufactured by Toray Industries, Inc. It is preferable to use a commercially available product such as Emblet manufactured by Co., Ltd. The ultraviolet absorbing film of the present invention may be one containing a fluorescent whitening agent of the present invention in a support, or may have a binder layer containing a fluorescent whitening agent of the present invention and a binder on a support, You may have an adhesive layer on the binder layer and a release paper on it. Further, the fluorescent whitening agent of the present invention, in the constitution having a constitutional layer comprising a pressure-sensitive adhesive layer on a support and a release paper thereon, may be contained in the constitutional layer, and the constitutional layer may be an adhesive layer. Besides, a hard coat layer and a binder layer may be mentioned. By having the adhesive layer and the release paper, the ultraviolet absorbing film of the present invention becomes an ultraviolet absorbing adhesive film.

The optical brightener used in the present invention is
It is represented by the following general formula (I).

[Chemical 3] (In the formula, R₁And R_FourIs a hydrogen atom, an alkyl group or
Represents an alkoxy group, R ₂And R₃Represents an alkyl group
You [A] represents a substituted aryl or substituted ethenyl group.
You )

R ₁ in the general formula (I) of the present invention,
R ₂ , R ₃ , R ₄ and [A] will be described in detail below. R ₁ and R ₄ represent a hydrogen atom, an alkyl group or an alkoxy group, more specifically a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. More specifically, R ₁ and R ₄ are each a hydrogen atom, methyl, ethyl, n-propyl, n-butyl, n.
Alkyl groups such as octyl, isopropyl, isobutyl, 2-ethylhexyl, t-butyl, t-amyl, t-octyl, cyclopentyl or cyclohexyl, or methoxy, ethoxy, n-propoxy, n-butoxy, n-octyloxy, iso It is an alkoxy group such as propoxy, isobutoxy, 2-ethylhexyloxy, t-butoxy or cyclohexyloxy. R ₁ and R ₄ are preferably hydrogen atoms or alkyl groups, and particularly preferably hydrogen atoms.

R ₂ and R ₃ represent an alkyl group, more specifically an alkyl group having 1 to 16 carbon atoms, more specifically methyl, ethyl, n-propyl, n-butyl,
It represents an alkyl group such as n-octyl, n-hexadecanyl (cetyl), isopropyl, isobutyl, 2-ethylhexyl, t-butyl, t-amyl, t-octyl, cyclopentyl or cyclohexyl. Preferably,
R ₂ is a methyl, isopropyl, t-butyl or cyclohexyl group, R ₃ is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl or 2
-Ethylhexyl group. Particularly preferably, R ₂ is t
A -butyl or cyclohexyl group, and R ₃ is a methyl, n-butyl, n-octyl or 2-ethylhexyl group.

[A] represents a substituted aryl group or a substituted ethenyl group, more specifically, a substituted aryl group having 6 to 40 carbon atoms or a substituted ethenyl group having 8 to 40 carbon atoms. Preferred are the substituted aryl or substituted ethenyl groups shown below.

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

[Chemical 8]

In the formula, R ₁ 'and R ₄ ' have the same meanings as R ₁ and R ₄ described above. R ₂ 'is the same as R ₂ ,
R ₃ ′ has the same meaning as R ₃ . m represents an integer of 1 to 5. X and Y represent alkyl, aryl, alkoxy, alkylamino, arylamino, amino or hydroxyl group.

Explaining in detail X and Y other than amino and hydroxyl, an alkyl group such as methyl, ethyl, isopropyl, t-butyl or cyclohexyl, phenyl,
Aryl group such as tolyl or naphthyl, alkoxy group such as methoxy, ethoxy or isopropoxy, amino,
Alkylamino groups such as aminomethyl, ethylamino, octylamino, dimethylamino or N-methyl-N-ethylamino, anilino, 4-tolylamino or N-
An arylamino group such as methylanilino. X and Y are preferably aryl, alkoxy or anilino groups.

The compound represented by the general formula (I) is preferably a compound represented by the following general formula (II).

[0021]

[Chemical 9]

Where R_FiveAnd R₇Is the R₂Synonymous with
Group, R₆And R₈Is the R ₃Is synonymous with
It n represents an integer of 1 or 2. These compounds are
Synthesis by the method described in Kaihei 11-29556
Can be done.

