JP2002025431A - Manufacturing method of partition-forming resin composite element, and plasma display panel substrate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a partition forming resin composite element and a plasma display panel substrate using the same, in which a plasma display panel substrate and high quality can be manufactured easily and with a high yield using fewer number of processes. SOLUTION: The partition-forming resin composite element which comprises a resin composite layer formed, containing (a) a polymer binder having ethylene unsaturated group, (b) a mold-releasing agent and (c) an inorganic material on a support body film, is laminated on a dielectric material layer of a laminate formed by laminating a substrate, an electrode material of a pattern form and a dielectric material layer in this order. Then the support body film is removed, and after a base body having a recess is pressure fitted, the base body having the recess is removed. Then the pattern of the partition forming resin composite corresponding to the recess of the base body is formed. Then by firing the pattern of the partition-forming resin composite, the plasma display panel substrate is manufactured.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition element for forming a barrier and a method for manufacturing a substrate for a plasma display panel (hereinafter abbreviated as PDP) using the same.

[0002]

2. Description of the Related Art A PDP has a barrier and a phosphor layer inside two insulating plates (hereinafter abbreviated as a glass plate) having a front plate on which a transparent electrode is formed and a rear plate on which a data electrode and a dielectric layer are formed. Consists of a formed structure. This barrier forms a cell structure that maintains a certain space between the orthogonal transparent electrode group and the data electrode group, and is filled with a rare gas such as Ne or Xe. As a result, a pixel that discharges and emits light from the phosphor is formed, and an image is displayed.

The above barrier has a function of preventing erroneous discharge between cells and obtaining a constant discharge section by its height, width and pattern gap.

Conventionally, a thick film printing method has been used as a method for forming the barrier. This method comprises printing a paste-like barrier material through a predetermined printing pattern mask using a screen printer on an insulating plate on which electrodes are formed, and then performing drying. Here, the height of the barrier is generally 100 μm in order to obtain good discharge and light emission.
The required barrier height is obtained by repeating the printing and drying steps 5 to 10 times since about m to 200 μm is required.

However, in recent years, displays have tended to become larger and pixels have become smaller (for example, a screen width of 40 inches or more and a barrier width of 100 μm or less and a height of 100 μm or more). , The accuracy of the printing pattern is poor due to elongation of the screen, etc., the life of the screen is short, the alignment of the printing pattern is difficult at the time of the above-mentioned overcoating, and there is a problem that a skilled printing worker is required. Barrier formation methods are being studied.

In particular, the photolithographic method using a photosensitive material widely used for forming an IC circuit board and the like is vigorously studied because a large and fine panel barrier can be formed with high precision. Have been.

For example, in Japanese Patent Application Laid-Open No. Hei 5-234514, a resin pattern is formed by laminating a photosensitive resin film on a substrate, exposing it through a predetermined pattern mask, and then removing the unexposed portion by development. A method of forming a barrier by embedding a barrier material between the resin pattern and the resin pattern and removing the resin pattern after drying with an alkaline stripping solution has been proposed.In particular, this method is described as an additive method. are doing.

However, the above-described additive method has problems such as a large number of steps, damage to a substrate during development, and the like. In addition, a barrier material is buried between resin patterns, and after drying, the resin is dried. In the step of stripping and removing the pattern with an alkali stripper, particularly when the resin pattern is swollen and stripped by the alkali stripper, the barrier embedded between the resin pattern and the resin pattern may be deformed due to the swelling stress. Paste-like barrier materials used in existing printing methods, etc., which cannot be obtained with a satisfactory shape due to peeling or partial loss with the pattern, include glass, inorganic filler, resin binder, Made of organic solvent, especially ethylcellulose, nitrocellulose, etc. are used as resin binder to keep shape Because poor in alkali resistance, there is a problem between such barriers satisfactory shape tends collapsed shape alkaline stripping solution to a resin pattern peeled off can not be obtained. Also, if a dielectric paste is applied over the entire surface of the substrate on which the electrodes are formed and fired to form a dielectric layer, and then a barrier is formed by a photo process, the substrate shrinks during firing of the dielectric paste, Not only is it difficult to align the photomask in the photo process, but also because the shrinkage of the substrate always occurs with an error, it is not suitable for stable barrier formation in mass production, where a barrier must always be formed at the same position.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a barrier-forming resin composition element which can easily produce a high-quality substrate for a plasma display panel in a small number of steps and with good yield. It is another object of the present invention to provide a method of manufacturing a plasma display panel substrate that can easily manufacture a high-quality plasma display panel substrate with a small number of steps and with high yield.

[0010]

