JPH0219449B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an external light antireflection light shielding screen used for blocking external light incident on the image surface of a display tube of a television receiver, for example, and a method for manufacturing the same. Conventionally, light-shielding screens have been used in television receivers and the like to block incoming external light and prevent light emitted by external light from emitting light or degrading the received light image.
Various things have been proposed. For example, JP-A-51
-44186 and Japanese Patent Application Laid-open No. 51-75456,
A light-blocking screen is described that consists of three layers: a transparent plastic layer, a light-reflecting layer and a light-blocking layer. However, these conventional light-shielding screens have complicated manufacturing methods, and their products, especially the light-shielding screens described in the above-mentioned patent application, have problems such as difficulty in producing uniform thickness and roughening of the surface of the screen. Has a point. That is, in the methods described in these documents in which a block consisting of a transparent layer and a light-shielding layer is scraped off, the cut surface is inevitably rough, resulting in poor precision and unevenness. Furthermore, even if another transparent sheet is bonded to this cut surface, it is difficult to completely eliminate this roughness, and poor precision and unevenness will inevitably remain. Furthermore, these light-shielding screens have a ghost phenomenon in which images passing through the screen appear multiple. This ghost phenomenon occurs when light rays from a display tube such as a television screen are regularly reflected from the sides of the striped or checkered pattern that forms the transparent layer of the screen, and this reflected light appears as if it were straight light, creating a virtual image. It's for a reason. Therefore, in order to prevent this ghost phenomenon, it is possible to prevent the ghost phenomenon by preventing regular reflection on the side surfaces of the striped or checkered pattern.
As a screen to prevent this ghost phenomenon, JP-A-50-92751 discloses a transparent plastic layer,
A light-blocking screen is described that consists of three layers: a light-scattering layer and a light-blocking layer. However, this screen also
Like the previous screen, this method involves scraping off blocks, so it has the same drawbacks as the previous screen. Further, although this screen is provided with a light scattering layer, since a transparent plastic layer is present between the light scattering layers, the light scattering layer has a drawback that the antireflection ability is not sufficient. Furthermore, Japanese Patent Laid-Open No. 139250/1983 discloses an antireflection plate formed of a photocurable resin or the like on a transparent plate. However, with the dimensions of the relief described here, the anti-reflection function of external light against obliquely incident light is insufficient, and when used in a television receiver, a ghost phenomenon occurs due to reflections on the sides of the relief, resulting in a sharp image. It is difficult to visually recognize images. The present inventors conducted various studies on light-shielding screens in the above-mentioned situation, and found that when a photosensitive resin composition containing a surface matting agent is used as the light-reflecting layer and the light-shielding layer, the manufacturing method thereof The present invention was completed based on the discovery that a light-shielding screen can be manufactured easily and without surface roughness. That is, the first invention of the present invention has stripes or lattice-like protrusions formed from a photosensitive resin composition that has been photocured and has at least a roughened side surface in the vertical and/or horizontal directions on a transparent plate. A light-shielding screen for preventing reflection of external light and a second invention include a transparent image carrier having a transparent plate, a photosensitive resin composition layer containing a surface matting agent, and a striped or checkered pattern consisting of straight lines in transparent and non-transparent areas. After stacking in this order,
This is a method for producing an external light antireflection light-shielding screen, in which actinic light is irradiated from the side of the transparent image carrier, and then unexposed areas of the transparent image carrier and the photosensitive resin composition containing a surface matting agent are removed. Since the external light anti-reflection light-shielding screen of the present invention is a relief with a uniform and sharp pattern, the image does not appear uneven, and the ghost phenomenon caused by reflection on the sides of the relief can be prevented. It has the advantage of being easily manufactured without requiring complicated steps. Furthermore, since this screen has an air layer between the patterns, the roughening of the side surface has a large anti-reflection effect, and the ghost phenomenon is significantly prevented. The striped or checkered sides of this screen also
This is the interface between the photocured portion and the uncured portion of the photosensitive resin composition, that is, the exposed area and the unexposed area, and the surface can be efficiently roughened by adding a known surface matting agent to the photosensitive resin composition. It can be achieved. The transparent plate used in the present invention is a sheet or film having a smooth surface and substantially transmitting light, such as transparent glass, polymethyl methacrylate, polystyrene, polyvinyl chloride, polycarbonate, polypropylene, polyethylene terephthalate. , acetyl cellulose,
Examples include polyacrylonitrile, polyamide, polyvinyl alcohol, etc., and the thickness is usually 1 to 1.
