JP2006286429A - Transfer film and method for manufacturing plasma display panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transfer film which has high sensitivity and superior workability and by which a barrier rib of a PDP and a dielectric layer having excellent dimensional accuracy can be preferably formed, and to provide a method for manufacturing the PDP using it. <P>SOLUTION: In the transfer film and the method for manufacturing the PDP using it, a radiation-sensitive film-forming material layer containing glass powder and organic components is provided on a support film, and the linear transmittance (Tp) is 0.01-10% and the diffuse transmittance (Td) is 1-50% at a wave length of 405 nm in the film forming material layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a transfer film suitably used for manufacturing a plasma display panel and a method for manufacturing a plasma display panel using the transfer film.

  In recent years, a plasma display has attracted attention as a flat fluorescent display. FIG. 1 is a schematic view showing a cross-sectional shape of an AC type plasma display panel (hereinafter also referred to as “PDP”). In the figure, reference numerals 1 and 2 denote glass substrates arranged opposite to each other, 3 denotes a partition, and cells are defined by the glass substrate 1, the glass substrate 2, and the partition 3. 4 is a transparent electrode fixed on the glass substrate 1, 5 is a bus electrode formed on the transparent electrode 4 for the purpose of reducing the resistance of the transparent electrode 4, 6 is an address electrode fixed on the glass substrate 2, and 7 is Fluorescent material held in the cell, 8 is a dielectric layer formed on the surface of the glass substrate 1 so as to cover the transparent electrode 4 and the bus electrode 5, and 9 is on the surface of the glass substrate 2 so as to cover the address electrode 6. The formed dielectric layer 10 is a protective film made of, for example, magnesium oxide. In the color PDP, a color filter (red / green / blue) or a black matrix may be provided between the glass substrate and the dielectric layer in order to obtain a high contrast image.

  Such a PDP dielectric, partition, electrode, phosphor, color filter, black stripe (matrix), etc. are produced by forming a photosensitive inorganic powder-containing resin layer on a substrate and forming a pattern. A photolithography method in which a pattern is left on a substrate by irradiating the film corresponding to the above with ultraviolet rays and developed, and then baked, is preferably used.

JP-A-6-67425 JP 2000-305262 A

However, when a thick film pattern such as a partition wall is formed using a photolithography method, there is a problem that a member with high dimensional accuracy cannot be obtained because the sensitivity at the time of exposure processing becomes insufficient.
The present invention has been made based on the above situation.
A first object of the present invention is to provide a transfer film in which a PDP partition wall and a dielectric layer can be suitably formed with high sensitivity, excellent workability, and excellent dimensional accuracy.
A second object of the present invention is to provide a PDP manufacturing method capable of suitably forming PDP partition walls and dielectric layers having excellent dimensional accuracy.
Further objects of the present invention will become apparent from the following description.

The transfer film of the present invention has a radiation-sensitive film-forming material layer containing glass powder and an organic component on a support film, and the film-forming material layer has a linear transmittance (Tp) at a wavelength of 405 nm of 0. The diffusion transmittance (Td) is 1 to 50%.
In the method for producing the PDP of the present invention, the film forming material layer in the transfer film of the present invention is transferred onto a substrate, and the film forming material layer is exposed to form a latent image of the pattern. It includes a step of forming a member selected from a partition wall and a dielectric layer by forming a pattern by developing and baking the pattern.

Hereinafter, the present invention will be described in detail.
<Transfer film>
The transfer film of the present invention comprises a support film and a radiation-sensitive film-forming material layer formed on the support film. A protective film may be provided on the surface of the film forming material layer.
In the transfer film of the present invention, the film-forming material layer has a linear transmittance (Tp) at a wavelength of 405 nm of 0.01 to 10%, preferably 0.05 to 5%, and the film-forming material layer has a wavelength of 405 nm. The diffusion transmittance (Td) is 1 to 50%, preferably 5 to 45%. By using the film forming material layer having the above-described linear transmittance and diffuse transmittance, the sensitivity at the time of exposure is improved, and a pattern with excellent dimensional accuracy can be formed.
As a method for obtaining such a film-forming material layer having a high light transmittance, there can be mentioned a method in which the glass powder used and the organic component have a similar refractive index. Each component constituting the film forming material layer will be described later.

(1) Support film:
The support film constituting the transfer film is preferably a resin film having heat resistance and solvent resistance and flexibility. Since the support film has flexibility, the paste-like composition can be applied by a roll coater, and the film-forming material layer can be stored and supplied in a state of being wound in a roll. Examples of the resin forming the support film include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, polyfluoroethylene, and other fluorine-containing resins, nylon, and cellulose. The thickness of the support film is, for example, 20 to 100 μm.
In addition, it is preferable that the mold release process is performed to the surface of the support film. Thereby, peeling operation of a support film can be easily performed in the transfer process mentioned later.

(2) Film forming material layer:
The film-forming material layer constituting the transfer film is prepared by applying a paste-like radiation-sensitive glass paste composition containing glass powder and an organic component as essential components onto the support film, drying the coating film, It can be formed by removing part or all of it.

(3) Glass paste composition The glass paste composition used for producing the transfer film is a paste-like composition containing glass powder and an organic component, and the organic component includes a binder resin (alkali-soluble). Resin or water-soluble resin), a radiation-sensitive component, and a solvent as essential components.

