JPH0950762A - Method for forming black matrix for cathode-ray tube - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a black matrix for a cathode-ray tube with dry photolithographing with high productivity and high positioning accuracy with the simple structure. SOLUTION: A photosensitive adhesive layer is provided on the face plate surface of a cathode-ray tube, and a shadow mask or an opening pattern of an aperture grill is provided for exposure so as to lower the adhesiveness of the exposure part of the adhesive layer, and thereafter, the surface of a black matrix sheet, which is provided with a masking pigment layer, in the masking pigment layer side is overlapped with the photosensitive adhesive layer surface for adhesion. Thereafter, the black matrix sheet is peeled to form the pattern of the black matrix on the face plate surface.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a black matrix for a cathode ray tube, and more particularly to the above method for forming a black matrix on a face plate surface of a cathode ray tube easily and with high accuracy. Is.

[0002]

2. Description of the Related Art Conventionally, as a method for forming a black matrix on a face plate surface of a cathode ray tube, a so-called wet photolithographic method by slurry coating, exposure and wet development has been used. However, the device is complicated and lacks in productivity. Therefore, a method using a printing method such as a screen printing method has been proposed as an alternative method of forming a highly productive black matrix (for example, JP-B-55-46674 and JP-A-6-49398). ).

[0003]

However, the above-mentioned screen printing method has high productivity and is extremely advantageous in terms of production equipment, but it is inferior in positional accuracy as compared with the wet photolithographic method. There is a problem as a method of forming a large-sized cathode ray tube. The present invention has been made in view of the above circumstances, and an object thereof is to form a black matrix by a dry photolithographic method that provides high productivity as a method for forming a black matrix, and that is simple and has high positional accuracy. To provide a method.

[0004]

The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, as a result of the dry photolithographic method comprising a specific means, the pattern of the black matrix can be easily and highly accurately formed. The present invention has been achieved by finding out what can be obtained by.

That is, the gist of the present invention is to attach a photosensitive adhesive layer to the face plate surface of a cathode ray tube, install an opening pattern of a shadow mask or an aperture grill, and perform projection exposure to adhere the exposed portion of the adhesive layer. After reducing the adhesiveness, the surface of the black matrix sheet having the masking pigment layer provided on the surface of the photosensitive adhesive layer is adhered to the masking pigment layer side, and then the black matrix sheet is peeled off to remove the face. A method of forming a black matrix for a cathode ray tube is characterized by forming a black matrix pattern on the plate surface.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The photosensitive pressure-sensitive adhesive layer in the present invention may be one that has a photosensitivity that adheres to the face plate surface of the cathode ray tube and exhibits low or non-adhesiveness upon exposure. Usually, it contains a photopolymerizable composition as a main component. As the photopolymerizable composition, for example, an addition-polymerizable compound containing at least one ethylenically unsaturated double bond (hereinafter,
An abbreviated as ethylenic compound) and a photopolymerization initiator composed of a sensitizer and / or a sensitizing dye that absorbs ultraviolet rays or visible light are used. And the said photoinitiator may contain an activator as needed.

Further, the photosensitive pressure-sensitive adhesive layer is required to have a pressure-sensitive adhesiveness such that the concealing pigment layer of the black matrix sheet described below can be transferred onto it. By curing the compound in response to ultraviolet rays or visible light, it is possible to impart an appropriate decrease in tackiness to the exposed portion to the extent that the hiding pigment layer of the black matrix sheet is not transferred. Further, the tackiness may be adjusted by further adding an organic polymer substance to the photopolymerizable composition.

The ethylenic compound and the above organic polymer substance are not particularly limited, but for example, JP-A-2-69, JP-A-51-150322, JP-A-55-26597, JP-A-55-26596
Those described in various publications such as Japanese publication can be appropriately used.

Examples of the above ethylenic compound include unsaturated carboxylic acids; esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids; unsaturated carboxylic acids. And an ester obtained by the esterification reaction of a polyvalent carboxylic acid and a polyvalent hydroxy compound (such as the above-mentioned aliphatic polyhydroxy compound and aromatic polyhydroxy compound).

