JPH11277665A - Laminating method, manufacture of fluorescent material pattern, fluorescent material pattern, and plasma display panel back plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing and laminating method for a PDP base plate for laminating thermoplastic resin layers of respective films on the base plate with good workability by using films of two kinds or more having thermoplastic resin layers, provided a method for manufacturing a fluorescent material pattern of high accuracy using the laminating method, and also provide a PDP back plate with the fluorescent material pattern formed with high accuracy. SOLUTION: A thermoplastic resin layer of a film A with the thermoplastic resin layer A 6 on a substrate film 5 and another thermoplastic resin layer of a film B with the thermoplastic layer B8 on a substrate film 7 are bonded together, a part of which is bonded through a viscous substance, and then the substrate film of the film A is released from a site on which the viscous substance is provided, and the film having the thermoplastic resin layer B 8 and the thermoplastic resin layer A 6 are bonded on the substrate film thus formed so that the thermoplastic resin layer A 6 is bonded on the base plate in a laminating method. A manufacturing method for a fluorescent material pattern of high accuracy using the laminating method, the fluorescent material pattern formed with high accuracy and a PDP back plate with the fluorescent material pattern formed with high accuracy are provided by the arrangement.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for laminating a thermoplastic resin layer, a method for producing a phosphor pattern, a phosphor pattern, and a back plate for a plasma display panel.

[0002]

2. Description of the Related Art As a method of laminating a film having a thermoplastic resin layer on a substrate, a normal pressure laminating method, a vacuum laminating method of laminating under reduced pressure, and the like are known (JP-A-57-19).
No. 7891, JP-A-57-34947, etc.).

[0003] All of the above methods are limited to laminating one type of film, and no consideration is given to workability when laminating two or more types of films.

In recent years, as one of the flat panel displays, a plasma display panel (hereinafter, referred to as a PDP) which enables a multicolor display by providing a phosphor which emits light by plasma discharge has been actively studied.

In a PDP, a flat front plate and a rear plate made of glass are arranged in parallel and opposite to each other, and both are held at a fixed interval by barrier ribs provided therebetween. , And discharges in a space surrounded by the back plate and the barrier ribs.

[0006] In such a space, a phosphor for display is applied, and the phosphor is illuminated by ultraviolet rays generated from the sealed gas by discharge, so that the light can be visually recognized by an observer.

Conventionally, as a method of providing this phosphor,
A method of applying a slurry liquid or paste in which phosphors of each color are dispersed by a printing method such as screen printing has been proposed, and is disclosed in JP-A-1-115027, JP-A-1-124929, and JP-A-1-124930. And Japanese Patent Application Laid-Open No. 2-155142.

However, since the above-mentioned phosphor dispersion slurry is in a liquid state, poor dispersion due to precipitation of the phosphor is likely to occur, and when a liquid photosensitive resist is used as the slurry, the dark reaction is accelerated. It has disadvantages such as poor storage stability. Further, since printing methods such as screen printing are inferior in printing accuracy, there is a problem that it is difficult to cope with a larger PDP in the future.

In order to solve these problems, a method using a photosensitive element (also referred to as a photosensitive film) containing a phosphor has been proposed (JP-A-6-273925).
No.).

[0010] The method using a photosensitive element means that a photosensitive resin layer containing a phosphor of a photosensitive element comprising a photosensitive resin layer containing a phosphor and a support film is heat-pressed (laminated) to the PDP. Embedded in the space of the substrate for the next, then, using a negative film, imagewise exposed to actinic light such as ultraviolet light by photographic method, then remove the unexposed portion with a developing solution such as an aqueous alkali solution, Unnecessary organic components are removed by firing, and a phosphor pattern is formed only in a necessary portion.

Therefore, when forming the phosphor pattern in the space of the PDP substrate, it is not necessary to confirm the dispersibility of the phosphor, and the storage stability is lower than that of the phosphor dispersion slurry or paste. Is also excellent. Furthermore, since a photographic method is used, a phosphor pattern can be formed with high accuracy.

However, when a photosensitive resin layer containing a phosphor is buried in a space (in a cell) of the PDP substrate by lamination using a photosensitive element by a conventional method, the barrier rib wall surface and the bottom surface of the space become invisible. It was difficult to form a phosphor pattern with a uniform thickness and shape.

Therefore, various methods for forming a phosphor pattern with a uniform thickness and shape have been studied.