Glass powder:
The glass powder used in the present invention includes a low melting point glass powder having a softening point of preferably 300 to 700 ° C.
Preferred glass powder compositions are: 1. Mixture of zinc oxide, boron oxide and silicon oxide (ZnO—B ₂ O ₃ —SiO ₂ system) _2. a mixture of zinc oxide, phosphorus oxide and silicon oxide (ZnO—P ₂ O ₅ —SiO ₂ system); _3. A mixture of zinc oxide, boron oxide and potassium oxide (ZnO—B ₂ O ₃ —K ₂ O system). 4. Mixture of phosphorus oxide, boron oxide and aluminum oxide (P ₂ O ₅ —B ₂ O ₃ —Al ₂ O ₃ system) _5. a mixture of zinc oxide, phosphorus oxide, silicon oxide, aluminum oxide (ZnO—P ₂ O ₅ —SiO ₂ —Al ₂ O ₃ system); 6. a mixture of zinc oxide, phosphorus oxide, titanium oxide (ZnO—P ₂ O ₅ —TiO ₂ system); 7. A mixture of zinc oxide, boron oxide, silicon oxide, potassium oxide (ZnO—B ₂ O ₃ —SiO ₂ system—K ₂ O system); 8. a mixture of zinc oxide, boron oxide, silicon oxide, potassium oxide, calcium oxide (ZnO—B ₂ O ₃ —SiO ₂ —K ₂ O—CaO system); 9. Mixture of boron oxide, silicon oxide, aluminum oxide (B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ system) And a mixture of zinc oxide, boron oxide, silicon oxide, potassium oxide, calcium oxide, aluminum oxide (ZnO—B ₂ O ₃ —SiO ₂ —K ₂ O—CaO—Al ₂ O ₃ system), and the like.

The content of the glass powder in the film forming material layer is preferably 50 to 90% by mass, particularly preferably 60 to 80% by mass. When the glass powder is 50% by mass or less, shrinkage during firing is large, and it becomes difficult to obtain a predetermined thickness after firing. On the other hand, when the glass powder is 90% by mass or more, the transfer property of the obtained transfer film to the glass substrate may be insufficient, or the resolution of the partition walls and the dielectric may be lowered.
Moreover, as an average particle diameter of the glass powder used for this invention, it is preferable that it is 0.3-10 micrometers, Most preferably, it is 0.5-5 micrometers. If the average particle size is smaller than 0.3 μm, the viscosity increases rapidly during the production process of the glass paste composition, and it may be difficult to obtain a fluid and homogeneous composition. In some cases, it is difficult to form a film-forming material layer having an in-plane uniformity of partition walls and dielectric layers obtained after firing.
Furthermore, it is preferable that the refractive index of the glass powder used for this invention is 1.5-1.7. By using a glass powder having a refractive index in the above range, a film forming material layer having a preferable transmittance can be formed.

Binder resin:
The binder resin used in the present invention serves as a binder for uniformly dispersing the glass powder, obtaining a film-forming material layer having a specific thickness, and further imparting adhesion to the substrate to the film-forming material layer. Have a role. The binder resin has a property of being dissolved in a developing solution in a developing step in a PDP manufacturing method described later, and specifically, an alkali-soluble resin, a water-soluble resin, or the like is used.

Alkali-soluble resins;
“Alkali-soluble” in the alkali-soluble resin used in the present invention refers to the property of being dissolved in an alkaline developer and having solubility to the extent that the intended development processing is performed.
Specific examples of such alkali-soluble resins include (meth) acrylic resins, hydroxystyrene resins, novolac resins, and polyester resins. Of these, (meth) acrylic resins are particularly preferably used.
As said (meth) acrylic-type resin, the copolymer of the monomer which has the following alkali-soluble functional group, and another copolymerizable monomer can be mentioned.

As a monomer having an alkali-soluble functional group, for example,
Acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, succinic acid mono (2- (meth) acryloyloxyethyl), ω-carboxy-polycaprolactone mono Carboxyl group-containing monomers such as (meth) acrylate;
Hydroxyl-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene Etc.

Examples of other copolymerizable monomers include:
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopenta (meth) acrylate (Meth) acrylic acid esters such as nil;
Aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene;
Conjugated dienes such as butadiene and isoprene;
Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile;
A macro having a polymerizable unsaturated group such as a (meth) acryloyl group at one end of a polymer chain such as polystyrene, poly (meth) acrylate methyl, poly (meth) ethyl acrylate, poly (meth) acrylate benzyl, etc. And macromonomers such as monomers.
These can be used alone or in combination of two or more.

In the alkali-soluble resin used in the present invention, the copolymerization ratio of the monomer having an alkali-soluble functional group is preferably 1 to 60% by mass, particularly preferably 5 to 50% by mass.
Particularly preferred compositions for the alkali-soluble resin used in the present invention include methacrylic acid / 2-hydroxypropyl methacrylate / n-butyl methacrylate copolymer, and methacrylic acid / succinic acid mono (2-methacryloyloxyethyl) / Examples include 2-hydroxypropyl methacrylate / n-butyl methacrylate copolymer.

