JPH11114481A - Transfer sheet for phosphor layer formation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily form a phosphor layer at high precision on a back plate of a plasma display panel, in which barrier walls are formed, by forming a peeling layer on a base film in a manner the layer can be peeled and forming a photosensitive resin layer containing a phosphor on the peeling layer. SOLUTION: This transfer sheet 1 comprises a base film 2 manufactured by uniaxially or biaxially stretching a film of a resin material such as a polyethylene film, an ethylene-vinyl acetate copolymer film, an ethylene-vinyl alcohol copolymer film, etc., and coated with a peeling layer 3 containing water-soluble resin as a main component by gravure coating in a manner the peeling layer can be peeled. A photosensitive resin layer 4 is formed by applying a photosensitive resin composition containing a phosphor to the peeling layer 3 by a slit die coating method and drying the composition and a protective film 5 is put on the photosensitive resin layer 4. Consequently, a phosphor layer can be formed at high precision.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a transfer sheet for forming a phosphor layer, and more particularly to a transfer sheet for forming a phosphor layer for forming a phosphor layer of a plasma display panel with high accuracy.

[0002]

2. Description of the Related Art In recent years, plasma display panels (P
In DP), it is required that the formation of fine patterns and barriers such as electrodes and dielectrics can be performed with higher accuracy and at a lower manufacturing cost. Along with this,
For the phosphor layer formed so as to cover the wall surface of the barrier and the bottom surface of the cell, an easier and more accurate forming means is desired.

Conventionally, a red light-emitting phosphor layer, a green light-emitting phosphor layer, and a blue light-emitting phosphor layer are formed in a predetermined pattern on a back panel for a PDP having a barrier formed thereon. There is a method using a transfer sheet in which a photosensitive resin layer containing a phosphor is formed on a base film so as to be peelable. In this method, the photosensitive resin layer of the transfer sheet is pressed against the barrier side of the back plate, exposed in a pattern from the base film side via a mask, and then the base film is peeled off from the back plate, thereby exposing the exposed portion. By transferring only the photosensitive resin layer to a desired position covering the wall surface of the barrier of the back plate and the bottom surface of the cell, repeating this operation for the required number of colors, baking to remove the resin component, A phosphor layer composed of a phosphor pattern of a color is provided.

[0004]

However, the conventional transfer sheet used in the above-described method is difficult to perform in the operation of transferring the second color photosensitive resin layer onto the back plate on which the first color photosensitive resin layer has already been transferred. When the base film is peeled off from the back plate, part or all of the first color photosensitive resin layer adheres to the base film and is peeled off, or an unexposed portion of the second color photosensitive resin layer is removed. However, there is a problem that the abnormal transfer is performed by adhering to the photosensitive resin layer of the first color. This problem is the same in the operation of transferring the third color photosensitive resin layer onto the back plate on which the first color and second color photosensitive resin layers have already been transferred.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described circumstances, and has been developed in view of the above circumstances. An object of the present invention is to provide a transfer sheet for forming a body layer.

[0006]

In order to achieve the above object, the present invention provides a base film, a release layer provided on the base film so as to be peelable, and a fluorescent film provided on the release layer. And a photosensitive resin layer containing a body.

Further, in the present invention, the release layer is constituted so that a water-soluble resin is a main component.

Further, the present invention is configured such that the water-soluble resin is hardly soluble or insoluble in methyl alcohol, ethyl alcohol and isopropyl alcohol.

The present invention further comprises a primer layer between the release layer and the photosensitive resin layer, wherein the primer layer mainly comprises a resin soluble in at least one of methyl alcohol, ethyl alcohol and isopropyl alcohol. It was configured to be a component.

Further, the present invention is configured such that the water-soluble resin contained in the release layer is mainly composed of polyvinyl alcohol.

In the present invention as described above, the release layer transferred to the back plate for the plasma display panel together with the photosensitive resin layer is brought into contact in the subsequent transfer operation of the other color photosensitive resin layer. It exerts a peeling action on the layer and prevents adhesion of photosensitive resin layers of different colors.

[0012]

Embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a schematic sectional view showing one embodiment of a transfer sheet for forming a phosphor layer of the present invention. In FIG. 1, a transfer sheet 1 for forming a phosphor layer has a photosensitive resin layer 4 formed on a base film 2 via a release layer 3, and includes a protective film 5 on the photosensitive resin layer 4. is there. The release layer 3 is formed so as to be peelable from the base film 2.

[0014] Such a transfer sheet 1 for forming a phosphor layer.
May be in the form of a sheet or a long sheet. In the case of the long sheet, the sheet may be in the form of a roll wound around a core. The core used is preferably a core formed of ABS resin, vinyl chloride resin, bakelite or the like in order to prevent generation of dust and paper dust.

Next, the structure of the transfer sheet 1 for forming a phosphor layer will be described. Base Film The base film 2 constituting the transfer sheet 1 for forming a phosphor layer of the present invention must be made of a material which has flexibility and does not cause significant deformation by tension or pressure.
Further, since the photosensitive resin layer 4 is exposed in a transfer step described later, it is necessary to use a material having light transmittance.