In the case of plastic, a film or sheet having a thickness of 20 μm or more, preferably 50 μm or more can also be used. Among these, a glass plate is preferable, and furthermore, this glass plate can be used with a silane compound (vinyltrichlorosilane, vinyltriethoxysilane, β-(3,4 epoxycyclohexyl)ethyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane). , γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, etc.) are particularly preferred. The striped or lattice-like protrusions formed by the photocured photosensitive resin composition of the present invention are required to substantially not transmit light, and in the case of the present invention, the side surfaces are roughened, Although it is not necessarily necessary to color the photocured stripes or lattice pattern protrusions as necessary since they do not substantially transmit light, it is effective to color the photocured stripes or lattice pattern protrusions as needed. In this case, the coloring method is
This can be done by dyeing, applying paint, spraying, etc. In this case, staining methods are useful. The surface matting agent used in the present invention includes:
Substances that, when added to the photosensitive resin composition, have little coloring, do not have a very high ultraviolet absorption rate, and do not have an adverse effect on relief forming properties, such as titanium oxide, mica, calcium carbonate, powdered glass,
(product name: Glass Pearl, particle size 5-15μ), fine particulate silica (product name: Thyroid, Aerosil, etc., particle size 0.5-20μ), alumina powder, clay, etc., and the amount added to the photosensitive resin composition. is 0.1 to 20% by weight, preferably 0.5 to 10% by weight. If the amount added is less than 0.1% by weight, there is no effect of reflecting external light, and if it is more than 20% by weight, the effect of roughening the surface is small, and the transparency of the photosensitive resin composition is also poor. There is a reduction in relief resolution due to scattering. Further, the amount added is determined by the effect of roughening the side surface of the relief to be created, and is carried out so that the reflectance is 20% or less as measured by the reflectance measuring method described later. Among these surface matting agents, particulate silica is a preferred surface matting agent in terms of dispersibility, optical refractive index, and the like. A representative example of the photosensitive resin composition used in the present invention is a composition comprising a prepolymer having an ethylenically polymerizable unsaturated group and, if necessary, an ethylenically unsaturated monomer, a photopolymerization sensitizer, and a thermal polymerization inhibitor. There is.
Examples of the above prepolymers include unsaturated polyesters, unsaturated polyurethanes, oligoester acrylates, unsaturated polyamides, unsaturated polyimides, unsaturated polyethers, unsaturated poly(meth)acrylates, and various modified products thereof, and carbon-carbon dioxide. Examples include various rubber compounds having multiple bonds. These prepolymers generally have a number average molecular weight of substantially 500 or more. To give more specific examples, examples of unsaturated polyesters and alkyds include unsaturated dibasic acids such as maleic acid, fumaric acid, and itaconic acid, or their acid anhydrides, and ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and glycerin. , trimethylolpropane, pentaerythritol, 1,4-polybutadiene with terminal hydroxyl groups, hydrogenated or non-hydrogenated 1,2
- Polyesters with polyhydric alcohols such as polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, and some of the above acid components are succinic acid, adipic acid, phthalic acid, isophthalic acid, phthalic anhydride, trimellitic acid Examples of unsaturated polyurethanes include polyesters substituted with saturated polybasic acids, such as polyesters, and polyesters modified with drying oil fatty acids or semi-drying oil fatty acids.