Water-soluble resin;
The “water-soluble” in the water-soluble resin used in the present invention means a property that is soluble to the extent that it is dissolved in water and the intended development processing is performed.
Examples of such water-soluble resins include (meth) acrylic resins that are copolymers of (meth) acrylates having water-soluble functional groups and other copolymerizable monomers. By using a water-soluble resin as the binder resin, the interaction with the inorganic powder is not too strong compared to other resins, so that a glass paste composition having excellent storage stability can be obtained.

Examples of the monomer having a water-soluble functional group include methoxypolyethylene glycol mono (meth) acrylate, methoxypolypropylene glycol mono (meth) acrylate, methoxypolybutylene glycol mono (meth) acrylate, methoxypoly (ethylene glycol-propylene glycol) mono ( Examples include alkoxy polyalkylene glycol (meth) acrylates such as meth) acrylate and methoxypoly (propylene glycol-butylene glycol) mono (meth) acrylate. Of these, methoxypolyethylene glycol mono (meth) acrylate is particularly preferred.
Examples of commercially available products of the above-mentioned compounds include “Blemmer” series manufactured by Nippon Oil & Fats Co., Ltd., particularly “Blemmer PME-100”, “Same PME-200”, “Same PME-350” and the like.

Examples of other copolymerizable monomers include the hydroxyl group-containing monomers described above;
(Meth) acrylamide, N, N-dimethylacrylamide, N, N-dimethylaminopropylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide,
Amides such as acryloylmorpholine;
Examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl trimethyl acetate, and vinyl phenyl acetate.

In the water-soluble resin used in the present invention, the copolymerization ratio of the monomer having a water-soluble functional group is preferably 50 to 100 mol%, more preferably 70 to 100 mol%, particularly preferably 80 to 95 mol%. is there.
The weight average molecular weight (hereinafter also referred to as “Mw”) of the binder resin used in the present invention is preferably 5,000 to 5,000,000, particularly preferably 10,000 to 300,000. When Mw is in the above range, the film-forming property when the transfer film is formed is good, and the patterning property is also excellent. In addition, said Mw is the weight average molecular weight of polystyrene conversion by GPC measurement.

In the binder resin used in the present invention, the content ratio of the repeating unit having an aromatic ring contained in the binder resin is 5 to 50% by mass from the viewpoint of achieving both the transmittance and the combustibility of the obtained film-forming material layer. It is preferable that If this ratio is less than 5% by mass, the transmittance of the film-forming material layer may not be sufficient, and if it exceeds 50% by mass, the combustibility is poor when the film-forming material layer is sintered. There is a case.
The content ratio of the binder resin in the film forming material layer is usually 1 to 200 parts by weight, preferably 5 to 150 parts by weight, and particularly preferably 10 to 120 parts by weight with respect to 100 parts by weight of the glass powder. Part. In particular, the content ratio when using a water-soluble resin is preferably 1 to 50 parts by mass.

Radiation sensitive components:
As the radiation-sensitive component used in the present invention, for example, (a) a combination of a polyfunctional monomer and a radiation polymerization initiator, (b) a radiation-sensitive acid generator that forms an acid upon irradiation is preferable. It can be illustrated as.

As the polyfunctional monomer, polyfunctional (meth) acrylate is preferably used. Preferable specific examples include two or more functionalities such as polypropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc. And polyfunctional acrylates thereof, oligomers thereof, ethylene oxide modification, and propylene oxide modification.
Among these, polypropylene glycol diacrylate, trimethylolpropane ethylene oxide-modified triacrylate, and pentaerythritol triacrylate are particularly strong in that the resist pattern has high strength and is less likely to cause soiling or film residue in areas other than the pattern formation area. preferable.
The molecular weight of the polyfunctional (meth) acrylate is preferably 100 to 2,000.
The usage ratio of the polyfunctional monomer is usually 5 to 100 parts by weight, preferably 10 to 70 parts by weight, with respect to 100 parts by weight of the alkali-soluble resin. When this ratio is less than 5 parts by weight, the pattern strength tends to be insufficient. On the other hand, when this ratio exceeds 100 parts by weight, the alkali resolution tends to be reduced, or background contamination other than the pattern forming part, film residue, etc. tend to occur.

Examples of the radiation polymerization initiator include benzyl, benzoin, benzophenone, bis (N, N-dimethylamino) benzophenone, bis (N, N-diethylamino) benzophenone, camphorquinone, 2-hydroxy-2-methyl-1-phenylpropane -1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- [4 ′-(methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2 -Carbonyl compounds such as dimethylamino-1- (4-morpholinophenyl) -butan-1-one; azo compounds or azide compounds such as azoisobutyronitrile and 4-azidobenzaldehyde; mercaptan disulfides, mercaptobenzothiazoles, etc. Organic Sulfur compounds; organic peroxides such as benzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, paraffin hydroperoxide; 1,3-bis (trichloromethyl) -5- ( 2'-chlorophenyl) -1,3,5-triazine, trihalomethanes such as 2- [2- (2-furanyl) ethylenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine; 2 , 2′-bis (2-chlorophenyl) 4,5,4 ′, 5′-tetraphenyl1,2′-biimidazole and other imidazole dimers. These can be used alone or in combination of two or more.
The ratio of the radiation polymerization initiator used in the present invention is usually 0.5 to 50 parts by weight, preferably 1 to 30 parts by weight, and particularly preferably 1 to 20 parts by weight with respect to 100 parts by weight of the polyfunctional monomer. is there. If the amount is less than 0.5 part by weight, curing due to radiation irradiation becomes insufficient, and there is a possibility that the pattern may be missing, deficient or undercut. On the other hand, if the amount exceeds 50 parts by weight, the formed pattern will fall off the substrate during development. It becomes easy. Moreover, there exists a possibility that a baking residue may become easy to generate | occur | produce.