Specific examples thereof will be given below, but the present invention is not limited thereto.

[0024]

[Chemical 10]

[0025]

[Chemical 11]

[0026]

[Chemical 12]

[0027]

[Chemical 13]

[0028]

[Chemical 14]

[0029]

[Chemical 15]

[0030]

[Chemical 16]

[0031]

[Chemical 17]

[0032]

[Chemical 18]

[0033]

[Chemical 19]

[0034]

[Chemical 20]

The optical brightener of the present invention absorbs ultraviolet rays (adhesion)
In the film, it may be added to any of the hard coat layer, support, binder layer and adhesive layer, and one kind or two or more kinds may be used in combination. The addition amount to them varies depending on the thickness of each of the hard coat layer, the support and the adhesive layer, the properties of the fluorescent whitening agent, the presence or absence of the ultraviolet absorber, the properties, and the addition amount, and therefore cannot be unambiguously determined. The vendor can easily determine by doing some testing. Generally, in the case of an adhesive layer having a thickness of 50 μm, 0.1 to 30% by mass, preferably 4 to 15% by mass is sufficient. It can be considered that the blending amount and the thickness of the added material are almost in inverse proportion to each other. For example, by adding 4% by mass of the compound of formula (2) to a 50-micron adhesive layer,
Light of 10 nm or less can be substantially cut. Further, the glass shatterproof function is defined by JIS A5759. The attached figure is a graph showing the results of measuring the absorption spectrum of the adhesive film of the present invention on a glass plate using an ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation. It shows that it has low yellowness and high transparency despite absorbing light up to 410 nm.

As described above, in the present invention, the object can be achieved by blending the fluorescent whitening agent in the support or any layer, but the fluorescent whitening agent or the hard coat layer, the support, and the binder. When there is concern about the light resistance of the layer and the adhesive layer, and when the fluorescent whitening agent alone cannot sufficiently cut the short wavelength region, it is desirable to use an ultraviolet absorber together.
Generally, an ultraviolet absorber is a compound having the property of absorbing ultraviolet rays and converting them into heat. They are roughly classified into benzotriazole type, benzophenone type, salicylic acid type, and cyanoacrylate type, but can be arbitrarily selected from known ones. Benzotriazole-based effective absorption wavelength is about 270 to 380 nm, and a typical example is 2- (2 '
-Hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-
5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2-
(2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2- (2'-hydroxy-
4'-octoxyphenyl) benzotriazole etc. can be mentioned.

The effective absorption wavelength of benzophenone is about 27.
0 to 380 nm, as typical examples, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2′- Dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-
5-sulfobenzophenone etc. can be mentioned.

The salicylic acid-based effective absorption wavelength is about 290 to 290.
At 330 nm, a typical example is phenyl salicylate,
Examples thereof include p-t-butylphenyl salicylate and p-octylphenyl salicylate.

The effective absorption wavelength of cyanoacrylates is about 270 to 350 nm, and a typical example is 2-ethylhexyl-2-cyano-3,3-diphenylacrylate,
Examples thereof include ethyl-2-cyano-3 and 3-diphenyl acrylate. These ultraviolet absorbers can be used alone or in combination of two or more. The suitable addition amount cannot be unambiguously determined because it varies depending on the thickness of each of the hard coat layer, support, binder layer, adhesive layer, properties of the optical brightener, etc., but those skilled in the art will carry out some tests. It can be easily determined.
Generally, it is 0.1 for a 50-micron thick adhesive layer.
-30% by mass, preferably 4-15% by mass is sufficient. It can be considered that the blending amount and the thickness of the added material are almost in inverse proportion to each other. The method of adding and mixing the above components to the hard coat layer, the support, the pressure-sensitive adhesive layer, and the binder layer provided separately is arbitrary.