Specific examples of the base film include a polyethylene film, an ethylene-vinyl acetate copolymer film, an ethylene-vinyl alcohol copolymer film, a polypropylene film, a polystyrene film, a polymethacrylic acid film, a polyvinyl chloride film, and a polyvinyl alcohol film. , Polyvinyl butyral film, nylon film, polyetheretherketone film, polysulfone film, polyethersulfone film, polytetrafluoroethylene-perfluoroalkylvinylether film, polyvinyl fluoride film, tetrafluoroethylene-ethylene film, tetrafluoroethylene- Hexafluoropropylene film, polychlorotrifluoroethylene film, polyvinyl Denfluoride film, polyethylene terephthalate film, polyethylene naphthalate film, polyester film, cellulose triacetate film, polycarbonate film, polyurethane film, polyimide film, polyetherimide film, films containing fillers in these resin materials, these resins A uniaxially or biaxially stretched film made of a material, a biaxially stretched film using these resin materials and a stretching ratio in the width direction higher than the flow direction, and a flow from the width direction using these resin materials Biaxially stretched film with a higher stretching ratio in the direction, a film obtained by laminating the same or different kinds of films among these films,
And a composite film formed by co-extruding the same or different resin selected from the raw resin used for these films.

Among the above films, it is particularly preferable to use a biaxially stretched polyester film. Release layer The release layer in the transfer sheet for forming a phosphor layer of the present invention is formed so as to be peelable from the base film as described above, and transfers the photosensitive resin layer formed on the release layer. At this time, the release layer itself is also released from the base film. Such a release layer is formed from a non-water-soluble resin and a water-soluble resin having appropriate adhesion and release properties to the base film, and is volatilized and decomposed by baking to form a carbide in the phosphor layer or on the surface of the phosphor layer. Can be appropriately selected without leaving any of them.

Examples of the water-insoluble resin include polymethylpentene, polypropylene, acrylic resin, linear polyester, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyvinyl acetal, polyvinyl acetate, nitrocellulose, and cellulose acetate butyrate. Etc. can be used.

When the photosensitive resin layer 4 is made of a water-insoluble material, the release layer 3 can be formed mainly of a water-soluble resin. Here, the water-soluble resin in the present invention indicates a resin that dissolves at least 1 g in 100 g of water or hot water. Further, the main component in the present invention,
The component occupying 50% by weight or more of the total resin component of the release layer 3 is indicated. Examples of the water-soluble resin include polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral, polyvinyl formal, polyvinyl pyrrolidone, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl ethyl cellulose, ethyl hydroxyethyl cellulose, and the like. Can be used alone or as a mixture of two or more.

When a water-insoluble photocurable low molecular weight compound such as acrylate monomer is blended as a binder for the photosensitive resin layer 4, it is difficult to use methyl alcohol, ethyl alcohol and isopropyl alcohol as the water-soluble resin. Resins that are soluble or insoluble can be used. Examples of such a water-soluble resin include polyvinyl alcohol, particularly polyvinyl alcohol having a saponification degree of 50 or more. Here, the hardly-soluble resin in the present invention means that the amount dissolved in 100 g of the solvent is 1
Indicates resin that is less than g. By using the water-soluble resin as described above, the softening temperature and cohesive force of the release layer 3,
The adhesive force to the photosensitive resin layer 4, the adhesive force to the base film 2, and the peeling force become stable.

The release layer 3 is formed on the base film 2 by dissolving the above-mentioned water-insoluble resin or a water-soluble resin to which an additive is added as necessary, in a suitable organic solvent or water. Or a dispersion prepared by dissolving in a mixed solvent of organic solvent and water, or dispersing in an organic solvent or water, and applying this to gravure direct coating, gravure reverse coating, reverse roll coating, or slide die coating. It can be carried out by applying and drying on the base film 2 by a known application means such as a coating method, a slit die coating method, and a comma coating method. When the slide die coating method is used, the release layer 3 and the photosensitive resin layer 4 can be formed simultaneously.

The thickness of the release layer 3 can be set in the range of 0.05 to 5 μm, preferably 0.1 to 2 μm.
If the thickness of the release layer 3 is less than 0.05 μm, the film strength required for the release layer cannot be obtained, and if it exceeds 5 μm, the uniformity of the surface of the release layer may decrease, which is not preferable. .

In order to further improve the film-cutting property in the peeling of the base film after the exposure operation to be described later, a microcrystalline wax, carnauba wax, paraffin wax, Fischer-Tropsch wax, various low molecular weight polyethylene, wood Wax, beeswax, whale wax, Ibota wax, wool wax, shellac wax, candelilla wax, petrolactam, partially modified wax, waxes such as fatty acid esters, fatty acid amides, silicone waxes, one kind of polystyrene, polyester, polyurethane and the like or 0.5 to 20% by weight of two or more
May be contained in the range. Photosensitive resin layer The photosensitive resin layer 4 is formed by coating a photosensitive resin composition containing at least a curable binder, a non-curable binder, a photopolymerization initiator, and a phosphor on the release layer 3 by a direct gravure coating method, a gravure reverse It can be formed by coating and drying by known coating means such as a coating method, a reverse roll coating method, a slide die coating method, a slit die coating method, and a comma coating method. Further, after coating and forming on the protective film 5, the base film 2 having the release layer 3 formed thereon may be overlaid and pressed.