The present invention comprises a support film containing (a) a polymer binder having an ethylenically unsaturated group, (b) a release agent, and (c) an inorganic material. The present invention relates to a barrier-forming resin composition element having a resin composition layer. Further, the present invention also provides a support film after laminating the barrier-forming resin composition element on a dielectric material layer of a laminate in which a substrate, a patterned electrode material and a dielectric material layer are sequentially laminated. After the substrate having the concave portion is pressed thereon, the substrate having the concave portion is removed, and a pattern of the barrier-forming resin composition corresponding to the concave portion of the substrate having the concave portion is formed. The present invention relates to a method for producing a substrate for a plasma display panel, which comprises firing a pattern of a resin composition for a plasma display panel. Further, the present invention also provides a support film after laminating the barrier-forming resin composition element on a dielectric material layer of a laminate in which a substrate, a patterned electrode material and a dielectric material layer are sequentially laminated. After the substrate having the concave portion is pressed thereon, the substrate having the concave portion is removed to form a pattern corresponding to the concave portion of the substrate having the concave portion. The present invention relates to a method for manufacturing a substrate for a plasma display panel, which comprises baking a pattern of a resin composition for forming a barrier and a multicolor pattern after forming a color pattern.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The barrier-forming resin composition element of the present invention comprises, on a support film, (a) a polymer binder having an ethylenically unsaturated group, (b) a release agent, and (c) a release agent.
It has a resin composition layer containing an inorganic material. Examples of (a) the polymer binder having an ethylenically unsaturated group in the resin composition layer of the present invention include a functional group such as a carboxyl group, a hydroxyl group, an amino group, an isocyanate group, an oxirane ring, and an acid anhydride. The vinyl copolymer has at least one ethylenically unsaturated group, an oxirane ring,
Radical polymerizable copolymers having an ethylenically unsaturated group on the side chain obtained by subjecting a compound having one functional group such as an isocyanate group, a hydroxyl group, and a carboxyl group to an addition reaction are exemplified.

The carboxyl group, hydroxyl group, amino group,
Oxirane ring, as an essential vinyl monomer used for producing a vinyl copolymer having a functional group such as an acid anhydride,
For example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, cinnamic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylamide, methacrylamide, ethyl isocyanate methacrylate, glycidyl acrylate, glycidyl methacrylate And vinyl monomers having a functional group such as a carboxyl group such as maleic anhydride, a hydroxyl group, an amino group, an oxirane ring, and an acid anhydride. These are used alone or in combination of two or more.

For the production of the vinyl copolymer, other vinyl monomers can be copolymerized if necessary. Other vinyl monomers, for example, methyl acrylate, methyl methacrylate, ethyl acrylate,
Ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, iso-propyl acrylate, iso-propyl methacrylate, n-butyl acrylate,
N-butyl methacrylate, iso-butyl acrylate,
Iso-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, ter acrylate
t-butyl, tert-butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate,
Octyl methacrylate, nonyl acrylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl acrylate, methacrylic acid Octadecyl, eicosyl acrylate, eicosyl methacrylate, docosyl acrylate, docosyl methacrylate, cyclopentyl acrylate, cyclopentyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, cycloheptyl acrylate, cycloheptyl methacrylate, benzyl acrylate, benzyl methacrylate Benzyl, phenyl acrylate, phenyl methacrylate, methoxyethyl acrylate, methacrylate Shiechiru, methoxy acrylic acid diethylene glycol methacrylate methoxy diethylene glycol, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate,
Methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, acrylic acid 2-chloroethyl, 2-chloroethyl methacrylate, 2-fluoroethyl acrylate, 2-fluoroethyl methacrylate, 2-cyanoethyl acrylate, 2-cyanoethyl methacrylate, styrene, α-methylstyrene, vinyl toluene, vinyl chloride, acetic acid Examples include vinyl, N-vinylpyrrolidone, fudadiene, isoprene, chloroprene, acrylonitrile, methacrylonitrile, and the like.
These are used alone or in combination of two or more.

As a compound having at least one ethylenically unsaturated group to be subjected to an addition reaction to a vinyl copolymer and one functional group such as an oxirane ring, an isocyanate group, a hydroxyl group, a carboxyl group, an amino group, and an acid anhydride. Is, for example, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, α-ethyl acryl glycidyl, crotonyl glycidyl ether, glycidyl crotonate, glycidyl isocrotonic acid, ethyl isocyanate methacrylate, 2-hydroxyethyl acrylate, 2-hydroxymethacrylate Ethyl, acrylic acid,
Examples include methacrylic acid, maleic acid, fumaric acid, itaconic acid, cinnamic acid, acrylamide, methacrylamide, and maleic anhydride. These are used alone or in combination of two or more.

The weight-average molecular weight of the polymer binder having an ethylenically unsaturated group (a) in the present invention (measured by gel permeation chromatography and converted to standard polystyrene) is from 1,000 to 300,000. And more preferably 5,000 to 150,000. This weight average molecular weight is 1,000
If it is less than 300,000 or more, barrier formability tends to decrease.

In the present invention, the (a) ethylenically unsaturated group concentration of the polymer binder having an ethylenically unsaturated group is as follows:
Is preferably set to 3.0 × ¹⁰ -4 ~6.0 × ^{10 -3} mol / g, more preferably to 6.0 × ¹⁰ -4 ~5.5 × ^{10 -3} mol / g, 9 × 10 ^{-4 to} 5.
It is particularly preferred to be 0 × 10 ⁻³ mol / g. If the ethylenically unsaturated group concentration is less than 3.0 × 10 ⁻⁴ mol / g, the strength of the barrier portion tends to decrease, and
If it exceeds 10 ⁻³ mol / g, gelation tends to occur when (a) the polymer binder having an ethylenically unsaturated group is produced. The glass transition temperature of (a) the polymer binder having an ethylenically unsaturated group in the present invention is preferably 30 ° C. or lower, more preferably 25 ° C. or lower, and particularly preferably 20 ° C. or lower. Preferably 15 to
It is very preferable that the temperature be -100 ° C. (A) When the glass transition temperature of the polymer binder having an ethylenically unsaturated group exceeds 30 ° C., a substrate having a concave portion, which will be described later, is pressed into contact with the resin composition layer, and then the substrate having a concave portion is formed. In the step of forming a pattern corresponding to the concave portion of the substrate having the concave portion, the concave portion is not sufficiently filled with the resin composition layer, and the pattern formability tends to decrease.