Examples of the polycondensation resin component used in the binder layer include polyurethane, polyester, polyamide, polyurea and polycarbonate. Specific examples are shown below in the form of raw material monomers. However, P-2
3 and P-34 and the following are exemplified in the form of a polymer, but the present invention is not limited thereto. All acidic groups in each polymer are shown in undissociated form. Further, regarding the polyester, polyamide, etc. produced by the condensation reaction, the constituent components are all represented by dicarboxylic acids, diols, diamines, hydroxycarboxylic acids, aminocarboxylic acids, etc. regardless of the raw materials. The ratio in parentheses means the molar percentage ratio of each component.

P-1: Toluene diisocyanate / ethylene glycol / 1,4-butanediol (50/15
/ 35) P-2: 4,4'-diphenylmethane diisocyanate / 1,3-propanediol / polypropylene glycol (Mw = 1000) (50/45/5) P-3: toluene diisocyanate / hexamethylene diisocyanate / ethylene glycol / Polyethylene glycol (Mw = 600) / 1,4-butanediol (40/10/20/10/20) P-4: 1,5-naphthylene diisocyanate / hexamethylene diisocyanate / diethylene glycol /
1,6-hexanediol (25/25/35/15)

P-5: 4,4'-diphenylmethane diisocyanate / hexamethylene diisocyanate / tetraethylene glycol / ethylene glycol / 2,2-
Bis (hydroxymethyl) propionic acid (40/10 /
20/20/10) P-6: 4,4'-diphenylmethane diisocyanate / hexamethylene diisocyanate / butanediol /
Ethylene glycol / 2,2-bis (hydroxymethyl) propionic acid (40/10/20/20/10) P-7: 1,5-naphthylene diisocyanate / butanediol / 4,4′-dihydroxy-diphenyl-2 ，
2'-propane / polypropylene glycol (Mw = 4
00) / 2,2-bis (hydroxymethyl) propionic acid (50/20/5/10/15) P-8: 1,5-naphthylene diisocyanate / hexamethylene diisocyanate / 2,2-bis (hydroxymethyl) Butanoic acid / polybutylene oxide (Mw = 50
0) (35/15/25/25)

P-9: Isophorone diisocyanate / diethylene glycol / neopentyl glycol / 2,2
-Bis (hydroxymethyl) propionic acid (50/20
/ 20/10) P-10: Toluene diisocyanate / 2,2-bis (hydroxymethyl) butanoic acid / Polyethylene glycol (Mw = 1000) / Cyclohexanedimethanol (50/10/10/30) P-11: Diphenylmethane diisocyanate / Hexamethylene diisocyanate / tetraethylene glycol / butanediol / 2,4-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid (40/10 /
10/33/7) P-12: Diphenylmethane diisocyanate / hexamethylene diisocyanate / butanediol / ethylene glycol / 2,2-bis (hydroxymethyl) butanoic acid / 2,4-di (2-hydroxy) ethyloxycarbonylbenzene sulfone Acid (40/10/20/15/1
0/5)

P-13: terephthalic acid / isophthalic acid /
Cyclohexanedimethanol / 1,4-butanediol / ethylene glycol (25/25/25/15/1
0) P-14: terephthalic acid / isophthalic acid / 4,4′-dihydroxy-diphenyl-2,2-propane / tetraethylene glycol / ethylene glycol (30/20 /
20/15/15) P-15: terephthalic acid / isophthalic acid / cyclohexanedimethanol / neopentyl glycol / diethylene glycol (20/30/25/15/10) P-16: terephthalic acid / isophthalic acid / 4,4 ′ -Benzene dimethanol / diethylene glycol / neopentyl glycol (25/25/25/15/10)

P-17: terephthalic acid / isophthalic acid /
5-sulfoisophthalic acid / ethylene glycol / neopentyl glycol (24/24/2/25/25) P-18: terephthalic acid / isophthalic acid / 5-sulfoisophthalic acid / cyclohexanedimethanol / 1,4-butanediol / Ethylene glycol (22/22/6 /
25/15/10) P-19: isophthalic acid / 5-sulfoisophthalic acid / cyclohexanedimethanol / ethylene glycol (40
/ 10/10/40/10) P-20: cyclohexanedicarboxylic acid / isophthalic acid / 2,4-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid / cyclohexanedimethanol /
Ethylene glycol (30/20/5/25/20)