The curable binder, the non-curable binder and the photopolymerization initiator constituting the photosensitive resin layer 4 are as follows:
A material that does not volatilize and decompose by firing and does not leave carbide in the phosphor layer is used. (1) Curable binder As the curable binder, a compound having at least one polymerizable carbon-carbon unsaturated bond can be used. Specifically, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl Acrylate, isobonyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, ethylene glycol diacrylate,
Diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,3-propanediol acrylate, 1,4-
Cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene glycol diacrylate,
Glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyl trimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-
Butanetriol triacrylate, 2,2,4-trimethyl-1,3-pentanediol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, dipentaerythritol hexaacrylate, and the above acrylate group as a methacrylate group Γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, 2-hydroxyethylacryloyl phosphate, tetrahydrofurfuryl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, 3-butane Diol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, hydroxypivalic acid ester neopentyl glycol dia Acrylate, phenol-ethylene oxide modified acrylate, phenol-propylene oxide modified acrylate, N-vinyl-2-pyrrolidone, bisphenol A-ethylene oxide modified diacrylate, pentaerythritol diacrylate monostearate, tetraethylene glycol diacrylate, polypropylene glycol diacrylate Acrylates, acrylate monomers such as trimethylolpropane propylene oxide modified triacrylate, isocyanuric acid ethylene oxide modified triacrylate, trimethylolpropane ethylene oxide modified triacrylate, pentaerythritol pentaacrylate, pentaerythritol hexaacrylate, pentaerythritol tetraacrylate, and , These Acrylate groups in which acrylate groups are substituted with methacrylate groups, urethane acrylate oligomers in which acrylate groups are bonded to oligomers having a polyurethane structure, polyester acrylate oligomers in which acrylate groups are bonded to oligomers having a polyester structure, and acrylate groups in oligomers having epoxy groups A methacrylate group is bonded to an epoxy acrylate oligomer having a methacrylate group bonded to an epoxy acrylate oligomer having a methacrylate group bonded to an oligomer having a polyurethane structure, a polyester methacrylate oligomer having a methacrylate group bonded to an oligomer having a polyester structure, or an oligomer having an epoxy group. Epoxy methacrylate oligomer, polyurethane acrylate having an acrylate group, Polyester acrylates having acrylate group, an epoxy acrylate resin having an acrylate group, a polyurethane methacrylate having a methacrylate group, a polyester methacrylate having a methacrylate group, an epoxy methacrylate resins having a methacrylate group.

These are examples of curable binders that can be used, and the present invention is not limited to these. Further, the content of such a curable binder is preferably in the range of 20 to 80% by weight based on the total solid content of the photosensitive resin composition. (2) Non-curable binder Examples of the non-curable binder include ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethylene vinyl copolymer, polystyrene, acrylonitrile-styrene copolymer, ABS resin, and polymethacryl. Acid resin, ethylene methacrylic acid resin, polyvinyl chloride resin, chlorinated vinyl chloride, polyvinyl alcohol, cellulose acetate propionate, cellulose acetate butyrate,
Nylon 6, nylon 66, nylon 12, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl acetal, polyether ether ketone, polyether sulfone, polyphenylene sulfide, polyarylate, polyvinyl butyral, epoxy resin, phenoxy resin, polyimide resin,
Polyamide imide resin, polyamic acid resin, polyether imide resin, phenol resin, urea resin and the like, and polymerizable monomers methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, Isopropyl acrylate, isopropyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert
-Butyl methacrylate, n-pentyl acrylate,
n-pentyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n
-Octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, styrene, α-methylstyrene, N-vinyl-2-
One or more of pyrrolidone, acrylic acid, methacrylic acid,
Acrylic acid dimer (for example, M manufactured by Toa Gosei Chemical Co., Ltd.)
-5600), itaconic acid, crotonic acid, maleic acid,
Examples thereof include polymers or copolymers of one or more of fumaric acid, vinyl acetic acid, and acid anhydrides thereof.

Further, there may be mentioned, for example, polymers obtained by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the above copolymer, but the invention is not limited thereto.

Among the above-mentioned non-curable binders, polymethyl methacrylate resins, polyethyl methacrylate resins, polymethyl methacrylate resins are used from the viewpoints of compatibility with the curable binder used together and yellowing to heat. Copolymers of resins and polyethyl methacrylate resins, phenoxy resins, epoxy resins, polycarbonate resins, polystyrene resins, cellulose acetate propionate, cellulose acetate butyrate, ethyl hydroxyethyl cellulose, cellulose triacetate, and the like can be preferably used. Particularly preferably, polymethyl methacrylate resin, polyethyl methacrylate resin, copolymer of polymethyl methacrylate resin and polyethyl methacrylate resin, phenoxy resin, epoxy resin, and modified products thereof can be used. .

The content of the non-curable binder is preferably in the range of 5 to 50% by weight based on the total solid content of the photosensitive resin composition. (3) Photopolymerization initiator As the photopolymerization initiator constituting the photosensitive resin composition, benzophenone, Michler's ketone, N, N'tetramethyl-4,4'-diaminobenzophenone, 4-methoxy-
Aromatic ketones such as 4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-ethylanthraquinone and phenanthrene, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether, methyl benzoin, ethyl benzoin and the like Benzoin, 2- (o-
(Chlorophenyl) -4,5-phenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5- Diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, 2-benzyl-2-dimethylamino-
1- (4-morpholinophenyl) -butanone, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4 -Oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,
Halomethylthiazole compounds such as 4-oxadiazole, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine, 2,4-bis (trichloromethyl) -6- (1-p- Dimethylaminophenyl-1,3-butadienyl) -S-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-S-triazine, 2- (naphth-1-yl) -4,6
-Bis-trichloromethyl-S-triazine, 2- (4
-Ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-butoxy-
Halomethyl-S-triazine compounds such as naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl- 1- [4- (methylthio) phenyl] -2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,1-hydroxy-cyclohexyl-phenyl ketone And Irgacure 369 (Ciba-Geigy), Irgacure 651 (Ciba-Geigy), and Irgacure 907 (Ciba-Geigy). In the present invention, these photopolymerization initiators can be used alone or in combination of two or more to increase the photocuring reaction rate.