As the organic material constituting the resin composition layer of the present invention, a photopolymerization initiator which generates free radicals by irradiating with active light is used for the purpose of improving the barrier strength and the shape retention before firing. Can be. For the same purpose, a thermal polymerization initiator which generates free radicals by heating can be used.

Examples of photopolymerization initiators that generate free radicals upon irradiation with active light include aromatic ketones (benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N '-Tetraethyl-4,4'-diaminobenzophenone, 4-
Mesoxy-4'-dimethylaminobenzophenone, 2-
Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,
2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1-
(4- (methylthio) phenyl) -2-morpholinopropanone-1,2,4-diethylthioxanthone, 2-
Ethyl anthraquinone, phenanthrene quinone, etc.), benzoin ether (benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, etc.), benzoin (methyl benzoin, ethyl benzoin, etc.), benzyl derivative (benzyl dimethyl ketal, etc.), 2,4,5- Triaryl imidazole dimer (2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,
5-bis (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl)-
4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-bis (p-methoxyphenyl) -5-phenylimidazole dimer, -(2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer and the like, and acridine derivatives (9-phenylacridine,
1,7-bis (9,9'-acridinyl) heptane and the like
And the like. These are used alone or in combination of two or more.

Examples of the thermal polymerization initiator that generates free radicals upon heating include acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, 2-chlorobenzoyl peroxide, and peroxide. 3-chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide,
2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1
-Hydroperoxide, pertriphenylacetic acid-tert
-Butyl, tert-butyl hydroperoxide, tert-butyl formate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl per-4-methoxyacetate, perN- (3
-Toluyl) peroxides such as tert-butyl carbamate, 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo (methylethyl) di Acetate, 2,2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis (2-amidinopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutylamide, 2,2'-
Azobisisobutyronitrile, 2,2'-azobis-2
-Methyl methyl propionate, 2,2'-dichloro-
2,2'-azobisbutane, 2,2'-azobis-2-
Methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, 1,1'-azobis (sodium 1-methylbutyronitrile-3-sulfonate), 2- (4-methylphenylazo) -2-methylmalonodi Nitrile, 4,4 '
-Azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-methylmalonodinitrile, 2
-(4-bromophenylazo) -2-allylmalonodinitrile, 2,2'-azobis-2-methylvaleronitrile, dimethyl 4,4'-azobis-4-cyanovalerate,
2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobiscyclohexanenitrile, 2,
2'-azobis-2-propylbutyronitrile, 1,
1'-azobis-1-chlorophenylethane, 1,1 '
Azobis-1-cyclohexanecarbonitrile, 1,
1'-azobis-1-cycloheptanenitrile, 1,
1'-azobis-1-phenylethane, 1,1'-azobiscumene-4-nitrophenylazobenzyl cyanoacetate ethyl, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1 ' Azobis-1,2-diphenylethane, poly (bisphenol A-4,4'-azobis-4-cyanopentanoate), azo such as poly (tetraethylene glycol-2,2'-azobisisobutyrate) Compounds, 1,4-bis (pentamethylene) -2
-Tetrazene, 1,4-dimethoxycarbonyl-1,4
-Diphenyl-2-tetrazene, benzenesulfonyl azide and the like. These are used alone or in combination of two or more.

A plasticizer can be used in the organic material constituting the resin composition layer of the present invention, if necessary, for the purpose of, for example, exhibiting flexibility when used as an element. Known plasticizers can be used, and examples thereof include polyethylene glycol diacetate and polypropylene glycol diacetate.

The (b) release agent in the resin composition layer of the present invention includes, for example, fatty acids such as stearic acid, cystic acid, and palmitic acid; fatty acid metal salts such as calcium stearate and zinc stearate; And a surfactant such as a phosphate ester. These are used alone or in combination of two or more.

The inorganic material (c) in the resin composition layer of the present invention includes, for example, known glass powder such as low melting point glass, titanium oxide, aluminum oxide, magnesium oxide, calcium oxide, zinc oxide, iron oxide, and iron oxide. chromium,
Examples thereof include copper oxide and zirconium oxide, and these can be used alone or in combination of two or more. As a glass composition of the above glass powder, a combination of lead oxide, boron oxide, silicon oxide, zinc oxide, barium oxide, bismuth oxide, calcium oxide, aluminum oxide, zirconium oxide, lithium oxide, sodium oxide, potassium oxide, etc. No. The softening point of these glass powders is 350 to 650 ° C, and the particle size is 0.1 to
A thickness of 30 μm is preferable in terms of workability, barrier strength, and the like. In the inorganic material, the content of the glass powder is from 30 to 30 from the viewpoint of the strength of the formed barrier and the shape retention during firing.
It is preferably 75% by weight.

The amount of the polymer binder (a) having an ethylenically unsaturated group in the resin composition layer of the present invention is 1 to 100 parts by weight of the total amount of the inorganic material contained in the resin composition layer. 200 parts by weight, preferably 2 to 15 parts by weight.
It is more preferably 0 parts by weight, more preferably 3 to 130 parts by weight, more preferably 4 to 100 parts by weight, particularly preferably 5 to 90 parts by weight, and more preferably 5 to 80 parts by weight. It is very preferable to use a part.
If the amount is less than 1 part by weight, the strength of the barrier before firing tends to decrease, and if it exceeds 200 parts by weight, the volume shrinkage of the barrier after firing tends to increase, and the barrier formed on the substrate tends to increase. Tend to peel off.