  A radiation-sensitive acid generator is a compound that generates an acid upon irradiation with radiation. Examples thereof include 1,2-benzoquinone diazide sulfonic acid ester, 1,2-naphthoquinone diazide sulfonic acid ester, 1,2-benzoquinone diazide sulfonic acid amide, 1,2-naphthoquinone diazide sulfonic acid amide, and the like. Specifically, J. et al. Kosar, “Light-Sensitive Systems” 339-352 (1965), John Wiley & Sons (New York); S. De Forest, “Photoresist” 50 (1975), McGraw-Hill, Inc. 1,2-quinonediazide compounds described in (New York).

  Among these, compounds having good transparency in the visible light region of 400 to 800 nm after irradiation, such as 2,3,4-trihydroxybenzophenone and 2,3,4,4′-tetrahydroxybenzophenone 3′-methoxy-2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 5,5′-tetramethyl-2 ′, 4,4′-trihydroxytriphenylmethane, 4,4 ′ -[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol and 2,4,4-trimethyl-2 ′, 4 ′, 7-trihydroxy-2- 1,2-benzoquinonediazide-4-sulfonic acid ester such as phenylflavan, 1,2-naphthoquinonediazide-4-sulfonic acid ester, and 1,2-naphtho It may be mentioned as being preferred quinonediazide-5-sulfonic acid ester.

  The content of the radiation-sensitive acid generator is preferably 1 to 100 parts by mass, particularly preferably 5 to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin. If the content is less than 1 part by mass, the amount of acid generated by absorbing radiation is reduced, so that the solubility in an alkaline aqueous solution before and after radiation irradiation cannot be made different, and patterning becomes difficult. There is a risk that a defect may occur in the heat resistance of the pattern to be formed. On the other hand, when the content exceeds 100 parts by mass, most of the added radiation-sensitive acid generator still remains as it is after irradiation for a short time, so that the effect of insolubilization in an aqueous alkali solution is too high. It may be difficult to develop.

UV absorber:
The glass paste composition used in the present invention preferably further contains an ultraviolet absorber. As the ultraviolet absorber, an organic dye having a high UV absorption coefficient in a wavelength range of 300 to 500 nm is preferable because it does not remain in the member after firing and does not deteriorate the member characteristics. Is preferably used.
Specifically, azo compounds, triazine compounds, amino ketone compounds, xanthene compounds, quinoline compounds, quinone compounds, benzophenone compounds, benzoic acid compounds, cyanoacrylate compounds, spiro compounds, fluorenone compounds, fulgide compounds, imidazole compounds, perylene compounds, phenazines Compound, phenothiazine compound, polyene compound, diphenylmethane compound, triphenylmethane compound, polymethine compound, acridine compound, acridinenon compound, carboostyryl compound, coumarin compound, diphenylamine compound, quinacridone compound, quinophthalone compound, phenoxazine compound, phthaloperinone compound, A phthalocyanine compound can be used. Among them, azo compounds represented by 1-phenylazo-2-naphthol, 1-phenyl-3-methyl-4- (4-methylphenylazo) -5-oxypyrazole and the like, represented by 1,4-diamilaminoanthraquinone Particularly preferred are quinone compounds and phenolic compounds represented by curcumin.
When an organic dye is used, the addition amount is 0.005 to 0.1% by mass, preferably about 0.01 to 0.05% by mass, based on the total content in the organic component excluding the solvent. It is. When the addition amount is less than the above range, the effect of adding the ultraviolet absorber is not so much, and when it exceeds the above range, the characteristics of the obtained PDP member may be deteriorated.

solvent;
The glass paste composition for forming the film-forming material layer usually contains a solvent. The solvent used here has good affinity with glass powder and good solubility of the alkali-soluble resin, can impart an appropriate viscosity to the resulting composition, and is a solvent that can be easily removed by evaporation. preferable.
Specific examples of such solvents include ketones such as diethyl ketone, methyl butyl ketone, dipropyl ketone, and cyclohexanone; n-pentanol, 4-methyl-2-pentanol, cyclohexanol, diacetone alcohol, and the like. Alcohols; ether-based alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; saturated aliphatic mono such as acetic acid-n-butyl and amyl acetate Carboxylic acid alkyl esters; Lactic acid esters such as ethyl lactate and lactate-n-butyl; methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ester Ether acetate, and the like ether esters such as ethyl 3-ethoxypropionate. These solvents can be used alone or in combination of two or more.
In the present invention, the solvent is preferably 40 parts by weight or less, more preferably in the range of 5 to 30 parts by weight with respect to 100 parts by weight of the glass powder, from the viewpoint that the viscosity of the glass paste composition can be adjusted to a suitable range. Desirably included.