That is, compounds in which addition-polymerizable unsaturated groups are introduced using the terminal isocyanate groups or hydroxyl groups of compounds that are linked via urethane groups derived from polyols and polyisocyanates having two or more terminal hydroxyl groups, such as the polyols mentioned above. Polyols such as alcohols, polyester polyols, and polyether polyols have terminal hydroxyl groups,
1,4-polybutadiene, hydrogenated or non-hydrogenated 1,2
-Polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer and toluylene diisocyanate, diphenylmethane-
4,4'-diisocyanate, hexamethylene diisocyanate, and other polyisocyanates into which unsaturated groups are introduced using the terminal isocyanate or hydroxyl group reactivity of polyurethane, i.e., among the above-mentioned unsaturated carboxylic acids or their esters. Compounds into which an unsaturated group is introduced by reacting a compound having active hydrogen such as a hydroxyl group, carboxyl group, or amino group with an isocyanate, or a compound into which an unsaturated group is introduced by reacting a compound having a carboxyl group with a hydroxyl group, or the unsaturated group mentioned above. Compounds such as saturated polyester linked with polyisocyanate, etc.
Oligoester acrylates are produced by co-condensing acrylic acid or methacrylic acid in the ester reaction system of polybasic acid and polyhydric alcohol, adjusting the molar ratio of each, and producing a molecular weight of 200.
~5000, such as adipic acid, phthalic acid, isophthalic acid, or acid anhydride, and polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, glycerin, trimethylolpropane, and pentaerythritol. Condensed by coexisting acrylic acid or methacrylic acid in an ester reaction system, epoxy acrylates, such as polyhydric alcohols, polyphenols, or polyphenols with epoxy groups obtained by polycondensation reaction with epichlorohydrin or alkylene oxide. Esters of compounds and acrylic acid or methacrylic acid, polymeric compounds with addition-polymerizable carbon-carbon double bonds in their side chains, such as polyvinyl alcohol, polymeric compounds with hydroxyl groups such as cellulose, and unsaturated carboxylic acids or their An unsaturated alcohol, glycidyl acrylate, or methacrylate is ester bonded to a compound obtained by reacting with an acid anhydride or a polymer compound having a carboxyl group such as a polymer or copolymer of acrylic acid or methacrylic acid. products, reaction products of copolymers containing maleic anhydride with allyl alcohol, hydroxyalkyl acrylate or methacrylate, and reaction products of copolymers containing glycidyl acrylate or methacrylate as a copolymerization component with acrylic acid or methacrylic acid. etc. can be mentioned. In addition, various rubber compounds include ()1,4-polybutadiene, 1,
2-polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer,
EPDM, () Hydrogenated products of () above, isobutyley-isobrene copolymer, ethylene propylene copolymer, and unsaturated compounds in which ethylenically unsaturated groups are introduced by known techniques into various rubbers or higher compounds shown in (). Examples include modified rubber. The compounds in parentheses can be used as is, but
In order to introduce the unsaturated group, it is convenient to use various rubber compounds having a terminal functional group. Also,
In the case of a rubber compound having a 1,2-polybutadiene segment, the unsaturated group can be easily introduced by adding maleic anhydride to the compound. As prepolymers other than those mentioned above, there is no problem in using compounds that do not contain double bonds and are photopolymerized by a mechanism other than the addition of ethylenic double bonds, such as water-soluble nylon, polyvinyl alcohol, and derivatives thereof. Various known compounds can be used as the ethylenically unsaturated monomer, and examples of such compounds include unsaturated carboxylic acids such as acrylic acid and methacrylic acid, or esters thereof, such as alkyl-, cyclo-, Mono- or Acrylamide, methacrylamide or derivatives thereof, such as diacrylates and methacrylates, trimethylolpropane triacrylates and methacrylates, pentaerythritate tetraacrylates and methacrylates, e.g. Allyl compounds such as allyl alcohol, allyl isocyanate, diallyl phthalate, triallyl cyanurate, etc., maleic acid, maleic anhydride, fumaric acid or esters thereof, such as mono- or dimaleates and fumarates of alkyl, alkyl halides, alkoxyalkyl, other unsaturated compounds such as styrene, vinyltoluene, divinylbenzene, N-vinylcarbazole, N-vinylpyrrolidone, etc. . In addition, a part of these monomers may be added to an azide compound such as 4,4'-diazidostilbene, p-phenylene-
Bisazide, 4,4′-diazidebenzophenone,
4,4'-diazidophenylmethane, 4,4'-diazidochalcone, 2,6-di(4'-azidobenzal)-cyclohexanone, 4,4'-diazidostilbene-α-carboxylic acid, 4, 4'-Diazido diphenyl, 4,4'-diazidostilbene-2,2'-
It can be replaced with sodium disulfonate, etc. These monomers may be added in an amount of 0 to 200 parts by weight per 100 parts by weight of the prepolymer. As the photopolymerization sensitizer, various known photosensitizers can be used. Examples of such substances include benzoin, benzoin alkyl ethers such as benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin butyl ether, 2,2-dimethoxy-2-phenylacetophenone, These include benzophenone, benzyl, diacetyl, diphenyl sulfide, eosin, thionine 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, Michler's ketone, etc.