The amount of the photopolymerization initiator that generates free radicals upon irradiation with actinic light is preferably 0.01 to 30 parts by weight based on 100 parts by weight of the total amount of the component (a). More preferably, it is 1 to 20 parts by weight.
When the amount is less than 0.01 part by weight, the photocuring of the organic material constituting the resin composition layer tends to be insufficient. Active light absorption tends to increase and the internal light curing tends to be insufficient.

When using a thermal polymerization initiator which generates free radicals by heating, the amount of the component (a) is 1
The amount is preferably 0.1 to 20 parts by weight, more preferably 0.15 to 10 parts by weight, based on 00 parts by weight. If the amount is less than 0.1 part by weight, the thermosetting of the resin composition layer tends to be insufficient, and if it exceeds 10 parts by weight, the storage stability in the case of forming an element tends to decrease. .

The compounding amount of the plasticizer in the resin composition layer of the present invention is preferably 0 to 20 parts by weight based on 100 parts by weight of the total amount of the inorganic material (c) contained in the resin composition layer. More preferably, it is 0 to 10 parts by weight. When the compounding amount exceeds 20 parts by weight, when the element is used, the resin composition layer tends to exude from an end portion, and storage stability tends to decrease.

The amount of the release agent (b) in the resin composition layer of the present invention is 0.05 to 20 parts by weight based on 100 parts by weight of the total amount of the inorganic material (c) contained in the resin composition layer. It is more preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight. If the compounding amount is less than 0.05 parts by weight, the substrate having the concave portion is pressed after the substrate having the concave portion is brought into contact with the resin composition layer, and then the substrate having the resin composition layer and the concave portion is removed when the substrate having the concave portion is removed. When the amount exceeds 20 parts by weight, defects tend to occur in the pattern shapes of the dielectric layer and the barrier after firing.

The resin composition layer in the present invention is formed into a uniformly dispersed solution by dissolving or mixing each of the above-mentioned components constituting the resin composition layer in a solvent capable of dissolving or dispersing. , Applied and dried.

As the support film in the present invention,
Chemically and thermally stable, and, furthermore, composed of a flexible substance, for example, polyethylene terephthalate, polycarbonate, polyethylene, polypropylene and the like, among them, polyethylene terephthalate, polyethylene is preferred, polyethylene terephthalate is preferred More preferred. The thickness of the support film is 5 to 100 μm.
m, more preferably 10 to 80 μm.

Examples of the solvent capable of dissolving or dispersing the above components constituting the resin composition layer include, for example, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like.
Methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, γ-butyrolactone, N-
Methylpyrrolidone, dimethylformamide, tetramethylsulfone, diethylene glycol dimethyl ether,
Examples thereof include diethylene glycol monobutyl ether, chloroform, methylene chloride, methyl alcohol, and ethyl alcohol. These are used alone or in combination of two or more.

As the coating method, a known method can be used, and examples thereof include a knife coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method, and a curtain coating method. The drying temperature is 6
The temperature is preferably from 0 to 130 ° C, and the drying time is preferably from 3 minutes to 1 hour. The thickness of the resin composition layer in the present invention is preferably 20 to 200 μm, in order to minimize luminous efficiency and unnecessary resin composition layer remaining on the substrate when PDP is used, and 30 to 200 μm.
More preferably, it is 150 μm.

In the resin composition element for forming a barrier according to the present invention, a cover film may be further laminated on the resin composition layer. As the cover film, polyethylene, polypropylene, polyethylene terephthalate,
A film made of polycarbonate or the like and having a thickness of about 5 to 100 μm is exemplified. The barrier-forming resin composition element thus obtained can be stored in a roll or stored or used.

Hereinafter, an example of the method for manufacturing a PDP substrate of the present invention will be described. The substrate used in the present invention is not particularly limited, and examples thereof include a ceramic plate, a plastic plate, a glass plate, and a metal plate. On this substrate, an insulating layer,
An electrode, a protective layer and the like may be provided, and it is preferable that the substrate is a laminate in which a substrate, a patterned electrode material, and a dielectric material layer are sequentially laminated.

In the present invention, the method of laminating the barrier-forming resin composition element on a substrate includes, when a cover film or a support film is in contact with the resin composition layer, the cover film Alternatively, after removing the support film, the film can be pressed on a substrate with a pressure roll.

The pressing roll is heated so that it can be heated and pressed.
Means may be provided.
The heating temperature is preferably 10 to 200 ° C., and 2
The temperature is more preferably 0 to 180 ° C, and 30 to 160 ° C.
It is particularly preferable that the temperature is set to ° C. This heating temperature is 10 ° C
If it is less than 30, the adhesiveness between the resin composition layer and the substrate tends to decrease.
If the temperature exceeds 200 ° C., the resin composition layer is formed.
Organic materials tend to thermally decompose. Also, when heating and pressing
Is 50 to 1 × 10⁵N / m
And preferably 2.5 × 10²~ 5 × 10⁴N / m
More preferably 5 × 10²~ 4 × 10⁴N / m
It is particularly preferred that This pressure is 50 N /
If it is less than m, the adhesion between the resin composition layer and the substrate decreases.
Tend to 1 × 10 ⁵If N / m is exceeded, the substrate will break
Tend to be.

If the barrier-forming resin composition element is heated as described above, it is not necessary to preheat the substrate, but from the viewpoint of further improving the adhesion between the resin composition layer and the substrate, the substrate is heated. It is preferable to perform a preheat treatment. The preheating temperature at this time is preferably 30 to 180 ° C., and the preheating time is preferably 0.5 to 20 minutes.

