JPH0950761A - Method for forming color filter for color cathode-ray tube, and photosensitive adhesive pigment sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a color filter for a color cathode-ray tube with dry developing with high productivity and high accuracy with a simple device, and to provide a photosensitive adhesive pigment sheet for this method. SOLUTION: The surface of a photosensitive adhesive pigment sheet at the photosensitive adhesive pigment layer side is adhered to the face plate surface of a cathode-ray tube, and a shadow mask or an opening pattern of an aperture grill for exposure is provided for exposure so as to lower the adhesiveness of the exposure part, and thereafter, the photosensitive adhesive pigment sheet is peeled so as to form the pattern of the pigment on the face plate surface. This photosensitive adhesive pigment sheet is formed by providing a photosensitive adhesive pigment layer, which includes the ethylenic compound and the polymerization initiator and the pigment, in a support 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 color filter for a color cathode ray tube, and more particularly, to the above-mentioned forming method capable of easily and highly accurately forming a color filter on a face plate surface of a cathode ray tube. The present invention relates to a photosensitive pressure sensitive adhesive pigment sheet used for the formation.

[0002]

2. Description of the Related Art Recently, in order to improve the contrast of a color cathode ray tube, as a method for selectively suppressing reflection of external light, a pigment layer corresponding to each color, namely It has been announced that the method of providing a color filter is effective. For example, Japanese Patent Laid-Open No. 5-2
No. 75008, Technical Bulletin EID93-102 (19)
94-01), page 17. Then, as a method of forming the color filter, similar to the conventional method of forming a fluorescent film on the face plate surface of the cathode ray tube,
The so-called wet photolithographic method is used, which involves slurry coating, exposure and wet development.

[0003]

However, the wet photolithography method has a drawback that the number of steps is extremely large when the step of forming the fluorescent film is included, and the apparatus is complicated and diversified, resulting in lack of productivity. The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for forming a color filter by a dry developing method which has a simple apparatus, high productivity, and high accuracy.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to achieve the above-mentioned object, and as a result, the dry-developing method comprising a specific means makes it possible to easily and accurately form a color filter pattern. The inventors have found what is obtained and have reached the present invention.

That is, the first gist of the present invention is that the face of the cathode ray tube on the side of the photosensitive adhesive pigment layer of the photosensitive adhesive pigment sheet is brought into close contact with the face plate surface of the cathode ray tube and the opening pattern of the shadow mask or aperture grill is installed. A method for forming a color filter for a color cathode ray tube, characterized by forming a pigment pattern on the face plate surface by peeling off the photosensitive adhesive pigment sheet after the adhesiveness of the exposed portion is reduced by projecting and exposing And a second aspect of the present invention comprises a compound having at least one ethylenically unsaturated double bond, a sensitizer and / or a sensitizing dye on the surface of the support and, if necessary, A color fill for a color cathode ray tube, characterized by being provided with a photosensitive adhesive pigment layer containing a photopolymerization initiator containing an activator and a pigment. It consists in the photosensitive adhesive pigment sheet used to form the over.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The photosensitive adhesive pigment sheet used in the present invention comprises a support and a photosensitive adhesive pigment layer. The support is not particularly limited, and examples thereof include polyethylene terephthalate, polyethylene, polypropylene, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polystyrene, nylon, and polymer sheets such as cellulose acetate. 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 photosensitive adhesive pigment layer contains a photopolymerizable composition and a pigment as main components. As the photopolymerizable composition,
For example, a light comprising an addition-polymerizable compound containing at least one ethylenically unsaturated double bond (hereinafter abbreviated as an ethylenic compound) and a sensitizer and / or sensitizing dye that absorbs ultraviolet rays or visible light. Those containing a polymerization initiator are used. And the said photoinitiator may contain an activator as needed.

Examples of the ethylenic compound include various compounds known as radiation-curable compounds having an acryloyl group or a methacryloyl group, and specific examples thereof include dipentaerythritol hexa (meth) acrylate and trimethylol. Propane tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, epoxy acrylate, urethane acrylate, polyester acrylate, triethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, etc. (Meth) acrylate-based ethylenic compounds of N-vinylpyrrolidone may also be used.

In addition to the photopolymerizable composition and the pigment, an adhesive agent such as an organic polymer or a plasticizer may be added to the photosensitive adhesive pigment layer for the purpose of adjusting the adhesiveness. Good. Examples of the organic polymer substance include (meth) acrylic acid copolymers, (meth) acrylic acid alkyl copolymers,
Itaconic acid copolymer, partially esterified maleic acid copolymer, 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 and the like can be appropriately selected and used. In particular, an organic polymer substance having a glass transition point of 80 ° C. or lower is preferably used. On the other hand, as the plasticizer, a normal ester plasticizer such as a phthalic acid dialkyl ester type, an adipic acid dialkyl ester type, or a trimellitic acid trialkyl ester type is preferably used.