P-21: 11-aminoundecanoic acid (1
00) P-22: 12-aminododecanoic acid (100) P-23: reaction product of poly (12-aminododecanoic acid) and maleic anhydride (50/50) P-24: 11-aminoundecanoic acid / 7 -Aminoheptanoic acid (50/50) P-25: Hexamethylenediamine / adipic acid (50
/ 50) P-26: tetramethylenediamine / adipic acid (50
/ 50) P-27: hexamethylenediamine / sebacic acid (50
/ 50) P-28: N, N-dimethylethylenediamine / adipic acid / cyclohexanedicarboxylic acid (50/20/3
0)

P-29: Toluene diisocyanate /
4,4'-Diphenylmethane diisocyanate / hexamethylenediamine (30/20/50) P-30: Nonamethylenediamine / urea (50/50) P-31: Hexamethylenediamine / nonamethylenediamine / urea (25/25 / 50) P-32: Toluene diisocyanate / hexamethylenediamine / 2,2-bis (hydroxymethyl) propionic acid (50/40/10) P-33: 11-aminoundecanoic acid / hexamethylenediamine / urea (33/33) / 33)

Acrylic esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate are used as monomers for forming the vinyl polymer of the present invention. , Tert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-
Bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate,
Benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxybutyl Acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxy acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ) Ethyl acrylate, ω-methoxy polyethylene glycol acrylate (addition mole number n = 9), 1
-Bromo-2-methoxyethyl acrylate, 1,1-
Dichloro-2-ethoxyethyl acrylate, etc. may be mentioned. In addition, the following monomers can be used.

Methacrylic acid esters: Specific examples thereof include methyl methacrylate, ethyl methacrylate, and n.
-Propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, stearyl methacrylate, sulfopropyl Methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2- (3-phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate. , 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate,
2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (addition mole number n =
6), acrylic methacrylate, dimethylaminoethyl methyl chloride methacrylate salt, and the like.

Vinyl esters: Other specific examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenyl acetate, vinyl benzoate. , Vinyl salicylate and the like.

Acrylamides: for example, acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, isopropyl acrylamide,
n-butyl acrylamide, sec-butyl acrylamide, tert-butyl acrylamide, cyclohexyl acrylamide, benzyl acrylamide, hydroxymethyl acrylamide, methoxyethyl acrylamide, dimethylaminoethyl acrylamide, phenyl acrylamide, dimethyl acrylamide, diethyl acrylamide, β-cyanoethyl acrylamide, N-
(2-acetoacetoxyethyl) acrylamide, diacetone acrylamide, etc. are mentioned.

Methacrylamides: for example, methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, isopropylmethacrylamide, n-butylmethacrylamide, sec-butylmethacrylamide, tert-butylmethacrylamide, cyclohexylmethacrylamide, Benzyl methacrylamide, hydroxy methacrylamide, chlorobenzyl methacrylamide, octyl methacrylamide,
Stearyl methacrylamide, sulfopropyl methacrylamide, N-ethyl-N-phenylaminoethyl methacrylamide, 2- (3-phenylpropyloxy)
Ethyl methacrylamide, dimethylaminophenoxyethyl methacrylamide, furfuryl methacrylamide,
Tetrahydrofurfuryl methacrylamide, phenyl methacrylamide, cresyl methacrylamide, naphthyl methacrylamide, 2-hydroxyethyl methacrylamide, 4-hydroxybutyl methacrylamide, triethylene glycol monomethacrylamide, dipropylene glycol monomethacrylamide, 2-methoxy Ethyl methacrylamide, 3-methoxybutyl methacrylamide, 2-acetoxyethyl methacrylamide, 2-acetoacetoxyethyl methacrylamide, 2-ethoxyethyl methacrylamide, 2-iso-propoxyethyl methacrylamide, 2-butoxyethyl methacrylamide, 2 -(2-methoxyethoxy) ethyl methacrylamide, 2- (2-ethoxyethoxy) ethyl methacrylamide, 2- (2 Butoxyethoxy) ethyl methacrylamide, ω-methoxy polyethylene glycol methacrylamide (additional mol number n = 6), acryl methacrylamide, dimethylamino methacrylamide, diethylamino methacrylamide, β-cyanoethyl methacrylamide, N- (2-acetoacetoxyethyl) ) Methacrylamide and the like can be mentioned.