In the present invention, as a method of pressing a substrate having a concave portion in contact with a resin composition layer, when a support film is present in contact with the resin composition layer, the support film is used. After the removal, pressing with a pressure roll may be performed so that the resin composition layer is in contact with the surface of the substrate having the concave portions on which the concave portions are provided.

The substrate having a concave portion used in the present invention comprises:
Sheets made of materials such as metals, ceramics, glass, and plastics, rolls, and the like provided with concave portions on the surface can be used, and these substrates are integrally formed of a material having a single composition. Or a combination of a plurality of portions made of the same type of material having different compositions or a combination of a plurality of portions made of different types of material. From the viewpoint of workability when removing the substrate having the concave portion from the resin composition layer embedded in the concave portion, a sheet made of a flexible plastic or the like having a concave portion on the surface is preferable.

The pressing roll is heated so that it can be heated and pressed.
Means may be provided.
The heating temperature is preferably 10 to 200 ° C., and 2
The temperature is more preferably 0 to 180 ° C, and 30 to 160 ° C.
It is particularly preferable that the temperature is set to ° C. This heating temperature is 10 ° C
If it is less than 3, there is a tendency that the filling property of the (A) layer into the concave portion is reduced.
Yes, if the temperature exceeds 200 ° C., the resin composition layer
The machine material tends to thermally decompose. Also, the pressure at the time of thermocompression bonding
The contact pressure is 50 to 1 × 10 in linear pressure.⁵N / m
Preferably 2.5 × 10²~ 5 × 10⁴N / m
And more preferably 5 × 10²~ 4 × 10⁴N / m
Is particularly preferred. This pressure is not more than 50N / m
When full, the filling property of the resin composition layer into the concave portion tends to decrease.
There is 1 × 10 ⁵If it exceeds N / m, the substrate will be destroyed.
Tend to Further, the filling property of the resin composition layer into the concave portion is improved.
Laminate the barrier forming resin composition for further improvement
It is preferable to pre-heat the substrate having a recess and a recess.
Good. The preheating temperature at this time should be 30 to 180 ° C.
Preferably, the preheating time is 0.5 to 20 minutes.
Is preferred.

Further, for the same purpose, the above-mentioned press-bonding and heat-pressing operations can be performed under a reduced pressure of 5 × 10 ⁴ Pa or less. After the completion of crimping, 30 to 200
It can also be heated in the range of 1 to 120 minutes. In this way, the resin composition layer can be uniformly filled in the recess.

In the present invention, after filling the resin composition layer into the concave portions, the substrate having the concave portions is removed to form a pattern corresponding to the concave portions. And the like. Further, for the purpose of improving workability, a method of physically peeling the substrate having the concave portion using a force such as static electricity or suction force may be used.

Further, in the present invention, from the viewpoint of improving the barrier strength and the shape retention of the pattern corresponding to the concave portion before firing, it is also possible to perform irradiation with active light by a high-pressure mercury lamp or heating. At this time, the irradiation amount of the actinic ray is
Usually, it is 0.2 to 10 × 10 ⁴ J / m ² , and heating can be performed during irradiation. The heating temperature is 6
0 to 200 ° C, preferably 100 to 180 ° C
Is more preferable. The heating time is 15 to
Preferably, it is 90 minutes. In this manner, a pattern corresponding to the concave portion of the substrate having the concave portion can be formed.

For the purpose of removing organic components from the resin composition for barrier formation comprising the resin composition layer and improving the strength, gas impermeability, etc., the resin composition for barrier formation comprising the resin composition layer is fired. can do. The firing temperature and time are usually 350 to 650 ° C. and 0.5 to 20 hours. As described above, a PDP substrate having a barrier can be obtained, and further, a multicolor pattern can be formed on the side and bottom surfaces of the barrier or on the dielectric layer laminated on the substrate.

When a multicolor pattern is formed, a material containing a phosphor and an organic material is used. For example, a phosphor containing red, green and blue light-emitting phosphors each containing one color is contained. And a photosensitive resin composition. The photosensitive resin composition containing a phosphor used when forming a multicolor pattern is not particularly limited as long as it is a photosensitive resin composition containing a phosphor as an essential component, for example, a binder polymer, A photopolymerizable unsaturated compound having an ethylenically unsaturated group, a photoinitiator which generates free radicals upon irradiation with actinic light, and a phosphor are preferred. Such components include, for example, JP-A-9-265906. JP, JP-A-9-288973, JP-A-10-9
No. 2312, JP-A-10-92313, and JP-A-10-228103. Further, the blending amounts thereof and the additives can be used in accordance with the above-mentioned publication.

As a method of forming a multicolor pattern on the side and bottom surfaces of the barrier or on the dielectric layer, for example, each of phosphors containing red, green and blue light-emitting phosphors, each containing one color, respectively. Using the photosensitive resin composition, the layer of the photosensitive resin composition containing the phosphor described above is made to follow the inner surface of the recess formed by the barrier side surface and the bottom surface or the dielectric layer, and this is repeated for each color. And a method of forming a multicolor pattern including a phosphor emitting red, green, and blue light and an organic material. As a method of laminating each layer of the photosensitive resin composition containing the phosphor so as to follow the side surface and bottom surface of the barrier or the inner surface of the concave portion formed by the dielectric layer, for example, a substrate on which a barrier is formed above,
Examples include a method of directly applying, drying and laminating, and a method of laminating a photosensitive resin composition containing a phosphor as a photosensitive element by a known method.

After a layer of a photosensitive resin composition containing a phosphor is uniformly laminated on the side and bottom surfaces of the barrier or the inner surface of the recess formed by the dielectric layer so as to follow the layer uniformly, an actinic ray is applied via a photomask. Is imagewise irradiated, and development is performed by a known method such as spraying, rocking immersion, brushing, and scraping using a known developer to remove unnecessary portions.