The photopolymerization initiator is not particularly limited, but examples thereof include hexaarylbiimidazole, activator and dye system (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 No. 58-29803, Japanese Laid-Open Patent Publication No. 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 depending on the wavelength of the exposure light source and is used. Particularly, the tetrahydroquinoline-based photopolymerization initiator described in JP-A-2-69 is used. A sensitizer, biimidazole and thiol 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 pigment is not particularly limited as long as it has been conventionally used for a color filter of a fluorescent film, but as the red pigment, red iron oxide,
For blue pigments such as red lead, silver vermilion, and cadmium red,
Green pigments such as navy blue, cobalt blue, cerulean blue, kuresu and ultramarine blue are chrome green, zinc green, chrome oxide, viridian, emerald green,
Examples include cobalt green. The particle size of the pigment is
The range of 0.01 to 1 μm is preferable, and the proportion of the pigment in the photosensitive pressure-sensitive adhesive pigment layer is usually 10 to 70% by weight, preferably 20 to 50% by weight.

The photosensitive pressure-sensitive adhesive pigment layer is prepared by preparing a coating solution for the photosensitive pressure-sensitive adhesive pigment layer from the above-mentioned components and a suitable solvent, applying it on the surface of the support according to a usual coating method, and then drying it. can get. As a coating method, for example, a method using a reverse roll coater, a die coater, a gravure printing machine, etc. (see Yuji Harazaki, "Coating Method", Maki Shoten, 1979 issue). As the solvent of the coating solution, 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,
Examples thereof include alcohol solvents such as isopropyl alcohol, butanol and methyl cellosolve, halogen solvents such as trichloroethylene and chlorobenzene, ether solvents such as dioxane and tetrahydrofuran, which may be used alone or in combination of two or more. You may use it.
The total concentration of each of the above components in the coating liquid is usually preferably 5 to 50% by weight from the viewpoint of coatability. The thickness of the photosensitive adhesive pigment layer is preferably in the range of 1 μm to 10 μm. In addition,
A release layer may be provided between the support and the photosensitive adhesive pigment layer for the purpose of improving transferability. As the release layer, a generally known release agent is used, and waxes or silicone resins are used.

In order to form a pigment layer pattern on the face plate surface of a cathode ray tube using a photosensitive adhesive pigment sheet, first, a photosensitive adhesive pigment sheet is formed on the face plate surface provided with a black matrix by a conventional method. Layered so that the surface of the photosensitive pressure sensitive adhesive pigment layer side is in contact, pressure 1 to 10 kg
/ Cm ² , temperature 50 to 120 ° C., pressure and contact for 1 to 20 minutes, and then a shadow mask or aperture grille opening pattern corresponding to a desired position is set, and an ultraviolet exposure device is used for masking. Pattern exposure or aperture pattern is projected and exposed. The exposure dose at this time is
A high pressure mercury lamp of about 5 mJ / cm ² is suitable. Then, the photosensitive adhesive pigment sheet is peeled off. As a result, the pigment layer remains only on the unexposed portion (that is, the portion where the adhesiveness remains) on the face plate surface, and the pattern of the pigment layer is easily and highly accurately formed on the face plate surface.

[0017]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.

Example 1 (1) Preparation of Photosensitive Adhesive Pigment Sheet: (1-1) Red Photosensitive Adhesive Pigment Sheet: 25 μm thick biaxially stretched polyethylene terephthalate sheet having the composition shown in Table 1 below. The coating liquid for the photosensitive adhesive pigment layer was applied so that the dry film thickness was 2 μm, and then dried at 100 ° C. to prepare a red photosensitive adhesive pigment sheet.