Can be used in the range of 0.001-10% by weight. As a thermal polymerization inhibitor, hydroquinone, mono-tert-butylhydroquinone, benzoquinone, 2,5
-diphenyl-p-benzoquinone, picric acid,
Examples include di-p-fluorophenylamine, p-methoxyphenol, and 2,6-di-tert-butyl-p-cresol. It is desirable that these thermal polymerization inhibitors prevent thermal polymerization reactions (dark reactions). Therefore, it is desirable that the amount of the thermal polymerization inhibitor added is in the range of 0.005 to 5.0% by weight based on the total amount of the prepolymer and the crosslinking agent. In addition, a composition comprising polyele, polythiol, and photosensitizer disclosed in Japanese Patent Publication No. 46-29525 is also useful. Other diazo-based photosensitive resin compositions, such as diazoresins containing aromatic diazonium compounds as a main component, compositions of diazide compounds and rubber compounds, and cinnamate-based photosensitive resin compositions, as well as special Examples include photosensitive resin compositions comprising a compound that releases a Lewis acid when exposed to light and an oxirane-containing compound, as disclosed in Publication Nos. 14277 and 14278 of 1983. The method for producing an external light antireflection light-shielding screen of the present invention includes a transparent plate, a photosensitive resin composition layer containing a surface matting agent, and a transparent image support having a striped or lattice pattern made of straight lines of a transparent part and a non-transparent part. After laminating the transparent image carrier and the photosensitive resin composition in this order, the transparent image carrier is exposed to active light from the side, and then the transparent image carrier and the photosensitive resin composition containing a surface matting agent (hereinafter referred to as the composition) are exposed. Manufactured by removing the exposed part. Furthermore, if necessary, the exposed areas of the photosensitive resin composition of the product are dyed with a dye. The above-mentioned method for laminating the transparent plate, the composition and the transparent image carrier includes coating the composition on the transparent plate in a layered form, preferably with a thickness of 40 to 2000 μm, or adhering a sheet of the composition, and then layering the composition on the transparent plate. A striped or lattice pattern consisting of straight lines of transparent and non-transparent parts on a body, such as a negative film for photolithography using a silver salt image, a plastic film or sheet that is substantially transparent to actinic rays, a transparent glass sheet, cellophane, etc. A pattern having been provided by printing or the like, in which the width of the transparent part is preferably 20 to 500 µm, and the width of the non-transparent part is 20 to 1000 µm, is placed on the composition. Alternatively, on the contrary, after forming a composition layer on a transparent image carrier, a transparent plate may be placed in close contact with each other. set up and place it,
A liquid or molten composition may be injected into this gap. When irradiating with active light such as arc lamps, mercury lamps, xenon lamps, ultraviolet fluorescent lamps, and sunlight, it is preferable to place the composition and the transparent image carrier in close contact from the viewpoint of image reproducibility. Even if the composition is liquid or solid, if the surface is sticky, a transparent plastic film such as a polypropylene film, a polycarbonate film, a polyethylene terephthalate film, an acetyl cellulose film, etc. is used between the transparent image carrier and the composition. Providing an intermediate layer such as polyvinyl alcohol film or cellophane is effective because it protects the transparent image carrier and prevents adhesion between the transparent image carrier and the composition layer after irradiation. In addition, as a method for removing the unexposed areas of the composition after image-forming exposure, a known method may be used, for example, after image-forming exposure has been completed and the transparent image carrier has been removed, the plate is placed on a drum with the plate surface to be developed outside. Alternatively, the plate may be attached to a flat plate and a developing solution is sprayed onto the plate surface to wash out the unexposed areas, or a brush may be immersed in the developing solution and the unexposed areas can be removed with the brush. Furthermore, as a method for dyeing the composition with a dyeing agent if necessary, the composition may be immersed in a heated solution of a dyeing agent such as a cationic dye, a disperse dye, an acid dye, a reactive dye, a metal-containing dye, and then washed and dried. This can be done by At this time, since the transparent plate is dyed depending on the type of transparent plate, it is necessary to select a dyeing agent. Examples of such dyes include cationic dyes, acidic dyes, and reactive dyes. The reason for this is that the composition is -COOH, -