Olefins: Examples include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 2,3-dimethylbutadiene.

Styrenes: For example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, vinyl benzoic acid methyl ester. And so on.

Vinyl ethers: For example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether and the like can be mentioned.

Other examples include butyl crotonic acid, hexyl crotonic acid, dibutyl itaconate, dimethyl maleate, dibutyl maleate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, glycidyl. Acrylate, glycidyl methacrylate, N-vinyl oxazolidone, N-vinyl pyrrolidone, acrylonitrile,
Methacrylonitrile, methylene molone nitrile, vinylidene, etc. can be mentioned.

The monomers used in the polycondensate and polymer of the present invention are two or more kinds of monomers which are comonomers with each other for various purposes (for example, improvement in solubility, hardness, softness, tensile strength, etc.). May be used as The monomers of the invention in the polymer are preferably methacrylate-based,
Acrylamide type and methacrylamide type. In particular, a copolymer of methyl methacrylate and styrene is preferable.

Examples of the adhesive component in the adhesive layer include highly transparent acrylic resins, natural rubbers, and styrene-butadiene resins. For example, as an acrylic resin type, Olibain BPS 1109 two-component [Toyo Ink Mfg. Co., Ltd.] is used.
Product name], Fine Tac TD-3208 two-part type [Product name of Dainippon Ink and Chemicals, Inc.], Nisetsu KP-
Examples include commercially available ones such as 491 one-liquid type (trade name, manufactured by Nippon Carbite Industry Co., Ltd.), but an adhesive having a novel composition developed as needed may be used. It is desirable that there is no residual solvent, but 10 to 2000 ppm of residual solvent may remain in the film after coating the binder and the adhesive. The release paper protects the adhesive layer from the time of application to the time of sticking to the glass, and is coated with a fluororesin, a silicone resin or the like on the surface in contact with the adhesive layer for easy peeling. The hard coat layer is usually formed by subjecting the surface to a curing treatment of, for example, a pencil hardness of about 2H so as not to be scratched when stains are wiped off.

The pressure-sensitive adhesive film of the present invention is generally composed of a transparent support, a pressure-sensitive adhesive layer, a release paper, a hard coat layer, a binder layer, etc., and their thicknesses are generally as follows. Transparent support: 25 to 100 μ Binder layer: 10 to 50 μ Adhesive layer: 10 to 100 μ Release paper: 10 to 50 μ Hard coat layer: 2 to 50 μ

[0060]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. Here, the transmittance was measured with an ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation, with the film being attached to a glass plate and using the same glass plate as a reference. [Example 1] 50 g of toluene was added to 100 g of an adhesive having the following composition.
ml and 50 ml of methyl ethyl ketone were added and dissolved at 40 ° C. This mixed solution was used as a PET film [trade name of Toray Industries, Inc., Lumirror, film thickness 25 μm, visible light transmittance 95%].
The reverse coater was used for coating, and the coating was dried at 65 ° C. for 5 minutes to form a pressure-sensitive adhesive layer having a film thickness of 50 μm. Then, release paper is laminated on the adhesive layer,
An ultraviolet absorbing transparent adhesive sheet of the present invention was prepared. -Acrylic resin [manufactured by Dainippon Ink & Co., Inc., trade name Acritech] 88 mass% -Compound represented by formula (1) 4 mass% 2- (2'-hydroxy-5'-t-butylphenyl) ) Benzotriazole 8% by mass

Example 2 The following resin, UV absorber and fluorescent whitening agent were added to 50 ml of toluene and 50 of methyl ethyl ketone.
It was added to ml and dissolved at 40 ° C. -Methyl methacrylate: styrene = 60:40 mass% copolymer 17.6 g-2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole 1.2 g-Fluorescent brightener Formula of compound example ( 2) 1.2 g This mixed solution was applied onto a PET film (trade name, manufactured by Toray Industries, Inc., trade name, Lumirror, film thickness 25 μm, visible light transmittance 95%) using a reverse coater at 65 ° C. It was dried under a drying condition for 5 minutes to form a binder layer having a film thickness of 25 μm.