[0019]

[Table 1] <Coating liquid for photosensitive adhesive pigment layer> Solvent: Methyl ethyl ketone / tetrahydrofuran 50 parts by weight (4: 1 by weight) Ethylenic compound: Trimethylolpropane triacrylate 7 parts by weight Organic polymer: Copolymer -1 3 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: Compound of the following formula [1] 0.1 part by weight Red pigment: Bengara 3 parts by weight

[0020]

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The method for synthesizing the copolymer-1 was performed as follows. First, 3 parts by weight of the monomer mixture liquid shown in Table 2 and a surfactant (“Newcol 51” manufactured by Nippon Emulsifier Co., Ltd.)
6 ") 0.6 part by weight and 30 parts by weight of water were stirred under a nitrogen atmosphere to prepare an emulsion solution. Then, 0.009 parts by weight of potassium persulfate and 0.009 parts by weight of sodium sulfite are added to the above emulsion solution,
Heat at 70 ° C. for 30 minutes, then 2 parts by weight of an aqueous solution containing 12 parts by weight of the monomer mixture of Table 2 and 0.081 parts by weight of potassium persulfate and 0.08 parts of sodium sulfite.
2 parts by weight of an aqueous solution containing 1 part by weight was added dropwise at 70 ° C. for 2 hours and further stirred at 70 ° C. for 2 hours to obtain an emulsion polymer. The obtained emulsion polymer was coagulated and precipitated with methanol, and this precipitate was washed to prepare a copolymer-1. The glass transition point of copolymer-1 is 40 ° C.
Met.

[0022]

<Table 2> <Monomer mixture> (molar ratio) Methyl methacrylate (MMA) 25 iso-butyl methacrylate (iso-BMA) 30 Methacrylic acid (MA) 20 iso-butyl acrylate (iso-BA) 15 4- Hydroxybutyl acrylate (4HBA) 5

(1-2) Blue photosensitive pressure-sensitive adhesive pigment sheet: A blue photosensitive pressure-sensitive adhesive pigment sheet is prepared by the same procedure as above except that cobalt aluminate, which is a blue pigment, is used in place of the red pigment shown in Table 1. Got

(1-3) Green photosensitive adhesive pigment sheet: TiO ₂ .Z which is a green pigment instead of the red pigment shown in Table 1.
A green photosensitive pressure-sensitive adhesive pigment sheet was obtained by the same procedure as above except that the nO / CoO / NiO-based composite oxide was used.

(2) Formation of color filter: The red light-sensitive adhesive pigment sheet obtained as described above was applied to the photosensitive adhesive pigment layer side on the face plate surface of a 14-inch color cathode ray tube provided with a black matrix by a conventional method. Were stacked so that the surfaces of them contacted each other, and they were brought into pressure contact with each other at a pressure of 5 kg / cm ² and a temperature of 80 ° C. for 2 minutes. Then, using a corresponding shadow mask, it was exposed to ultraviolet light at room temperature. Then, the exposed sheet was peeled off to obtain a pattern of the red pigment layer.

Further, the blue and green photosensitive adhesive pigment sheets obtained above are brought into close contact with the face plate surface in order, and the position of the exposure light source is shifted to the positions corresponding to the positions where the blue and green picture elements are provided, respectively. UV exposure was performed using a shadow mask, and then peeling was performed to obtain a face plate provided with red, blue and green color filters. The pattern of the pigment layer was extremely accurate.

[0027]

According to the present invention described above, the face of the cathode ray tube on the side of the photosensitive adhesive pigment layer of the photosensitive adhesive pigment sheet is brought into close contact with the face plate surface of the cathode ray tube, and the opening pattern of the shadow mask or aperture grill is installed. Then, the pattern of the pigment layer can be easily and highly accurately formed with high productivity by the dry developing method which comprises a simple operation of peeling the photosensitive adhesive pigment sheet after projection exposure.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location H01J 29/89 H01J 29/89 (72) Inventor Hiroshi Uchida 1060 Narita, Odawara-shi, Kanagawa Kasei Optonix Co., Ltd. Odawara Inside the factory (72) Inventor Satoshi Ohno 6-735 Kitashinagawa, Shinagawa-ku, Tokyo Sony Corporation (72) Inventor Yu Ihara 6-35 Kitashinagawa, Shinagawa-ku, Tokyo Sony Corporation

Claims (2)

[Claims] 1. A surface of a cathode ray tube of a cathode ray tube is adhered to a surface of a photosensitive adhesive pigment sheet on the side of the photosensitive adhesive pigment layer, an opening pattern of a shadow mask or an aperture grill is installed, and projection exposure is performed to expose the exposed portion. A method for forming a color filter for a color cathode ray tube, which comprises forming a pigment pattern on the face plate surface by peeling the photosensitive adhesive pigment sheet after reducing the adhesiveness. 2. A photopolymerization initiator comprising a compound containing at least one ethylenically unsaturated double bond, a sensitizer and / or a sensitizing dye on the surface of the support and optionally containing an activator, and A photosensitive pressure-sensitive adhesive pigment sheet for use in forming a color filter for a color cathode ray tube, characterized by comprising a photosensitive pressure-sensitive adhesive pigment layer containing a pigment.