The above-described steps from lamination to development are repeated for each color to form a multicolor pattern composed of a layer of a photosensitive resin composition containing a phosphor that emits red, green and blue. Can be. For the purpose of removing the organic components of the multicolor pattern, the multicolor pattern formed on the side and bottom surfaces of the barrier or the inner surface of the concave portion formed by the dielectric layer can be fired. The firing temperature and time are usually 350 to 650 ° C. and 0.5 to 20 hours.

In addition, in that the manufacturing process of the PDP substrate can be simplified, after the barrier-forming resin composition element is laminated on the substrate, the support film is removed, and the base having the concave portion is formed of the resin composition. After being pressed in contact with the layer, the substrate having the concave portion was removed to form a pattern corresponding to the concave portion of the substrate having the concave portion, and then a multicolor pattern was formed on the inner surface of the concave portion of the pattern. Thereafter, the multi-color pattern and the barrier-forming resin composition comprising the resin composition layer can be simultaneously fired. In this case, as a method of forming a pattern of a barrier-forming resin composition composed of a resin composition layer, a method of forming a multicolor pattern, and a method of baking,
The method described above can be used.

[0049]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Production Example 1 [Polymer binder solution having ethylenically unsaturated group (a-
Preparation of 1)] A flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer was charged with (1) shown in Table 1, and the temperature was raised to 80 ° C. under a nitrogen gas atmosphere. 8
While maintaining the temperature at 0 ° C. ± 2 ° C., (2) shown in Table 1 was dropped uniformly over 4 hours. After the dropwise addition of (2), stirring was continued at 80 ° C. ± 2 ° C. for 6 hours, and then (3) shown in Table 1 was added.
After adding (3), the temperature of the reaction system was raised to 100 ° C., and (4) shown in Table 1 was added dropwise over 0.5 hour. After the dropwise addition of (4), stirring was continued at 100 ° C. for 20 hours, and then cooled to room temperature, and a polymer bond having an ethylenically unsaturated group having a weight average molecular weight of 25,000 and a glass transition temperature of about 10 ° C. Agent solution (solid content: 40.1% by weight, ethylenically unsaturated group concentration: 1.75 × 10 ⁻³ mol / g) (a-1) was obtained.

[0051]

[Table 1] Comparative Production Example 1 [Preparation of Polymer Solution (a-2)] In a flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer,
(1) shown in Table 2 was charged, and 80 ° C. in a nitrogen gas atmosphere.
Temperature and keeping the reaction temperature at 80 ° C. ± 2 ° C.
(2) shown in the above was dropped uniformly over 4 hours. After the dropwise addition of (2), stirring was continued at 80 ° C. ± 2 ° C. for 6 hours, and a solution of a binder polymer having a mass average molecular weight of 30,000 and a glass transition temperature of about 0 ° C. (solid content: 40.1% by weight) (a- 2)
I got

[0052]

[Table 2] Production Example 2 [Preparation of Film-Containing Polymer Solution (c-1) for Photosensitive Resin Composition Containing Phosphor] Stirrer, Reflux Cooler,
Table 3 was added to a flask equipped with an inert gas inlet and a thermometer.
(1) shown in Table 3 was heated to 80 ° C. in a nitrogen gas atmosphere, and (2) shown in Table 3 was uniformly dropped over 4 hours while maintaining the reaction temperature at 80 ° C. ± 2 ° C. After dripping, 80
Stirring was continued for 6 hours at a temperature of ± 2 ° C, and the weight average molecular weight was 80,
000, a film-forming polymer solution for photosensitive resin composition (solid content: 40% by weight) (c-1) containing a phosphor having an acid value of 130 mgKOH / g was obtained.

[0053]

[Table 3] Production Example 3 [Production of Solution (A-1) for Resin Composition Layer] The materials shown in Table 4 were mixed for 3 hours using a ball mill to prepare a solution (A-1) for resin composition layer.

[0054]

[Table 4] Comparative Production Example 2 [Production of Resin Composition Layer Solution (A-2)] The materials shown in Table 5 were mixed for 3 hours using a ball mill to prepare a resin composition layer solution (A-2).

[0055]

[Table 5] Production Example 4 [Preparation of Photosensitive Element (P-1) Having Layer of Photosensitive Resin Composition Containing Phosphor] The materials shown in Table 6 were mixed for 15 minutes using a Raikai machine to obtain a red phosphor. A solution of a photosensitive resin composition containing was prepared.

[0056]

[Table 6] The obtained solution is uniformly coated on a polyethylene terephthalate film having a thickness of 20 μm, and dried with a hot air convection dryer at 80 to 110 ° C. for 10 minutes to remove the solvent, and to obtain a photosensitive material containing a red phosphor. A layer of the conductive resin composition was formed. The thickness of the obtained layer of the photosensitive resin composition containing the red phosphor after drying was 50 μm. Next, on the layer of the photosensitive resin composition containing the red phosphor, a polyethylene film having a thickness of 25 μm is laminated as a cover film, and has a layer of the photosensitive resin composition containing the red phosphor. Photosensitive element (P-1)
I got

Production Example 5 [Preparation of Photosensitive Element (P-2) Having Layer of Photosensitive Resin Composition Containing Phosphor] The materials shown in Table 7 were mixed for 15 minutes using a Raikai machine to obtain a green color. A solution of the photosensitive resin composition containing the phosphor was prepared.