[0014]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method of laminating two or more films each having a thermoplastic resin layer so that the thermoplastic resin layer of each film can be laminated on a substrate with good workability. It is to provide a method.

Another object of the present invention is to provide a laminating method capable of laminating a thermoplastic resin layer with good workability on a substrate having irregularities such as a PDP substrate.

Another object of the present invention is to further provide a PDP substrate,
An object of the present invention is to provide a lamination method suitable for a method of manufacturing an EL substrate or the like.

Another object of the present invention is to provide a laminating method suitable for a method of manufacturing a PDP substrate or the like.

Another object of the present invention is to provide a laminating method which is more excellent in workability in addition to the above-mentioned effects.

Another object of the present invention is to provide a method for manufacturing a phosphor pattern with high accuracy.

Another object of the present invention is to provide a phosphor pattern formed with high precision.

Another object of the present invention is to provide a PDP back plate having a phosphor pattern formed with high precision.

[0022]

According to the present invention, a thermoplastic resin layer of a film having a thermoplastic resin layer on a carrier film and a thermoplastic resin layer of a film having a thermoplastic resin layer on a support film are combined. After adhering only a part through the adhesive substance, the support film of the film 剥離 is peeled from the portion where the adhesive substance is present, and the thermoplastic resin layer B and the thermoplastic resin layer are formed on the obtained support film. The present invention relates to a laminating method, which comprises laminating a film having Α such that the thermoplastic resin layer 密 着 adheres to the substrate.

The present invention also relates to (I) a film A having a photosensitive resin composition layer containing a phosphor as a thermoplastic resin layer 上 on a support film and a thermoplastic resin layer B on the support film. After adhering only a part of the thermoplastic resin layers of the film B having an adhesive substance therebetween, (I
I) a step of peeling the support film of the film か ら from the site where the adhesive substance is present, and (III) a film having the thermoplastic resin layer B and the thermoplastic resin layer に on the obtained support film has irregularities. Laminating a thermoplastic resin layer 上 on the uneven surface of the substrate so as to be in close contact with the substrate, (I
V) a step of peeling the thermoplastic resin layer B from the laminated film, (V) a step of imagewise irradiating the photosensitive resin composition layer containing the phosphor with actinic rays, and (VI) a step of containing the phosphor by development. A method of forming a pattern by removing unnecessary portions from the photosensitive resin composition layer and a step of forming a phosphor pattern by removing unnecessary components from the pattern by baking (VII). .

The present invention also relates to a phosphor pattern manufactured by the above-described method for manufacturing a phosphor pattern.

The present invention also relates to a back plate for a plasma display panel comprising the above phosphor pattern on a substrate for a plasma display panel.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION The laminating method of the present invention relates to a method in which a thermoplastic resin layer of a film having a thermoplastic resin layer on a support film and a thermoplastic resin layer of a film having a thermoplastic resin layer on the support film are combined. After adhering only a part of the film through the adhesive substance, the film is removed from the site where the adhesive substance is present.
Is characterized in that a film having a thermoplastic resin layer B and a thermoplastic resin layer に is laminated on the obtained support film such that the thermoplastic resin layer 密 着 adheres to the substrate. .

The substrate in the present invention is not particularly limited. For example, a substrate for producing a printed wiring board (copper-clad laminate, glass epoxy substrate, paper phenol substrate, etc.), a substrate for producing a color filter (transparent glass plate, plastic Substrates, metal substrates (aluminum, copper, nickel, stainless steel, etc.), plasma display panel manufacturing substrates (P
DP substrate) (a substrate on which electrodes and barrier ribs are formed on a substrate such as a glass plate, a ceramic substrate, an insulated metal substrate, or a synthetic resin plate, which may be subjected to a surface treatment for transparent bonding) ), Substrates for manufacturing organic EL (transparent glass plate, plastic substrate, metal substrate (aluminum,
Copper, nickel, stainless steel, etc., ceramic substrate, substrate on which electrodes are formed, substrate for field emission display phosphor formation (transparent glass plate, plastic substrate, metal substrate (aluminum, copper, nickel, stainless steel, etc.), ceramic substrate) Etc.).

Examples of the substrate having irregularities in the present invention include a substrate for a plasma display panel (PDP substrate) on which barrier ribs are formed.

As the PDP substrate, for example, a substrate such as a glass plate, a ceramic substrate, an insulated metal substrate, a synthetic resin plate or the like, which may be subjected to a surface treatment for transparent bonding, is provided with electrodes and barrier ribs. Are formed.