It is relatively easy to incorporate functional groups such as OH, >NH, -SO ₃ H, etc., and while many materials have these functional groups, plastics used as transparent plates are It has almost no of these functional groups. The degree of dyeing at this time may be such that the exposed and photocured photosensitive resin composition becomes opaque to light, and in many cases, it is sufficient that the surface is dyed. The external light antireflection light shielding screen of the present invention has a first
As shown in FIG. 2, the transparent plate 2 has a structure in which striped or lattice-like protrusions 1 made of a photosensitive resin composition photocured and roughened at least on the side surfaces are provided on the surface of the transparent plate 2, The height C of the striped or lattice pattern protrusions 1 is preferably 40 to 2000μ, more preferably 200 to 1200μ, and the width a is preferably 20 to 500μ.
Particularly preferably 100-300μ, interval b 20-1000μ
Particularly preferably 200 to 600μ, width/interval=
1/5 to 1/1, spacing/height = 1/0.6 to 1/2
is preferable, and particularly preferably spacing/height=1/0.85 to 1/2. The anti-reflection of external light light-shielding screen of the present invention can be used to prevent reflection of external light in television receiver screens, traffic signals, instrument panels, and the like. Example 1 Diethylene glycol diethylene methacrylate 12
Part, tetraethylene glycol dimethacrylate
30 parts, 2-hydroxyethyl methacrylate 12
1 part, 6 parts of diacetone acrylamide, 2 parts of benzoin isobutyl ether, and 0.03 part of 4-tert-butylcatechol to obtain a photosensitive resin composition.Furthermore, the matting agent shown in Table 1 was added to this composition to erase it. A photosensitive resin composition containing the agent was produced. Next, a non-transparent part of 300μ was placed on a transparent glass plate.
The above photosensitive resin composition containing a matting agent is poured onto a board on which a negative film having a striped pattern with a transparent area of 150 μm and a polypropylene film with a thickness of 20 μm are superimposed, and γ-methacryloxypropyl trifluoride is poured onto this composition. A 5 mm thick glass plate whose surface had been treated with methoxysilane was placed in contact with the resin composition. At this time, the thickness of the resin layer was adjusted to 300 μm using a spacer. From the negative film side of the assembly thus assembled, the negative film was exposed for 120 seconds using a 3KW ultra-high pressure mercury lamp to photocure it into a striped pattern. After exposure, the glass plate, negative film, and polypropylene film of this assembly are removed, and the assembly is heated to a liquid temperature.
Using a spray method, a weak alkaline solution (1% sodium borate solution) at 40 to 45°C is discharged at a pressure of 1 kg/cm ² , a discharge rate of approximately 20/min, and a distance of approximately 5 mm between the resin layer of the assembly and the nozzle tip. The resin composition in the non-exposed areas was removed by spraying. After removing this unexposed area, the plate was washed with water and post-exposed (irradiation amount: 1000 mJ/cm ² , 20 minutes)
and drying (50℃, 10 minutes), then 70-80℃
0.5% by weight of disperse dye (manufactured by Nippon Kayaku,
It was dyed by immersing it in a water bath containing Kayakalan Blue BLack RL (trade name: Kayakalan Blue BLack RL) for 10 minutes, followed by washing with water and drying (50°C, 10 minutes) to produce a light-shielding screen that prevents the reflection of external light. This screen was used to evaluate ghost phenomena and surface reflectance. The results are shown in Table-1.

【table】

[Table] The surface reflectance marked with * is on a glass plate with a thickness of 9μ.