The addition amount of such a photopolymerization initiator is preferably in the range of 0.1 to 10% by weight based on the total solid content of the photosensitive resin composition. 0.1% by weight of photopolymerization initiator
If less than, regardless of the type of photopolymerization initiator used,
It is very difficult to exhibit the effect as a photopolymerization initiator. When the content exceeds 10% by weight, although the reaction rate of photopolymerization becomes very fast, the degree of curing caused by light leaking into the area where light is shielded by the mask at the time of exposure is increased, and the desired area is reduced. It becomes difficult to transfer from the transfer film to a predetermined portion of the back layer of the PDP with high accuracy. (4) Phosphor As the phosphor that can be used in the present invention, a known phosphor that can be used for a color plasma display panel can be mentioned. Specifically, NTSC green, Zn ₂
SiO ₄ , BaAl ₁₂ O ₁₉ : Mn, BaMgAl
₁₄ O ₂₃ : Mn, SrAl ₁₂ O ₁₉ : Mn, ZnAl
_{12 O 19: Mn, CaAl 12} O 19: Mn, YBO 3: T
b, LuBO ₃ : Tb, GdBO ₃ : Tb, ScBO
₃ : Tb, Sr ₄ Si ₃ O ₈ Cl ₄ Eu, (Zn, M
n) ₂ SiO ₄ , NTSCred, Y ₂ O ₃ : Eu, Y
₂ SiO ₅ : Eu, Y ₃ Al ₅ O ₁₂ : Eu, Zn ₃ (P
O ₄ ) ₂ : Mn, YBO ₃ : Eu, (Y, Gd) BO
₃ : Eu, GdBO ₃ : Eu, ScBO ₃ : Eu, Lu
BO ₃ : Eu, (Y, Gd, Eu) BO ₃ , NTSCb
lue, CaWO ₄ : Pb, Y ₂ SiO ₅ : Ce, Ba
MgAl ₁₄ O ₂₃ : Eu, (Ba, Eu) MgAl ₁₀ O ₁₇
And the like.

The content of such a phosphor is preferably in the range of 10 to 50% by weight based on the total solid content of the photosensitive resin composition.

Further, in the above-mentioned photosensitive resin composition, additives such as a plasticizer, a sensitizer, a polymerization terminator, a chain transfer agent, a leveling agent, a dispersant, a stabilizer, a defoaming agent, and a thickener are added. ,
A precipitation inhibitor and the like can be contained as necessary.

The plasticizer is added for the purpose of improving transferability and fluidity of the photosensitive resin composition.
Normal alkyl phthalates such as dimethyl phthalate, dibutyl phthalate and di-n-octyl phthalate;
Phthalic acid esters such as di-2-ethylhexyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, tri-2-ethylhexyl trimellitate, tri-n- Trimellitate esters such as alkyl trimellitate, triisononyl trimellitate, triisodecyl trimellitate, dimethyl adipate, dibutyl adipate,
Di-2-ethylhexyl adipate, diisodecyl adipate, dibutyl diglycol adipate, di-2-ethylhexyl acetate, dimethyl sebacate, dibutyl sebacate, di-2-ethylhexyl sebacate, di-2-ethylhexyl malate, acetyl-tri -(2
-Ethylhexyl) citrate, acetyl-tri-n-
Aliphatic dibasic acid esters such as butyl citrate and acetyl tributyl citrate, glycol derivatives such as polyethylene glycol benzoate, triethylene glycol di (2-ethylhexoate) and polyglycol ether, glycerol triacetate and glycerol diacetyl Glycerin derivatives such as monolaurate, polyesters composed of sebacic acid, adipic acid, azelaic acid, phthalic acid, etc., low molecular weight polyethers having a molecular weight of 300 to 3000, low molecular weight poly-α-styrene, low molecular weight polystyrene, trimethyl Phosphate, triethyl phosphate, tributyl phosphate, tri-2
Orthophosphoric esters such as ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylendiphenyl phosphate, 2-ethylhexyl diphenyl phosphate, methyl acetyl lysate Polyesters such as ricinoleic acid esters such as nolate, poly-1,3-butanediol adipate, and epoxidized soybean oil;
Epoxidized esters, glycerin triacetate, 2
Acetates such as -ethylhexyl acetate;

Examples of the solvent used in the photosensitive resin composition include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol, and terpenes such as α- or β-terpineol. Ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbyl Tall, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Glycol ethers such as ethylene glycol monomethyl ether and triethylene glycol monoethyl ether, ethyl acetate, butyl acetate,
Cellosolve acetate, ethyl cellosolve acetate,
Examples thereof include acetates such as butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Protective Film The protective film 5 constituting the phosphor layer transfer sheet 1 for producing a plasma display panel according to the present invention has flexibility, does not undergo significant deformation due to tension or pressure, and is formed of a photosensitive resin. It is necessary to use a material having a releasability for the layer 4. Therefore, it is necessary to appropriately select the material according to the material configuration of the photosensitive resin layer 4.