For forming the barrier ribs, there is no particular limitation, and known materials can be used. For example, rib materials containing silica, thermosetting resin, low-melting glass (such as lead oxide), and solvents can be used. .

Further, in addition to the electrodes and barrier ribs, a dielectric film, an insulating film, an auxiliary electrode, a resistor, and the like may be formed on the PDP substrate, if necessary.

The method for forming these on a substrate is not particularly limited. For example, electrodes can be formed on the substrate by a method such as vapor deposition, sputtering, plating, coating, printing, and the like. The barrier ribs can be formed by a method such as a filling method or a filling method.

FIGS. 1 and 2 show a P having a barrier rib formed thereon.
A schematic diagram of an example of a DP substrate is shown. The barrier ribs usually have a height of 20 to 500 μm and a width of 20 to 200 μm. The shape of the discharge space surrounded by the barrier ribs is not particularly limited, and may be a lattice shape, a stripe shape, a honeycomb shape, a triangular shape, an elliptical shape, and the like.
Thus, a grid-like or stripe-like discharge space is formed.

1 and 2, a barrier rib 2 is formed on a PDP substrate 1. In FIG. 1, a grid-shaped discharge space 3 is formed, and in FIG. 2, a stripe-shaped discharge space 4 is formed.

The size of the discharge space is determined by the size and resolution of the PDP. Generally, in a grid-like discharge space as shown in FIG. 1, the vertical and horizontal lengths are 50 μm to 1 mm. In such a stripe-shaped discharge space, the interval is 30 μm to 1 mm.

The thermoplastic resin layer の of the film A in the present invention is not particularly limited as long as it is a resin having thermoplasticity.
A photosensitive resin composition layer or the like containing (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group and (c) a photoinitiator that generates free radicals upon irradiation with active light is preferably used for the production of a pattern. .

As the polymer (a) for imparting film property in the present invention, a vinyl copolymer is preferable, and as a monomer used in the vinyl copolymer, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid Acid, itaconic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, iso acrylate
-Propyl, iso-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-acrylate
so-butyl, iso-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, 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, methacrylic acid Dodecyl, tetradecyl acrylate, tetradecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, ray acrylate Sill, eicosyl methacrylic acid,
Docosyl acrylate, docosyl methacrylate, cyclopentyl acrylate, cyclopentyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate,
Cycloheptyl acrylate, cycloheptyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxydimethacrylate Propylene glycol, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxymethacrylate Propyl, 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-methacrylic acid
Examples include cyanoethyl, styrene, α-methylstyrene, vinyl toluene, vinyl chloride, vinyl acetate, N-vinylpyrrolidone, butadiene, isoprene, chloroprene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, and the like. These can be used alone or 2
Used in combination of more than one species.

The weight average molecular weight of the polymer (a) for imparting film properties in the present invention is from 5,000 to 300,000.
Preferably, 20,000 to 150,000
Is more preferable. This weight average molecular weight is
If it is less than 5,000, the film formability and flexibility tend to decrease when the thermoplastic resin layer A is used,
If it exceeds 000, the developability (the property that unnecessary portions can be easily removed by development) when developing with various known developing solutions described later tends to decrease.

The weight average molecular weight is a value measured by a gel permeation chromatography method and converted using a standard polystyrene calibration curve.

The (a) carboxyl group content (acid value (mg KOH
/ G)) can be appropriately adjusted.

For example, when developing with an aqueous alkali solution such as sodium carbonate or potassium carbonate, the acid value is preferably from 90 to 260. This acid value is
If it is less than 90, the development tends to be difficult, and if it exceeds 260, the developer resistance (the property that the remaining pattern portion which is not removed by development and is not attacked by the developer) tends to decrease.

When the development is carried out using an aqueous developer comprising water or an aqueous alkali solution and one or more organic solvents, the acid value is preferably from 16 to 260. If the acid value is less than 16, development tends to be difficult,
If it exceeds 260, the developer resistance tends to decrease.

Further, a developer (emulsion developer) comprising water and at least one organic solvent which is insoluble in water,
When developing using an organic solvent development such as 1,1-trichloroethane, the polymer imparting film properties of the photosensitive resin composition may not contain a carboxyl group.

As the photopolymerizable unsaturated compound (b) having an ethylenically unsaturated group in the present invention, all compounds conventionally known as photopolymerizable polyfunctional monomers can be used.