  The composition used in the present invention may further contain various additives such as a dispersant, a plasticizer, a silane coupling agent, a tackifier, a surface tension adjuster, a stabilizer, and an antifoaming agent as necessary. It may be added.

Preparation of the composition:
The composition for forming the film-forming material layer can be prepared by mixing the above components. Specifically, each of the above components can be prepared by kneading using a kneader such as a roll kneader, a mixer or a homomixer.
Moreover, the viscosity of a glass paste composition is 1,000-30,000 cp normally, Preferably it is 3,000-10,000 cp.

Production method of transfer film:
The transfer film of the present invention is formed, for example, by applying the composition described above on a support film, drying the coating film to form a film-forming material layer, and then forming a protective film layer on the film-forming material layer as necessary. Can be produced by applying (bonding, preferably thermocompression bonding). When the film forming material layer is a laminate, for example, a first layer can be formed on a support film, and a composition can be further applied on the first layer to form a second layer. Furthermore, it is good also as a laminated structure by forming a 1st layer on a support film, forming a 2nd layer on a protective film, and crimping | bonding both the 1st layer surface and 2nd layer surface. Examples of the laminated structure include, for example, a film forming material layer having a plurality of layers having different solubility in a developer. By adopting a laminated structure having different solubility in the developer, a pattern with more excellent shape and excellent dimensional accuracy can be obtained.

As a preferable method of applying the composition on the support film, a roll coater, a blade coater such as a doctor blade, from the viewpoint of efficiently forming a coating film having a large film thickness and excellent film thickness uniformity, Examples thereof include a coating method using a curtain coater or a wire coater. A part or all of the solvent is removed from the coating film by drying to form a film-forming material layer. The drying condition is preferably, for example, at 40 to 150 ° C. for about 0.1 to 30 minutes. The residual ratio of solvent in the film-forming material layer after drying (the solvent content in the film-forming material layer) is usually 10% by mass or less, and the film-forming material layer exhibits adhesiveness to the substrate and appropriate shape retention. In order to make it, 0.5-3 mass% is preferable.
The thickness of the film-forming material layer in the transfer film of the present invention is usually 20 to 200 μm, although it varies depending on the type and size of the member to be formed. In particular, when forming a partition, the film forming material layer preferably has a thickness of 70 to 200 μm, and when forming a dielectric layer, it is preferably 20 to 70 μm.

  Examples of protective films that may be provided on the surface of the film forming material layer include fluorine-containing resins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, and nylon. And cellulose. The thickness of the support film is, for example, 20 to 100 μm. Moreover, when providing a protective film, it is preferable that a protective film is a thing which peels easily in a support film and a protective film.

<Manufacturing method of PDP>
In the production method of the present invention, a PDP partition or dielectric layer is formed by [1] transfer step, [2] exposure step, [3] development step, and [4] firing step.
[1] Transfer process In the production method of the present invention, the film forming material layer is formed by a method of using the transfer film of the present invention and transferring the film forming material layer constituting the transfer film onto the surface of the substrate.
An example of the transfer process is as follows. After peeling off the protective film layer of the transfer film used as necessary, the transfer film is overlaid on the surface of the substrate so that the surface of the film-forming material layer is in contact with the transfer film. Thermocompression bonding. As a result, the film forming material layer is transferred and adhered to the surface of the substrate. Here, as the transfer conditions, for example, the surface temperature of the heating roller is 80 to 140 ° C., the roll linear pressure by the heating roller is 1 to 5 kg / cm, and the moving speed of the heating roller is 0.1 to 10.0 m / min. Can show. Further, the glass substrate may be preheated, and the preheat temperature can be set to 40 to 100 ° C., for example. The support film may be peeled off immediately after the transfer step or may be peeled off after the exposure step described later, but is preferably peeled off after the exposure step from the viewpoint of preventing oxygen inhibition.

[2] Exposure Step In this step, a latent image of a pattern is formed on the surface of the film forming material layer by a method of irradiating radiation such as ultraviolet rays through an exposure mask or a method of scanning with laser light. The exposure amount is usually 50 to 2000 mJ / cm ² , preferably 100 to 1000 mJ / cm ² . The radiation irradiation apparatus is not particularly limited, and examples thereof include a conventionally known ultraviolet irradiation apparatus used in a photolithography method and a conventionally known exposure apparatus used in manufacturing a semiconductor device or a liquid crystal display device. When laser light is used, the laser used is a solid laser, gas laser, semiconductor laser, liquid laser, etc., and its wavelength ranges from 350 nm in the ultraviolet region to about 600 nm in the visible light region. Can be used. Commonly used wavelengths in this region are 405 nm, 442 nm, 488 nm, 532 nm, and the like. Usually, after the exposure treatment, the support film present on the film-forming material layer is peeled off.

[3] Development Step In this step, the exposed film forming material layer is developed to reveal a pattern (latent image).
Here, as development processing conditions, depending on the type of alkali-soluble resin constituting the film-forming material layer, the type / composition / concentration of developer, development time, development temperature, development method (for example, dipping method, rocking) Method, shower method, spray method, paddle method), developing device and the like can be appropriately selected.
By this development step, a pattern composed of the film forming material layer remaining portion and the film forming material layer removing portion is formed.