Specific examples of the material used for the protective film 5 include a polyethylene film, an ethylene-vinyl acetate copolymer film, an ethylene-vinyl alcohol copolymer film, a polypropylene film, a polystyrene film, a polymethacrylic acid film, and a polychlorinated film. Vinyl film, polyvinyl alcohol film, polyvinyl butyral film, nylon film, polyetheretherketone film, polysulfone film, polyethersulfone film, polytetrafluoroethylene-perfluoroalkylvinylether film,
Polyvinyl fluoride film, tetrafluoroethylene-ethylene film, tetrafluoroethylene-hexafluoropropylene film, polychlorotrifluoroethylene film, polyvinylidene fluoride film, polyethylene terephthalate film, polyethylene naphthalate film, polyester film,
Cellulose triacetate film, polycarbonate film, polyurethane film, polyimide film, polyetherimide film, those coated with a release material such as silicone resin on the surface of these films, a layer in which a thermoplastic resin is crosslinked with a crosslinking agent A film provided on the surface, a film in which a filler is blended with the above resin material,
A film obtained by uniaxially or biaxially stretching a film using these resin materials, a biaxially stretched film in which the stretching ratio in the width direction is increased from the flow direction using these resin materials, and a width using these resin materials Biaxially stretched film with a higher draw ratio in the flow direction than in the direction, a film obtained by laminating films of the same or different types among these films, and
Composite films formed by co-extruding the same or different resins selected from the raw material resins used for these films can be used. Among these films, it is particularly preferable to use a polyethylene film or a polyethylene terephthalate film coated with a silicon-based release material.

The thickness of the protective film 5 is 4
It can be set in the range of up to 400 μm.

When the transfer sheet 1 for forming the phosphor layer is not formed in a roll shape, the protective film 5 need not be provided.

FIG. 2 is a schematic sectional view showing another embodiment of the transfer sheet for forming a phosphor layer of the present invention. In FIG. 2, a transfer sheet 11 for forming a phosphor layer is provided with a base film 12, a release layer 13 provided releasably on the base film 12, and a primer layer 16 provided on the release layer 13. The photosensitive resin layer 14 and the protective film 15 are provided. This transfer sheet 11 for forming a phosphor layer is different from the above-described phosphor layer transfer sheet 1 in that a primer layer 16 is provided between a release layer 13 and a photosensitive resin layer 14.

As described above, when the photosensitive resin layer 14 is made of a water-insoluble material and the release layer 13 is formed mainly of a water-soluble resin, the primer layer 16 It is formed for the purpose of enhancing the adhesion to the resin layer 14 and further improving the film breakability after exposure.
Such a primer layer 16 can be formed mainly of a resin soluble in at least one of methyl alcohol, ethyl alcohol and isopropyl alcohol. Examples of such a resin include polyvinylpyrrolidone,
Polyvinyl butyral and the like can be mentioned. Here, the main component in the present invention indicates a component occupying 50% by weight or more of the total resin component of the primer layer 16.

As described above, the primer layer 16 is formed by adding a resin soluble in at least one of methyl alcohol, ethyl alcohol, and isopropyl alcohol, if necessary, to a resin soluble in the resin. Dissolved in the above alcohol, or dissolved in a mixed solvent of an organic solvent and water, or, to prepare a dispersion dispersed in an organic solvent or water, apply this on the release layer 13 by known coating means, It can be performed by drying.

The thickness of the primer layer 16 is 0.05 to 5 μm.
m, preferably in the range of 0.1 to 2 μm. When the thickness of the primer layer 16 is less than 0.05 μm, the effect as a primer layer cannot be obtained due to defects in the film due to uneven coating, and when it exceeds 5 μm, a desired area when the desired region is peeled from the base film 12 is removed. It is not preferable because the film-cutting property is reduced.

The above-mentioned primer layer 16 is separated from the release layer 1
In the transfer sheet 11 provided between the transfer layer 3 and the photosensitive resin layer 14, the thickness of the release layer 13 can be set to be thinner than the release layer 3 described above, for example, 0.05 to 3 μm, preferably 0.1 to 3 μm. It may be set in a range of 1.5 μm.

Incidentally, the primer layer 16 is also provided with the following properties in order to further improve the film-cutting property in peeling the base film.
Microcrystalline wax, carnauba wax,
Paraffin wax, Fischer-Tropsch wax,
Various low molecular weight polyethylene, wood wax, beeswax, spermaceti, Ibota wax, wool wax, shellac wax, candelilla wax, petrolactam, partially modified wax,
One or more of fatty acids, fatty acid amides, waxes such as silicone wax, polystyrene, polyester, polyurethane and the like may be contained in the range of 0.5 to 20% by weight.

The base film 12, the release layer 13, and the photosensitive resin layer 1 constituting the transfer sheet 11 for forming the phosphor layer
4. The constituent materials and the forming method of the protective film 15 are the same as those of the base film 2, the release layer 3, the photosensitive resin layer 4, and the protective film 5, which constitute the transfer sheet 1 for forming the phosphor layer. The description here is omitted.