1.Place the polyester film of 1 on top of it.
Place a mm spacer. Pour the corresponding photosensitive resin composition containing a surface matting agent shown in Table 1 into it, and then place 100 μm of the surface matting agent on top of this as a support.
A 1 mm thick photosensitive resin composition layer was formed by laminating a polyester film and placing a glass plate thereon. By exposing this to constant light using a chemical lamp, the photosensitive resin composition is cured to a thickness of 0.5 mm on a 100 μm polyester film as a support. The uncured area is washed away with a 1% boric acid aqueous solution. After washing with water, the resin plate was immersed in a 0.5% Kayakalan Blue Black RL aqueous solution heated to 70 to 80°C for 10 minutes for dyeing. A color difference computer CDE-CH-4 (manufactured by Suga Test Instruments Co., Ltd.) that directly reads the specular reflectance of the dyed resin board.
This is the value measured at Example 2 A surface matting agent-containing photosensitive resin composition obtained by adding 5% by weight of a surface matting agent (fine particulate silica (particle size 3.5 μ)) to the photosensitive resin composition of Example 1, and a transparent part as a negative film. width of 100μ, width of non-transparent part
An anti-reflection light-shielding screen for computer CRTs and displays was prepared in the same manner as in Example 1, except that the pattern had a striped pattern of 250 μm and the thickness of the resin composition layer was 250 μm. When this screen was applied to a computer, the characters on the display were sharp and no ghosting was observed. Example 3 Using the photosensitive resin composition of Example 1 to which 15% by weight of particulate silica (average particle size 3.5μ) was added,
A light-shielding screen for preventing reflection of external light was manufactured by the same procedure as in Example 1 except that the dyeing was omitted, and the ghost phenomenon, contrast reduction, and surface reflectance were measured. As a result, the surface reflectance was 7%, there was no ghost phenomenon, and no decrease in contrast was observed.

[Brief explanation of drawings]

FIG. 1 is a front view of the external light reflection prevention light shielding screen of the present invention, in which the horizontal striped pattern projections,
Figure B shows a vertical striped pattern, Figure C shows an anti-reflection light-shielding screen for external light provided with checkered projections, and Figure 2 is a sectional view of Figure 1 A taken along the line A--A'. In the figure, 1 is a striped or checkered pattern provided on the surface of the transparent plate 2, 2 is the transparent plate, a is the width of the striped or checkered pattern projections 1, b is the gap between the stripes or checkered pattern 1, and c is the striped or checkered pattern. This is the height of the lattice pattern projections 1.

Claims (1)

[Scope of Claims] 1. A transparent plate is characterized by having stripes or lattice-like protrusions formed from a photosensitive resin composition that is photocured and has at least a roughened side surface in the vertical and/or horizontal direction. A blackout screen that prevents reflection of external light. 2. The external light antireflection light-shielding screen according to claim 1, wherein the striped or checkered projections are dyed. 3 Striped or checkered protrusions with a height of 40~
2000μ, width 20 to 500μ, interval 20 to 1000μ, and width/interval = 1/5 to 1/1, interval/height =
The external light antireflection light-shielding screen according to claim 1, wherein the outside light reflection prevention screen has a ratio of 1/0.6 to 1/2. 4. After laminating in this order a transparent plate, a photosensitive resin composition layer containing a surface matting agent, and a transparent image carrier having a striped or lattice pattern consisting of straight lines of transparent and non-transparent parts, the transparent image carrier is laminated in this order. A method for manufacturing an external light antireflection light-shielding screen, which comprises exposing the transparent image carrier and the photosensitive resin composition containing a surface matting agent to light from the side, and then removing the unexposed areas of the photosensitive resin composition containing the surface matting agent. . 5. Claim 4, characterized in that the thickness of the photosensitive resin composition layer is 40 to 2000μ, the width of the transparent part of the transparent image carrier is 20 to 500μ, and the width of the non-transparent part is 20 to 1000μ. A method for manufacturing the external light reflection prevention light-shielding screen described in Section 1. 6. The method for manufacturing an external light antireflection light-shielding screen according to claim 4, characterized in that amorphous silica is used as the surface matting agent.