The ethylenic compound has a viscosity of 100.
Those of 0 cps (25 ° C.) or less are particularly preferable. If the viscosity of the ethylenic compound is too high, the tackiness of the photosensitive pressure-sensitive adhesive layer may decrease, and transfer failure to the pressure-sensitive adhesive portion of the color material layer may occur. Examples of such ethylenic compounds include (meth) acrylates such as ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolethane tri (meth) acrylate. Examples include ethylenic compounds.

On the other hand, examples of the above organic polymer substances include (meth) acrylic acid copolymers, alkyl (meth) acrylate copolymers, itaconic acid copolymers, partially esterified maleic acid copolymers, Cellulose modified product, polyethylene oxide, polyvinylpyrrolidone, polyvinyl alcohol, vinyl chloride copolymer, vinylidene chloride copolymer, styrene copolymer, vinyl acetate copolymer, polyamide (including soluble nylon), polyurethane, polyvinyl butyral, polyester Etc. can be appropriately selected and used. As the organic polymer substance, one having a glass transition point of 80 ° C. or lower is particularly preferable.

The photopolymerization initiator is not particularly limited, but examples thereof include a system of hexaarylbiimidazole and an activator and a dye (Japanese Patent Publication No. 45-37377), hexaarylbiimidazole and (p-dialkylaminobenzylidene). ) Ketone systems (JP-A 47-2528, JP-A 54-155292), cyclic cis-α
A system of a dicarbonyl compound and a dye (JP-A-48-841)
No. 83), a system of substituted triazine and merocyanine dye (JP-A-54-151024), a system of ketocoumarin and an activator (JP-A-52-112681, JP-A-58-15503). JP-A-60-88005) and the like.

Further, a system of a substituted triazine and a sensitizer (Japanese Patent Laid-Open Nos. 58-29803 and 59-40302).
System), a system of biimidazole, a styrene derivative and a thiol (JP-A-59-56403), a system of organic peroxide and a dye (JP-A-59-140203, JP-A-59-189340). ), A system of a tetrahydroquinoline sensitizer and an activator (JP-A-2-69), and the like.

The photopolymerization initiator is appropriately selected from the above combinations according to the wavelength of the exposure light source and is used. Particularly, the biimidazole described in JP-A-2-69, The thiol and tetrahydroquinoline system is preferred. The addition amount of the activator is usually 1 to 100 parts by weight with respect to 1 part by weight of the sensitizer or the sensitizing dye.

With respect to 100 parts by weight of the ethylenic compound,
The addition amount of the organic polymer substance is usually 1 to 500 parts by weight, preferably 10 to 300 parts by weight, and the addition amount of the photopolymerization initiator is usually 0.1 to 100 parts by weight, preferably 0.2 to 5 parts by weight.
0 parts by weight.

The above-mentioned photosensitive pressure-sensitive adhesive layer is attached to the face plate surface by dissolving the above-mentioned photopolymerizable composition in a solvent to prepare a photosensitive pressure-sensitive adhesive layer coating solution, and using a generally used spin coating method. It can be done easily by adopting it. After the attachment, the temperature may be 50 to 200 ° C. and the time may be 1 to 30 minutes for drying.

As a solvent for the above coating liquid, toluene,
Aromatic solvents such as xylene, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexanone, methyl lactate, ethyl acetate, ester solvents such as butyl acetate, isopropyl alcohol, butanol, alcohol solvents such as methyl cellosolve, trichloroethylene, Halogen-based solvent such as chlorobenzene, dioxane,
Examples include ether solvents such as tetrahydrofuran, and the like, which may be used alone or in combination of two or more kinds. The photopolymerizable composition in the coating solution is generally preferably in the range of 5 to 50% by weight in terms of coatability, and
The thickness of the photosensitive adhesive layer after drying is usually 0.1 to 50 μm.
m, preferably 0.2 to 10 μm. If the photosensitive pressure-sensitive adhesive layer is too thin, uniform adhesiveness cannot be obtained, and if it is too thick, problems such as peeling tend to occur during the final baking process.