Next, an example of pattern formation of a phosphor layer of a plasma display panel (PDP) using the above-described transfer sheet for forming a phosphor layer of the present invention will be described.

FIG. 3 is a schematic structural view showing an AC type PDP, showing a state in which a front plate and a back plate are separated.
In FIG. 3, the PDP 21 has a front plate 31 and a back plate 41 arranged in parallel and opposed to each other, and a barrier 46 is formed on the front side of the back plate 41 so as to stand upright. The front plate 31 and the rear plate 41 are held at regular intervals by the barrier 46. The front plate 31 has a front glass substrate 32, and on the back side of the front glass substrate 32, composite electrodes composed of a sustain electrode 33 which is a transparent electrode and a bus electrode 34 which is a metal electrode are formed in parallel with each other. And a dielectric layer 35 is formed over the
An O layer 36 is formed. The rear plate 41 has a rear glass substrate 42, and an address electrode 44 is located on the front side of the rear glass substrate 42 between the barriers 46 so as to be orthogonal to the composite electrode via a base layer 43. Are formed in parallel with each other, a dielectric layer 45 is formed so as to cover them, and a phosphor layer 47 is provided so as to cover the wall surface of the barrier 46 and the bottom surface of the cell. In this AC type PDP, a predetermined voltage is applied from an AC power supply between the composite electrodes on the front glass substrate 32 to form an electric field, whereby the front glass substrate 32, the rear glass substrate 42, and the barrier 4 are formed.
Discharge is performed in each cell as a display element defined by the cells 6 and 6. Then, the phosphor layer 47 is caused to emit light by the ultraviolet light generated by the discharge, and the light transmitted through the front glass substrate 32 is visually recognized by the observer.

Next, the formation of the phosphor layer 47 on the back plate 41 of the PDP will be described.

FIG. 4 is a process chart for explaining the pattern formation of the phosphor layer 47 using the transfer sheet 1 for forming the phosphor layer of the present invention.

In FIG. 4, first, the photosensitive resin layer 4R (containing a red-emitting phosphor) of the transfer sheet 1 from which the protective film 5 has been peeled off is provided on the barrier 46 of the back plate 41 on which the barrier 46 is formed. The photosensitive resin layer 4R is exposed from the side of the base film 2 via a predetermined photomask. Thereafter, the base film 2 is peeled off, and only the photosensitive resin layer 4R and the peeling layer 3 in the exposed region are transferred.
The photosensitive resin layer 4R and the release layer 3 in the unexposed area are removed (development and development) together with the base film (FIG. 4A).

Next, together with the release layer 3, the photosensitive resin layer 4R
Is transferred to a desired position covering the wall surface of the barrier 46 and the bottom surface of the cell, on the barrier 46 of the back plate 41, the photosensitive resin layer 4G of the transfer sheet 1 from which the protective film 5 has been peeled off (containing a green-emitting phosphor. Is pressed, and the photosensitive resin layer 4G is exposed from the base film 2 side through a predetermined photomask. After that, only the photosensitive resin layer 4G and the release layer 3 in the area exposed by peeling the base film 2 are transferred,
The unexposed photosensitive resin layer 4G and the release layer 3 are removed together with the base film (FIG. 4B). In this transfer step, the release layer 3 is present on the surface of the photosensitive resin layer 4R that has already been transferred.
Even if the photosensitive resin layer 4G contacts, the close contact between the photosensitive resin layer 4G and the photosensitive resin layer 4R is prevented. Therefore, the photosensitive resin layer 4G in the unexposed region adheres to the photosensitive resin layer 4R to cause abnormal transfer, or the already transferred photosensitive resin layer 4R adheres to the photosensitive resin layer 4G in the unexposed region. It is not stripped and removed.

Further, the photosensitive resin layer 4 together with the release layer 3
R, the photosensitive resin layer 4B (blue) of the transfer sheet 1 from which the protective film 5 is peeled and removed is applied to the barrier 46 of the back plate 41 where the photosensitive resin layer 4G is transferred to a desired position covering the wall surface of the barrier 46 and the bottom surface of the cell. The side containing the luminescent phosphor) is crimped,
The photosensitive resin layer 4B is exposed from the side of the base film 2 via a predetermined photomask. Then, base film 2
Then, only the photosensitive resin layer 4B and the release layer 3 in the exposed area are transferred, and the photosensitive resin layer 4B and the release layer 3 in the unexposed area are removed together with the base film (FIG. 4).
(C)). In this transfer step, the release layer 3 is formed on the surfaces of the photosensitive resin layer 4R and the photosensitive resin layer 4G which have already been transferred.
Is present, the peeling action of the peeling layer 3 prevents the photosensitive resin layer 4B from contacting the photosensitive resin layers 4R and 4G even if the photosensitive resin layer 4B comes into contact. Therefore, the photosensitive resin layer 4B in the unexposed area is changed to the photosensitive resin layer 4R.
The photosensitive resin layer 4R, 4G, which has been transferred, does not adhere to the photosensitive resin layer 4G or the photosensitive resin layer 4G, and does not peel off.