[0058]

[Table 7] Hereinafter, in the same manner as in Production Example 4, a layer of a photosensitive resin composition containing a green phosphor is formed, and a photosensitive element (P) having a layer of a photosensitive resin composition containing a green phosphor is formed.
-2) was obtained. The thickness of the obtained layer of the photosensitive resin composition containing the green phosphor after drying was 50 μm.

Production Example 6 [Preparation of Photosensitive Element (P-3) Having Layer of Photosensitive Resin Composition Containing Phosphor] The materials shown in Table 8 were mixed for 15 minutes using a Raikai machine, and were mixed with blue. A solution of the photosensitive resin composition containing the phosphor was prepared.

[0060]

[Table 8] Hereinafter, in the same manner as in Production Example 4, a layer of the photosensitive resin composition containing the blue phosphor is formed, and the photosensitive element (P) having the layer of the photosensitive resin composition containing the blue phosphor is formed.
-3) was obtained. The thickness of the obtained layer of the photosensitive resin composition containing the blue phosphor after drying was 50 μm.

Production Example 7 [Film having embedded layer (thermoplastic resin layer) (U
-1) Preparation] A resin solution composed of the materials shown in Table 9 was mixed with 2
0 μm thick polyethylene terephthalate film uniformly coated, dried with a hot air convection dryer at 80 to 110 ° C. for 10 minutes to remove the solvent, a 25 μm thick polyethylene film was laminated as a cover film, A film having an embedded layer (thermoplastic resin layer) was produced. The thickness of the obtained embedded layer (thermoplastic resin layer) was 60 μm.

[0062]

[Table 9] Example 1 [Production of barrier-forming resin composition element (i)] The solution (A-1) for a resin composition layer obtained in Production Example 3 was used in an amount of 50 µl.
m, was uniformly coated on a polyethylene terephthalate film having a thickness of m, and dried by a hot air convection dryer at 110 ° C. for 10 minutes to remove the solvent, thereby forming a resin composition layer. The thickness of the obtained resin composition layer was 48 μm. Next, a polyethylene film having a thickness of 25 μm was further laminated on the resin composition layer as a cover film,
A barrier-forming resin composition element (i) was prepared.

Example 2 The electrode obtained in Example 1 was formed on a glass substrate on which electrodes were formed.
Polyethylene for the resin composition element (i) for forming a barrier
While peeling the film, so that the resin composition layer is in contact
Laminator (HLM-1 manufactured by Hitachi Chemical Co., Ltd.)
500 type), laminating temperature 100 ° C, laminating
Nate speed is 0.5m / min, crimping pressure (cylinder pressure)
Is 4 × 10⁵Pa (Thickness 3 mm, length 100 mm x width 1
Since a substrate of 00 mm was used, the linear pressure at this time was 9.8 ×
10³N / m), polyethylene terephthalate fill
Laminated through a system. Next, the laminated barrier forming resin set
Polyethylene terephthalate of the element (i)
Peel the film and place a rectangular cross-section on the resin composition layer.
Base material having a concave portion made of polycarbonate
Body thickness 300μm, length 100mm x width 100mm, concave
Part opening width 70 μm, convex part width 150 μm, concave part height 1
50 μm, arrangement of unevenness is stripe shape), and concave portion is resin
A laminator (Hitachi Chemical Industries, Ltd.)
(Trade name: HLM-1500 type)
Nate temperature 100 ° C, laminating speed 0.5m /
Min., Crimping pressure (cylinder pressure) is 4 × 10⁵Pa (thickness
Used a substrate of 3 mm, length 100 mm × width 100 mm.
Therefore, the linear pressure at this time is 9.8 × 10³N / m)
Was. Next, use Toshiba UV irradiator manufactured by Toshiba Electric Materials Co., Ltd.
3 × 10⁴J / m ²Purple
External radiation was applied.

Next, the substrate having the concave portion on the resin composition layer was peeled off and removed to obtain a sample of the pattern of the barrier-forming resin composition corresponding to the concave portion of the substrate having the concave portion. The cross section of the obtained sample was examined by a stereoscopic microscope and SEM.
And the pattern of the barrier-forming resin composition before firing was evaluated. The results are shown in Table 10. The evaluation criteria are as follows. ：: The pattern of the barrier-forming resin composition was well formed corresponding to the concave shape of the substrate having the concave portions. ×: The pattern of the barrier-forming resin composition is deformed,
It does not correspond to the concave shape of the substrate having the concave portion. next,
The obtained pattern of the barrier-forming resin composition was heated in a firing furnace at a rate of 5 ° C./min and a maximum temperature of 450 ° C., 450 ° C.
The sample was fired at a holding time of 30 ° C. for 30 minutes to obtain a sample on which a barrier was formed. The cross section of the obtained sample was observed with a stereoscopic microscope and an SEM, and the barrier pattern after firing was evaluated. The results are shown in Table 10.

Example 3 In the pattern of the barrier-forming resin composition corresponding to the concave portions of the substrate having the concave portions obtained in Example 2, the photosensitive resin composition containing the phosphor obtained in Production Example 4 was used. The photosensitive element (P-1) having a layer so that the layer of the photosensitive resin composition containing the phosphor of the photosensitive element (P-1) is in contact with the layer.
-1) While peeling off the polyethylene film, a laminator (trade name: HLM-3000, manufactured by Hitachi Chemical Co., Ltd.)
Mold), the heating temperature is 60 ° C, and the pressing pressure is 2.5 ×
Lamination was performed at 10 ³ N / m (linear pressure) at a substrate feeding speed of 0.5 m / min.