The black matrix sheet used in the present invention has a hiding pigment layer provided on the support surface. The support is not particularly limited as long as it can hold the masking pigment layer, and examples thereof include polyethylene terephthalate, polyethylene, polypropylene, polymethylmethacrylate, polyvinyl chloride, polyvinylidene chloride, polystyrene, nylon, cellulose triacetate and the like. Examples of the polymer sheet include, but a polyethylene terephthalate sheet is particularly preferable. The thickness of the support is usually 1 μm to 10 mm, preferably 5 μm to 1 mm.

The masking pigment layer provided on the support surface comprises a masking pigment and a binder resin, and the weight ratio of the binder resin to the pigment is usually 0.01: 1 to 2: 1, preferably 0.1 :. 1 to 1: 1. As the hiding pigment,
Black pigments such as graphite, carbon black and ruthenium oxide and metallic pigments such as Ni, Cu, Al, Ag and Au are used. The particle size of the hiding pigment is preferably 10 μm or less in order to obtain a sufficient hiding property. A particularly preferable hiding pigment is electroconductive fine particle graphite having a particle size of several μm to 0.1 μm.

The binder resin is not particularly limited, but thermoplastic resins such as vinyl acetate copolymers, polyvinyl butyral resins, ethylene-vinyl acetate copolymers, polyester resins, acrylic resins, Polyamide resin, urethane resin, etc. are used.

The masking pigment layer is obtained by applying a coating liquid containing a pigment and a binder resin on a support and then drying the coating liquid, and the thickness thereof is usually 0.2 μm to 20 μm.
It is preferably 0.5 μm to 5 μm. As the solvent for preparing the coating liquid, the above-mentioned respective solvents can be used.

In order to form a black matrix pattern on the face plate surface for a cathode ray tube provided with the above-mentioned photosensitive adhesive layer, first, a shadow corresponding to a desired position is formed on the face plate surface provided with the photosensitive adhesive layer. Install a mask or aperture grille opening pattern,
A mask pattern or an opening pattern is projected and exposed by an ultraviolet exposure device. At this time, an appropriate exposure amount is about 5 mJ / cm ² with a high pressure mercury lamp.

Then, the surface of the black matrix sheet on the side of the masking pigment layer is overlaid on the surface of the exposed face plate on the side of the photosensitive adhesive layer, and the pressure is 1 to 10 kg / cm.
^2. After pressing and adhering under the conditions of a temperature of 50 ° C. to 120 ° C. and a time of 1 to 20 minutes, the black matrix sheet is peeled off. As a result, the masking pigment layer remains only on the unexposed portion (that is, the portion where the tackiness remains) on the face plate surface, and the black matrix pattern is easily and highly accurately formed on the face plate surface.

[0024]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Example 1 (1) Preparation of coating liquid for photosensitive pressure-sensitive adhesive layer: A coating liquid for photosensitive pressure-sensitive adhesive layer was prepared by mixing and dissolving the respective raw materials shown in Table 1 below.

[0026]

<Table 1> <Photosensitive adhesive layer coating liquid> Solvent: Methyl ethyl ketone / tetrahydrofuran 50 parts by weight (4: 1 by weight) Ethylenic compound: Trimethylolpropane triacrylate 7 parts by weight Organic polymer substance: Copolymer- 13 parts by weight Activator (1): 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 2 parts by weight Activator (2): 2-mercaptobenzthiazole 0.5 parts by weight Sensitizing dye: 0.1 part by weight of the compound of the following formula [1]

[0027]

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(2) Synthesis of Copolymer-1: 3 parts by weight of a monomer mixture having the composition shown in Table 2 below, 0.6 part by weight of a surfactant ("Newcol 516" manufactured by Nippon Emulsifier Co., Ltd.), and 30 parts by weight of water was stirred under a nitrogen atmosphere to prepare an emulsion solution. Then potassium persulfate 0.0
09 parts by weight and 0.009 parts by weight of sodium sulfite are added to the emulsion solution and heated at 70 ° C. for 30 minutes,
Next, 12 parts by weight of the monomer mixture having the composition shown in Table 2,
0.081 parts by weight of potassium persulfate and 0.081 parts by weight of sodium sulfite were dropped, and the mixture was heated and polymerized at 70 ° C. for 1 hour to obtain an emulsion polymer. The obtained emulsion polymer was coagulated and precipitated with methanol, and the precipitate was washed to produce a copolymer-1. The glass transition point of copolymer-1 was 40 ° C.