[4] Firing step In this step, the pattern is fired to form a partition or a dielectric layer. By this step, the organic material in the remaining part of the film forming material layer is burned out, a glass sintered body is formed, and a panel material in which a partition wall or dielectric layer pattern is formed on the surface of the substrate can be obtained. .
Here, the temperature of the baking treatment needs to be a temperature at which the organic substance in the remaining part of the film forming material layer is burned out and the glass powder is fused, and is usually 400 to 600 ° C. The firing time is usually 10 to 90 minutes.

Below, the material used for each said process, various conditions, etc. are demonstrated.
<Board>
As the substrate material, for example, a plate-like member made of an insulating material such as glass, silicon, polycarbonate, polyester, aromatic amide, polyamideimide, polyimide or the like. For the surface of the plate-like member, chemical treatment with a silane coupling agent or the like, if necessary, plasma treatment; thin film formation treatment by an ion plating method, a sputtering method, a gas phase reaction method, a vacuum deposition method, etc. Such an appropriate pretreatment may be performed.

<Developer>
In the present invention, an alkaline developer or water is generally used in the development step. The type of the developer is selected according to the type of the binder resin, and an alkali developer is usually used when an alkali-soluble resin is used, and water is usually used when a water-soluble resin is used. Further, an alkaline developer may be used as a developer for the water-soluble resin.
As an active ingredient of the alkaline developer, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate , Inorganic such as potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia Alkaline compounds; tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropyl Triethanolamine, and organic alkaline compounds such as ethanol amine.
The alkaline developer used in the development step can be adjusted by dissolving one or more of the alkaline compounds in water. Here, the concentration of the alkaline compound in the alkaline developer is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass. In addition, after the development process with an alkali developer is performed, a washing process or a rinsing process with a poor solvent is usually performed.
In addition, when water is used as the developer, ultrapure water is usually used.

Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following, “part” means “part by mass”.
Moreover, Mw is the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) (brand name: HLC-8220GPC) by Tosoh Corporation. The GPC measurement conditions are as follows.
GPC column: (TSK guard column Super HZ-L manufactured by Tosoh Corporation)
Solvent: THF
Measurement temperature: 40 ° C

[Synthesis Example 1]
200 parts propylene glycol monomethyl ether, 30 parts lauryl methacrylate, 43 parts methyl methacrylate, 7 parts methacrylic acid, 20 parts (3-methyl-3-oxetanyl) methyl methacrylate and 1 part azobisisobutyronitrile in an autoclave with a stirrer The mixture was stirred and stirred at room temperature until uniform in a nitrogen atmosphere. Next, polymerization was carried out at 80 ° C. for 3 hours, and the polymerization reaction was further continued at 100 ° C. for 1 hour, followed by cooling to room temperature to obtain a polymer solution. The polymerization rate was 98%, and the Mw of the copolymer precipitated from this polymer solution (hereinafter referred to as “polymer (1)”) was 40,000.

[Synthesis Example 2]
120 parts of propylene glycol monomethyl ether, 60 parts of methyl methacrylate, 20 parts of lauryl methacrylate, 15 parts of methoxypolyethylene glycol methacrylate, 5 parts of methacrylic acid and 1 part of azobisisobutyronitrile were charged into an autoclave with a stirrer and a nitrogen atmosphere Under stirring at room temperature until homogeneous. Next, polymerization was carried out at 80 ° C. for 3 hours, and the polymerization reaction was further continued at 100 ° C. for 1 hour, followed by cooling to room temperature to obtain a polymer solution. The polymerization rate was 99%, and the Mw of the copolymer precipitated from the polymer solution (hereinafter referred to as “polymer (2)”) was 30,000.

[Synthesis Example 3]
200 parts of propylene glycol monomethyl ether, 60 parts of methoxydiethylene glycol monomethacrylate, 20 parts of acryloyl morpholine, 20 parts of 2-hydroxypropyl methacrylate and 0.5 part of azobisisobutyronitrile are charged into an autoclave equipped with a stirrer, under a nitrogen atmosphere The mixture was stirred at room temperature until uniform. Next, polymerization was carried out at 80 ° C. for 3 hours, and the polymerization reaction was further continued at 100 ° C. for 1 hour, followed by cooling to room temperature to obtain a polymer solution. The polymerization rate was 98%, and the Mw of the copolymer precipitated from this polymer solution (hereinafter referred to as “polymer (3)”) was 200,000.

[Preparation Example 1]
100 parts of B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ glass powder as glass powder, 25 parts of polymer (1) as alkali-soluble resin, 5 parts of trimethylolpropane triacrylate as multifunctional monomer, as radiation polymerization initiator 2,2-dimethoxy-1,2-diphenylethane-1-one 0.2 part and 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide 0.5 part, 3-methacryloxypropyltrimethoxysilane as adhesive By kneading 1 part, 0.01 part of 1-phenyl-3-methyl-4- (4-methylphenylazo) -5-oxypyrazole as a dye and 30 parts of propylene glycol monomethyl ether as a solvent, composition a1 (Hereinafter referred to as “composition (a-1)”).