Through the above-described transfer process, the photosensitive resin layers 4R, 4G, and 4B each having the release layer 3 on the surface are transferred to predetermined locations so as to cover the wall surface of the barrier 46 and the bottom surface of the cell. Then, by baking, the resin components of the photosensitive resin layers 4R, 4G, 4B and the release layer 3 are volatilized,
The phosphor layer 47 (47R, 47G, 47
B) is formed (FIG. 4D).

[0052]

Next, the present invention will be described in more detail with reference to examples. (Preparation of Transfer Sheet (Sample 1)) First, a coating solution for forming a release layer having the following composition was prepared.

Composition of coating liquid for forming release layer : polyvinyl alcohol: 100 parts by weight (degree of saponification: 91.0 to 94.0, AL-6 manufactured by Nippon Synthetic Chemical Co., Ltd.) Carnauba wax aqueous dispersion: 50 parts by weight (solid content concentration: 40% by weight) Water: 2,000 parts by weight Also, each of the following photosensitive resin compositions for red light emission, green light emission, and blue light emission was prepared.

Composition of photosensitive resin composition (for red emission) Polymethyl methacrylate: 10 parts by weight (weight average molecular weight: 95,000) Trimethylolpropane triacrylate: 20 parts by weight Urethane acrylate: 10 parts by weight (M-1600, manufactured by Toa Gosei Co., Ltd.) Photopolymerization initiator: 1 part by weight (Irgacure 369 manufactured by Ciba Geigy) Red phosphor (Y, Gd, Eu) BO ₃ : 80 parts by weight (KASEI OPTO CORPORATION ) KX-504A)-Methyl ethyl ketone ... 20 parts by weight-Toluene ... 20 parts by weight Composition of photosensitive resin composition (for green light emission)-Polymethyl methacrylate methacrylate ... 10 parts by weight (weight average molecular weight 95,000)-Tri Methylol propane triacrylate ... 20 parts by weight ・ Urethane acrylate ... 10 Parts by weight (M-1600, manufactured by Toa Gosei Co., Ltd.) Photopolymerization initiator: 1 part by weight (Irgacure 369 manufactured by Ciba Geigy) Green phosphor (Zn, Mn) ₂ SiO ₄ : 64 parts by weight (Chemical Opto ( P1-G1S manufactured by Co., Ltd.)-Methyl ethyl ketone ... 20 parts by weight-Toluene ... 20 parts by weight Composition of photosensitive resin composition (for blue light emission)-Polymethyl methacrylate methacrylate ... 10 parts by weight (weight average molecular weight 95,000)- Trimethylolpropane triacrylate 20 parts by weight Urethane acrylate 10 parts by weight (M-1600 manufactured by Toagosei Co., Ltd.) Photopolymerization initiator 1 part by weight (Irgacure 369 manufactured by Ciba Geigy) Blue phosphor (Ba) _{, Eu) MgAl 10 O 17 ...} 60 parts by weight (manufactured by Kasei opt (Ltd.) KX-501A) · methyl ethyl ketone ... 20 parts by weight Toluene 20 parts by weight Then, a polyethylene terephthalate film (Toray Co. Lumirror T-60 (thickness 25 as a base film
μm)), the above-mentioned coating solution for forming a release layer is applied on the base film by a wire bar, and dried (1 μm).
(30 ° C., 1 minute) to form a release layer having a thickness of 0.5 μm.

Next, the above-mentioned photosensitive resin composition for emitting red light was applied on the release layer by a wire bar and dried (1).
(30 ° C., 3 minutes) to form a 50 μm thick photosensitive resin layer.

Next, a silicone-coated polyethylene terephthalate film (SP-PETO2 (thickness: 25 μm) manufactured by Tosello Co., Ltd.) as a protective film on the photosensitive resin layer.
Was laminated to prepare a transfer sheet (sample 1) for forming a phosphor layer for red light emission as shown in FIG. Similarly, a phosphor layer transfer sheet (sample 1) for green light emission and blue light emission was prepared. (Preparation of Transfer Sheet (Sample 2)) Further, a coating solution for forming a primer layer having the following composition was prepared.

Composition of coating solution for forming primer layer : polyvinyl pyrrolidone (number average molecular weight: 900,000): 25 parts by weight; polyvinyl butyral: 25 parts by weight (# 3000-1 manufactured by Denki Kagaku Kogyo Co., Ltd.); isopropyl alcohol: 760 parts by weight-methyl ethyl ketone ... 190 parts by weight Next, as a base film, a polyethylene terephthalate film (Lumirror T-60 manufactured by Toray Industries, Inc. (thickness: 25)
μm)), the above-mentioned coating solution for forming a release layer is applied on the base film by a wire bar, and dried (1 μm).
(30 ° C., 1 minute) to form a release layer having a thickness of 0.4 μm. Further, the above-mentioned coating solution for forming a primer layer is applied on the release layer by a wire bar and dried (130).
C. for 1 minute) to form a 0.4 μm thick primer layer.

Next, a photosensitive resin layer for emitting red light was formed on the release layer in the same manner as in Sample 1 described above, and a protective film was laminated on the photosensitive resin layer, as shown in FIG. A transfer sheet (sample 2) for forming a phosphor layer for red light emission was prepared. Similarly, a phosphor layer transfer sheet for green light emission and blue light emission (sample 2) was prepared. (Preparation of Transfer Sheet (Comparative Sample)) On the other hand, as a comparison,
A base film similar to that of sample 1 was prepared, and the above-mentioned photosensitive resin composition for red light emission was applied on the base film by a wire bar and dried (130 ° C., 1 minute), and a 50 μm thick photosensitive resin layer was formed. Was formed.