Next, the polyethylene terephthalate film of the photosensitive element (P-1) having the layer of the photosensitive resin composition containing the phosphor is peeled off, and the layer of the photosensitive resin composition containing the phosphor is removed. Film having a buried layer (thermoplastic resin layer) obtained in Production Example 7 (U-
The laminator (Hitachi Kasei Kogyo Co., Ltd.) is peeled off the polyethylene film of 1) such that the embedded layer (thermoplastic resin layer) is in contact with the layer of the photosensitive resin composition containing the phosphor.
And a phosphor pressure of 5 × 10 ³ N / m (linear pressure) and a substrate feeding speed of 0.5 m / min. Was formed so as to follow the inner surface of the concave portion of the pattern of the barrier-forming resin composition.

Next, the film (U-1) having the burying layer (thermoplastic resin layer) was peeled off, and one of three stripe-shaped concave portions was formed on the photosensitive resin composition layer containing the phosphor. A photomask having an active light transmission width similar to the opening width created at the book interval is brought into close contact,
Using an HMW-201GX type exposure machine manufactured by Oak Manufacturing Co., Ltd., actinic rays were imagewise irradiated at 2 × 10 ³ J / m ² .

Next, spray development was performed at 30 ° C. for 40 seconds using a 1% by mass aqueous solution of sodium carbonate. After development
After drying at 80 ° C. for 10 minutes, ultraviolet irradiation of 3 × 10 ⁴ J / m ² was performed using a Toshiba UV irradiator manufactured by Toshiba Electric Materials Co., Ltd., followed by heating at 150 ° C. for 30 minutes.

The formation of the pattern of the photosensitive resin composition layer containing the above-mentioned phosphor was carried out using the photosensitive element (P-2) having the layer of the photosensitive resin composition containing the phosphor obtained in Production Example 5. ) And a photosensitive element (P-) having a layer of the photosensitive resin composition containing the phosphor obtained in Production Example 6.
Step 3) is carried out in the same manner, and the stripe of the layer of the photosensitive resin composition containing the red, green and blue phosphors is repeatedly formed on the substrate on which the pattern of the resin composition for barrier formation is formed. A multicolor pattern formed on the inner surface of the concave portion of the pattern of the resin composition for use was formed. next,
The obtained pattern of the barrier-forming resin composition was heated in a firing furnace at a rate of 5 ° C./min and a maximum temperature of 450 ° C., 450 ° C.
The substrate was fired at a holding time of 30 ° C. for 30 minutes to obtain a PDP substrate in which a multicolor pattern was formed on the side and bottom surfaces of the barrier or on the inner surface of the recess formed by the dielectric layer.

Comparative Example 1 In Example 1, the resin composition layer solution (A-1) obtained in Production Example 4 was replaced with the resin composition layer solution (A-2) obtained in Comparative Production Example 2. Was obtained in the same manner as in Example 1 except that the composition was replaced with Example 1. In the same manner as in Example 2, except that this resin composition element was used in Example 2 instead of the barrier-forming resin composition element (i) obtained in Example 1, the resin composition for forming a barrier was used. An object pattern and a fired barrier pattern were obtained. Observe the cross-section of the obtained barrier-forming resin composition pattern and the cross-section of the fired barrier pattern by a stereoscopic microscope and SEM,
The barrier pattern after firing was evaluated, and the results are shown in Table 10.

[0071]

[Table 10] From Table 10, it can be seen that in Example 2, the patternability of the barrier-forming resin composition was good, and the barrier pattern after firing could be formed in a good shape. On the other hand, in Comparative Example 1, the patternability of the barrier-forming resin composition was poor, and it was found that the barrier pattern could not be formed well even after firing.

[0072]

The resin composition element for forming a barrier according to the present invention is capable of easily producing a high-quality substrate for a plasma display panel with a small number of steps at a high yield. The method for manufacturing a substrate for a plasma display panel according to the present invention can easily manufacture a high-quality substrate for a plasma display panel in a small number of steps with a high yield.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court II (Reference) H01J 11/02 H01J 11/02 B (72) Inventor Seiji Tai 13-13-1, Higashi 4-chome Hitachi, Hitachi City, Ibaraki Prefecture Hitachi F-term in Kasei Kogyo R & D Co., Ltd.

Claims (3)

[Claims] 1. A resin film comprising (a) a polymer binder having an ethylenically unsaturated group, (b) a release agent and (c) an inorganic material on a support film. A resin composition element for forming a barrier. 2. The barrier-forming resin composition element according to claim 1, which is laminated on a dielectric layer of a laminate in which a substrate, a patterned electrode material, and a dielectric material layer are sequentially laminated, and then supported. After removing the body film and pressing the substrate having the concave portion thereon, the substrate having the concave portion is removed, and the pattern of the barrier-forming resin composition corresponding to the concave portion of the substrate having the concave portion is formed. A method for manufacturing a substrate for a plasma display panel, comprising firing a pattern of a resin composition for forming a barrier. 3. A dielectric material layer of a laminate in which a substrate, a patterned electrode material and a dielectric material layer are sequentially laminated,
After laminating the barrier-forming resin composition element according to claim 1, the support film is removed, and the substrate having the concave portion is pressed thereon, and then the substrate having the concave portion is removed to have the concave portion. After forming a pattern of the barrier-forming resin composition corresponding to the concave portion of the substrate, and then forming a multicolor pattern on the inner surface of the concave portion of the pattern, the pattern of the barrier-forming resin composition and the multicolor pattern are formed. A method for producing a substrate for a plasma display panel, characterized by firing.