[Preparation Example 2]
100 parts of B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ glass powder as the glass powder, 20 parts of the polymer (2) obtained in Synthesis Example 2 as the alkali-soluble resin, 1,2-as the radiation-sensitive acid generator 5 parts naphthoquinonediazide-4-sulfonic acid ester, 5 parts propylene glycol monooleate as plasticizer, 1 part 3-methacryloxypropyltrimethoxysilane as adhesive, 1-phenyl-3-methyl-4- (4- A composition a2 (hereinafter referred to as “composition (a-2)”) was prepared by kneading 0.01 part of methylphenylazo) -5-oxypyrazole and 30 parts of propylene glycol monomethyl ether as a solvent.

[Preparation Example 3]
100 parts of ZnO—B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ glass powder as glass powder, 25 parts of polymer (3) as water-soluble resin, 5 parts of trimethylolpropane triacrylate as multifunctional monomer, radiation polymerization started 2,2-dimethoxy-1,2-diphenylethane-1-one 0.2 parts and 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide 0.5 parts as an agent, 3-methacryloxypropyltri Composition was obtained by kneading 1 part of methoxysilane, 0.01 part of 1-phenyl-3-methyl-4- (4-methylphenylazo) -5-oxypyrazole as a dye, and 30 parts of propylene glycol monomethyl ether as a solvent. A product a3 (hereinafter referred to as “composition (a-3)”) was prepared.
[Preparation Example 4]
100 parts Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ glass powder as the glass powder, 25 parts polymer (1) as the alkali-soluble resin, 5 parts trimethylolpropane triacrylate as the polyfunctional monomer, 2,2-dimethoxy-1,2-diphenylethane-1-one 0.2 parts and 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide 0.5 parts as radiation polymerization initiator, 3-methacrylic as adhesive Kneading 1 part of loxypropyltrimethoxysilane, 0.01 part of 1-phenyl-3-methyl-4- (4-methylphenylazo) -5-oxypyrazole as a dye, and 30 parts of propylene glycol monomethyl ether as a solvent Thus, a composition a4 (hereinafter referred to as “composition (a-4)”) was prepared.

Example 1
(Production of transfer film)
The obtained composition (a-1) was coated on a support film (width 200 mm, length 30 m, thickness 50 μm) made of a polyethylene terephthalate (PET) film which had been subjected to a release treatment in advance by a roll coater. The solvent was removed by drying the formed coating film at 100 ° C. for 10 minutes to form a film-forming material layer (a-1) having a thickness of 160 μm. Further, a protective film (width 200 mm, length 30 m, thickness 38 μm) made of a polyethylene terephthalate (PET) film which has been subjected to a release treatment in advance is laminated on the film forming material layer (a-1) to form a film having a thickness of 160 μm. A transfer film having a material layer (hereinafter referred to as “transfer film (1)”) was produced. When the film-forming material layer of this transfer film (1) was transferred onto a glass substrate and the linear transmittance (Tp) at a wavelength of 405 nm was measured with a spectrophotometer (UV-2450: manufactured by Shimadzu Corporation), The value was 0.5%, and when the diffuse transmittance (Td) was measured, the value was 15%.

(Manufacture of partition walls for PDP)
[Transfer process]
The film-forming material layer (a-1) was superposed on the surface of the glass substrate with a dielectric layer for a 6-inch panel while peeling off the protective film, and thermocompression bonded with a heating roller. The pressure bonding conditions were such that the surface temperature of the heating roller was 90 ° C., the roll pressure was 4 kg / cm 2, and the moving speed of the heating roller was 0.5 m / min. As a result, the film forming material layer (a-1) was transferred and adhered to the surface of the glass substrate with a dielectric layer. When the thickness of this film-forming material layer (a-1) was measured, it was in the range of 160 μm ± 3 μm.

[Exposure process]
The film forming material layer (a-1) was irradiated with i-line (ultraviolet light having a wavelength of 365 nm) with an ultrahigh pressure mercury lamp through an exposure mask (a negative stripe pattern having a line width of 70 μm and a pitch of 200 μm). The irradiation amount was 1000 mJ / cm ² . After the exposure, the support film was peeled off from the film forming material layer (a-1).
[Development process]
The exposed film-forming material layer was subjected to a developing process by a shower method using a 0.3% by mass sodium carbonate aqueous solution (30 ° C.) as a developing solution. This removed the part of the uncured radiation-sensitive layer (a-1) that was not irradiated with ultraviolet rays, and developed. Next, washing with ultrapure water and drying were performed. Thereby, a partition pattern was formed.
[Baking process]
The glass substrate on which the partition pattern was formed was baked for 30 minutes in a baking furnace in a temperature atmosphere of 600 ° C. Thereby, the panel material by which a partition is formed in the surface of a glass substrate was obtained.

  The cross-sectional shape of the partition in the obtained panel material was observed with a scanning electron microscope, and the width and height of the bottom surface of the cross-sectional shape were measured. As a result, it was found that the bottom width was 70 μm ± 3 μm, the height was 120 μm ± 2 μm, the dimensional accuracy was extremely high, and a pattern with sharp edges of the partition walls could be formed. Moreover, the residue, pattern peeling, and deformation were not observed.