Example 3 On the binder layer of the film obtained in Example 2, 100 g of an acrylic resin (trade name, Acritech, manufactured by Dainippon Ink and Chemicals, Inc.) was added to 50 ml of toluene and 50 ml of methyl ethyl ketone at 40 ° C. Apply the solution dissolved in 2. using a reverse coater, and
It was dried at 5 ° C. for 5 minutes to form a pressure-sensitive adhesive layer having a film thickness of 50 μm. Then, release paper was laminated on the pressure-sensitive adhesive layer to prepare the ultraviolet absorbing transparent pressure-sensitive adhesive sheet of the present invention.

The films obtained in Examples 1 and 3 were attached to a glass plate and the absorption spectrum was measured. 410, which has a longer wavelength than the commercially available products as comparison examples, 3M ISCLARL (trade name) and Lintec Optron Clear (trade name)
It was possible to obtain an ultraviolet-absorbing film having a high degree of transparency without yellowing despite absorbing light up to nm. The film obtained in Example 2 also showed the same results as above.

[0064]

EFFECT OF THE INVENTION The ultraviolet absorbing film obtained by the present invention has no yellowish tint, has high transparency, and has no coloring in transmitted light. Therefore, in addition to window glasses for general houses, factories, cars, etc., show windows for displaying products. And glass of showcases, acrylic panels of vending machines, photographs, photographs with fluorescent lights as backlights (for example, G color from Fuji Photo Film Co., Ltd.), color output products of inkjet printers, outdoor exhibits such as posters, Even if it is used in a product such as a liquid crystal display display in which fading may occur, the natural color peculiar to the article is not impaired. In addition, since it does not leak the ultraviolet rays generated from lighting equipment such as fluorescent lamps, incandescent lamps, halogen lamps, and mercury lamps to the outside, it is possible to prevent the attraction of flying insects.

[Brief description of drawings]

FIG. 1 is a graph showing ultraviolet absorption spectra of Examples 1 and 3 and commercial products.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09B 57/00 C09B 57/00 D V F21V 9/06 F21V 9/06 // C08L 67:00 C08L 67: 00 (72) Tadahisa Sato 210, Nakanuma, Minamiashigara, Kanagawa Prefecture, Fuji Photo Film Co., Ltd. (72) Kazuyoshi Yamakawa, 210, Nakanuma, Minamiashigara, Kanagawa Prefecture, F Term, Fuji Photo Film Co., Ltd. 4F006 AA35 AB05 AB16 AB24 AB32 AB35 AB37 AB38 AB62 AB65 BA03 CA03 CA05 DA04 4F071 AA11A AA13A AA22A AA33A AA46 AB22 AE05 AF30 AF34 AH03 AH12 BB02 BC01 BC02 CA01 CB01 CA02 CA32 BA32C30 BA08B30BA30A30A30A00 JL13B JL14C JN01 JN28 4H056 CA03 CC02 CE02 CE03 DA02 DB01 DC01 DD23 DE03 DE11 EA16 FA02

Claims (5)

[Claims] 1. An ultraviolet absorbing film, which comprises:
Containing an optical brightener represented by formula (I) and having a wavelength of 410 nm or less.
UV rays having a lower transmittance of 90% or less
Absorption film. [Chemical 1] (In the formula, R₁And R_FourIs a hydrogen atom, an alkyl group or
Represents an alkoxy group, R ₂And R₃Represents an alkyl group
You [A] represents a substituted aryl or substituted ethenyl group.
You ) 2. The ultraviolet absorbing film according to claim 1, wherein the ultraviolet absorbing film has a fluorescent brightening agent layer containing the fluorescent brightening agent and a binder on a transparent support. 3. The ultraviolet absorbing film has a constituent layer having at least an adhesive layer on a transparent support and a release paper on the constituent layer, and the fluorescent whitening agent is contained in the constituent layer. The ultraviolet absorbing film according to claim 1, wherein 4. An ultraviolet absorbing film, wherein the fluorescent whitening agent layer according to claim 2 or the constituent layer according to claim 3 has a glass shatterproof function. 5. An ultraviolet absorbing film, wherein the fluorescent whitening agent layer according to claim 2 or the constituent layer according to claim 3 further contains an ultraviolet absorber.