[0029]

<Table 2> <Monomer mixture> (Molar ratio) Methyl methacrylate (MMA) 25 iso-butyl methacrylate (iso-BMA) 30 Methacrylic acid (MAA) 20 iso-butylacrylic acid (iso-BA) 154 -Hydroxybutyl acrylate (4HBA) 5

(3) Attaching to face plate: The coating solution for the photosensitive adhesive layer obtained in the above (1) was applied by a spin coater to a dry film thickness of 2 μm on the face plate of a 25-inch cathode ray tube. After applying, 5 at 100 ℃
The face plate was provided with a photosensitive adhesive layer by drying for a minute.

(4) Preparation of coating liquid for hiding pigment layer: A mixture having the composition shown in Table 3 below was mixed with glass beads (diameter: 1 m).
m) and a dispersion mill with a rotating disk, 3000
A coating liquid for a hiding pigment layer was prepared by performing a dispersion treatment for 1.5 hours at rpm.

[0032]

[Table 3] Organic polymer substance: polyvinyl acetate-vinyl versatate 10 g (80:20 weight ratio, weight average molecular weight 60,000) Solvent: methyl lactate / methyl ethyl ketone / tetrahydrofuran (2: 2: 1 weight ratio) 100 g concealment Pigment: Graphite powder (Hitasol GP-60S manufactured by Hitachi Powdered Metals Co., Ltd.) 10 g

(5) Preparation of black matrix sheet: The coating liquid for hiding pigment layer obtained in (4) above was dried to a thickness of 5 μm on the surface of a biaxially stretched polyethylene terephthalate sheet having a thickness of 25 μm. And then dry it,
A black matrix sheet was prepared.

(6) Formation of black matrix pattern: A shadow mask is placed on the face plate surface provided with the photosensitive adhesive layer obtained in (3) above, and the pattern of the shadow mask is projected and exposed by an ultraviolet exposure device. did. On the face plate surface that has been exposed,
The black matrix sheet obtained in 1 above was superposed so that the surface on the side of the concealing pigment layer was in contact with each other, and pressure-adhered for 2 minutes under the conditions of a pressure of 5 kg / cm ² and a temperature of 80 ° C. Then, the sheet was peeled off to form a black matrix pattern on the face plate surface. The pattern of the black matrix was extremely accurate and uniform.

[0035]

According to the present invention described above, a uniform black matrix pattern can be easily formed with high accuracy. Furthermore, after attaching the fluorescent film,
An organic material such as a binder resin can be easily baked, and a high quality cathode ray tube can be formed.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Uchida 1060 Narita, Odawara-shi, Kanagawa Kasei Optonix Co., Ltd. Odawara Plant (72) Inventor Masaru Ohno 6-735 Kita-Shinagawa, Shinagawa-ku, Tokyo Sony Incorporated (72) Inventor Yu Ihara 6-35 Kitashinagawa, Shinagawa-ku, Tokyo Sony Corporation

Claims (1)

[Claims] 1. After the photosensitive adhesive layer is attached to the face plate surface of the cathode ray tube and the opening pattern of a shadow mask or an aperture grill is installed and projection exposure is performed to reduce the adhesiveness of the exposed portion of the adhesive layer. The surface of the black matrix sheet provided with the masking pigment layer on the surface of the photosensitive adhesive layer is closely adhered by overlapping, and then the black matrix sheet is peeled off to form a black matrix on the face plate surface. A method for forming a black matrix for a cathode ray tube, which comprises forming a pattern.