Example 2
The obtained composition (a-2) was coated on a support film (width 200 mm, length 30 m, thickness 50 μm) made of a polyethylene terephthalate (PET) film which had been subjected to a release treatment in advance by a roll coater. The solvent was removed by drying the formed coating film for 10 minutes at 100 ° C. to form a film-forming material layer (a-2) having a thickness of 160 μm. Further, a protective film (width: 200 mm, length: 30 m, thickness: 38 μm) made of a polyethylene terephthalate (PET) film which has been subjected to release treatment in advance is laminated on the film forming material layer (a-2) to form a film having a thickness of 160 μm. A transfer film having a material layer (hereinafter referred to as “transfer film (2)”) was produced. Using this transfer film (2), the linear transmittance (Tp) measured in the same manner as in Example 1 was 1%, and the diffuse transmittance (Td) was 25%.
In the same manner as in Example 1, except that the transfer film (2) was used instead of the transfer film (1) and an exposure mask (positive stripe pattern having a line width of 70 μm and a pitch of 200 μm) was used. A panel material having barrier ribs formed on the surface was prepared.

  The cross-sectional shape of the partition in the obtained panel material was observed with a scanning electron microscope, and the width and height of the bottom surface of the cross-sectional shape were measured. As a result, it was found that the bottom width was 70 μm ± 3 μm, the height was 120 μm ± 2 μm, the dimensional accuracy was extremely high, and a pattern with sharp edges of the partition walls could be formed. Moreover, the residue, pattern peeling, and deformation were not observed.

Example 3
The obtained composition (a-3) was coated on a support film (width 200 mm, length 30 m, thickness 50 μm) made of a polyethylene terephthalate (PET) film which had been subjected to a release treatment in advance by a roll coater. The solvent was removed by drying the formed coating film and the formed coating film at 100 ° C. for 5 minutes to form a film-forming material layer (a-3) having a thickness of 40 μm. Further, a protective film (width: 200 mm, length: 30 m, thickness: 38 μm) made of a polyethylene terephthalate (PET) film previously subjected to release treatment is laminated on the film forming material layer (a-3) to form a film having a thickness of 40 μm. A transfer film having a material layer (hereinafter referred to as “transfer film (3)”) was produced. Using this transfer film (3), the linear transmittance (Tp) measured in the same manner as in Example 1 was 2%, and the diffuse transmittance (Td) was 35%.
A partition wall was formed on the surface of the glass substrate in the same manner as in Example 1 except that the transfer film (3) was used instead of the transfer film (1) and ultrapure water (30 ° C.) was used as the developer. A panel material was prepared.

  The cross-sectional shape of the partition in the obtained panel material was observed with a scanning electron microscope, and the width and height of the bottom surface of the cross-sectional shape were measured. As a result, it was found that the bottom width was 70 μm ± 3 μm, the height was 20 μm ± 2 μm, the dimensional accuracy was extremely high, and the pattern with sharp edges of the partition walls could be formed. Moreover, the residue, pattern peeling, and deformation were not observed.

Comparative Example The obtained composition (a-4) was applied on a support film (width 200 mm, length 30 m, thickness 50 μm) made of a polyethylene terephthalate (PET) film which had been subjected to a release treatment in advance by a roll coater. A film was formed, the solvent was removed by drying the formed coating film at 100 ° C. for 10 minutes, and a film forming material layer (a-4) having a thickness of 160 μm was formed. Further, a protective film (width 200 mm, length 30 m, thickness 38 μm) made of a polyethylene terephthalate (PET) film which has been subjected to release treatment in advance is laminated on the film forming material layer (a-4) to form a film having a thickness of 40 μm. A transfer film having a material layer (hereinafter referred to as “transfer film (4)”) was produced. Using this transfer film (4), the linear transmittance (Tp) measured in the same manner as in Example 1 was 0%, and the diffuse transmittance (Td) was 0.5%.
A panel material in which partition walls were formed on the surface of the glass substrate was produced in the same manner as in Example 1 except that the transfer film (4) was used instead of the transfer film (1).
The cross-sectional shape of the partition in the obtained panel material was observed with a scanning electron microscope, and the width and height of the bottom surface of the cross-sectional shape were measured. As a result, the width of the bottom surface was 100 μm ± 5 μm, the height was 120 μm ± 5 μm, the dimensional accuracy was low, and only a pattern in which the leveling occurred at the center of the partition wall was obtained.

It is a schematic diagram which shows the cross-sectional shape of an alternating current type plasma display panel.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Glass substrate 3 Partition 4 Transparent electrode 5 Bus electrode 6 Address electrode 7 Fluorescent substance 8 Dielectric layer 9 Dielectric layer 10 Protective layer

Claims (4)

On the support film, it has a radiation-sensitive film-forming material layer containing glass powder and an organic component, and the linear transmittance (Tp) at a wavelength of 405 nm of the film-forming material layer is 0.01 to 10%, A transfer film having a diffuse transmittance (Td) of 1 to 50%. The transfer film of Claim 1 whose content rate of the glass powder in a film forming material layer is 50-90 mass%. The transfer film according to claim 1, wherein the film forming material layer has a thickness of 20 to 200 μm. The film-forming material layer in the transfer film according to claim 1 is transferred onto a substrate, the film-forming material layer is exposed to light to form a latent image of the pattern, and the film-forming material layer is developed to form a pattern. A method for manufacturing a plasma display panel, comprising a step of forming a member selected from a partition wall and a dielectric layer by forming and firing the pattern.

Images