Next, a silicone-coated polyethylene terephthalate film (SP-PETO2 (thickness: 25 μm) manufactured by Tosello Co., Ltd.) as a protective film on the photosensitive resin layer
Were laminated to prepare a conventional transfer sheet (comparative sample) for forming a phosphor layer for red light emission. Similarly, phosphor layer transfer sheets for green light emission and blue light emission (comparative samples) were prepared. (Evaluation of transfer sheet for forming phosphor layer)
A plurality of glass substrates having barriers having a height of 120 μm and a height of 120 μm were formed at intervals of 170 μm, and a photosensitive layer was formed using the above-described transfer sheet for forming a phosphor layer for red emission (samples 1 and 2 and a comparative sample). The transfer of the resin layer (for red light emission) was performed. In this transfer, the photosensitive resin layer of the phosphor layer transfer sheet is pressed against the barrier, and the pattern mask of the phosphor layer for red light emission (opening width 80 μm, forming interval 5) from the base film side.
UV light (light source: ultra high pressure mercury lamp)
(100 mJ / cm ² ) to expose the photosensitive resin layer. Thereafter, the base film was peeled off, and the unexposed portion of the photosensitive resin layer was removed and developed to form a pattern (exposed layer on the surface) composed of the exposed portion of the photosensitive resin layer.

Similarly, the transfer of the photosensitive resin layer (for emitting green light) was performed using the above-mentioned phosphor layer transfer sheet for emitting green light (samples 1, 2 and comparative sample). Further, the photosensitive resin layer (for blue light emission) was transferred using the above-described phosphor layer transfer sheet for blue light emission (samples 1, 2 and comparative samples).

In the above-described transfer, when the sample 1 and the sample 2 are used, the photosensitive resin layers of different colors do not adhere to each other, and the photosensitive resin layer is attached to the wall surface of the barrier for each emission color. It was possible to transfer easily and reliably to a desired location on the cell bottom.

On the other hand, when the comparative sample was used, in the transfer of the green light-emitting photosensitive resin layer (second color), the already-transferred red light-emitting photosensitive resin layer was removed and removed. Adhesion of the green light emitting photosensitive resin layer to the red light emitting photosensitive resin layer that has already been transferred occurs,
The same occurred in the transfer of the photosensitive resin layer for blue light emission (third color).

Next, the resin component of the transferred photosensitive resin layer (including the peeling layer in the case of using Samples 1 and 2) is removed by raising the temperature from room temperature to 450 ° C. in a firing furnace for 1 hour, and the phosphor is removed. A layer was formed. The accuracy of the formed phosphor layer is of a high quality that can be practically used as a plasma display panel when the sample 1 is used and when the sample 2 is used, and when the comparative sample is used, Depending on the location, many problems such as a missing phosphor or a mixture of phosphors of a plurality of colors occurred, and it was not possible to produce a practical back plate.

[0064]

As described in detail above, according to the present invention, a photosensitive resin layer containing a phosphor is formed on a base film via a release layer, and the release layer is made releasable to form a phosphor layer. Since the release layer is transferred to the back plate for the plasma display panel together with the photosensitive resin layer, the photosensitive resin layer of a different color comes into contact in the subsequent transfer operation of the photosensitive resin layer of another color. However, a peeling effect is exerted on the photosensitive resin layer to prevent the photosensitive resin layers of different colors from sticking to each other, and furthermore, by providing the peeling layer, a boundary between the exposed portion and the unexposed portion is provided. And thus the photosensitive resin layer of a plurality of colors is easily and reliably transferred to a desired portion of a wall surface of a back plate and a bottom surface of a cell for each color, and a phosphor layer is formed with high precision. It is possible.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing one embodiment of a transfer sheet for forming a phosphor layer of the present invention.

FIG. 2 is a schematic sectional view showing another embodiment of the transfer sheet for forming a phosphor layer of the present invention.

FIG. 3 is a schematic configuration diagram illustrating an example of a plasma display panel.

FIG. 4 is a process chart for explaining an example of phosphor layer formation using a transfer sheet for phosphor layer formation of the present invention.

[Explanation of symbols]

 1, 11: transfer sheet for forming a phosphor layer 2, 12: base film 3, 13 ... release layer 4, 14 ... photosensitive resin layer 5, 15 ... protective film 16 ... primer layer

Claims (5)

[Claims] 1. A phosphor comprising: a base film; a release layer releasably provided on the base film; and a photosensitive resin layer containing a phosphor provided on the release layer. Transfer sheet for layer formation. 2. The transfer sheet according to claim 1, wherein the release layer contains a water-soluble resin as a main component. 3. The transfer sheet according to claim 2, wherein the water-soluble resin is hardly soluble or insoluble in methyl alcohol, ethyl alcohol and isopropyl alcohol. 4. A primer layer is provided between the release layer and the photosensitive resin layer, and the primer layer mainly contains a resin soluble in at least one of methyl alcohol, ethyl alcohol and isopropyl alcohol. The transfer sheet for forming a phosphor layer according to claim 3, characterized in that: 5. The transfer sheet for forming a phosphor layer according to claim 2, wherein the water-soluble resin contained in the release layer is mainly composed of polyvinyl alcohol.