For example, the following general formula (I)

[0046]

Embedded image [Wherein, R represents a hydrogen atom or a methyl group, and k represents 1 to 1
Is an integer of 0, and Y is a saturated or unsaturated hydrocarbon residue or a heterocyclic residue or a polyalkylene glycol residue which may have a substituent, or a compound represented by the formula (II)

[0047]

Embedded image (Wherein, R ¹ and R ² each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group or a trifluoromethyl group, and R ³ and R ⁴ each independently represent an alkylene group having 1 to 6 carbon atoms. And m and n each independently represent an integer of 1 to 20). The compound which has an ethylenically unsaturated group at the terminal represented by these.

In the general formula (I), the saturated or unsaturated hydrocarbon or heterocyclic residue optionally having a substituent represented by Y includes, for example, a halogen atom, a hydroxyl group, an amino group A straight-chain, branched or alicyclic alkane residue having 1 to 22 carbon atoms which may have a substituent such as a carboxyl group (methane residue, ethane residue, propane residue,
Cyclopropane residue, butane residue, isobutane residue, cyclobutane residue, pentane residue, isopentane residue, neopentane residue, cyclopentane residue, hexane residue,
Cyclohexane residue, heptane residue, cycloheptane residue, octane residue, nonane residue, decane residue, etc.), aromatic ring residue (benzene residue, naphthalene residue, anthracene residue, biphenyl residue, Phenyl residue), heterocyclic residue (furan residue, thiophene residue, pyrrole residue,
Oxazole residue, thiazole residue, imidazole residue, pyridine residue, pyrimidine residue, pyrazine residue, triazine residue, quinoline residue, quinoxaline residue and the like.

Specifically, examples of the monomer having one unsaturated bond include, for example, ester monomers of acrylic acid or methacrylic acid (methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, N-propyl acid, 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-methacrylate
Butyl, tert-butyl acrylate, t-methacrylate
tert-butyl, 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, methacrylic acid Dodecyl, tetradecyl acrylate, tetradecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, eicosyl acrylate, eicosyl methacrylate, docosyl acrylate, docosyl methacrylate, cyclopentyl acrylate, cyclopentyl methacrylate, Cyclohexyl acrylate, cyclohexyl methacrylate, cycloheptyl acrylate, cycloheptyl methacrylate, Benzyl acrylic acid, benzyl methacrylate, phenyl acrylate, phenyl methacrylate,
Methoxyethyl acrylate, methoxyethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, 2-methyl acrylate Fluoroethyl, 2-fluoroethyl methacrylate, 2-cyanoethyl acrylate, 2-cyanoethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate,
Methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, etc., styrene monomers (styrene, α-methylstyrene, pt-butylstyrene, etc.), Polyolefin monomers (butadiene, isoprene, chloroprene, etc.), vinyl monomers (vinyl chloride, vinyl acetate, etc.), nitrile monomers (acrylonitrile, methacrylonitrile, etc.), 1- (methacryloyloxyethoxycarbonyl) -2- (3 '-Chloro-
2'-hydroxypropoxycarbonyl) benzene (γ
-Chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate) and the like.

Examples of the photopolymerizable unsaturated compound having two ethylenically unsaturated groups include, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, and triethylene glycol. Glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, hexapropylene glycol diacrylate, hexapropylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, butylene glycol Diacrylate, Chi glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate,
1,4-butanediol dimethacrylate, 1,5-pentanediol diacrylate, 1,5-pentanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol diacrylate, Pentaerythritol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, 2,2-bis (4-acryloxyethoxyphenyl) propane, 2,2-bis (4- Methacryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxydiethoxyphenyl) propane,
2,2-bis (4-methacryloxydiethoxyphenyl) propane, 2,2-bis (4-acryloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, bisphenol Examples thereof include diglycidyl ether diacrylate, bisphenol diglycidyl ether dimethacrylate, and urethane diacrylate compound.

Examples of the photopolymerizable unsaturated compound having three ethylenically unsaturated groups include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, and ethylene oxide-modified trimethylol. Examples include propane triacrylate, ethylene oxide-modified trimethylolpropane trimethacrylate, trimethylolpropane triglycidyl ether triacrylate, and trimethylolpropane triglycidyl ether trimethacrylate.

Examples of the photopolymerizable unsaturated compound having four ethylenically unsaturated groups include tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol tetraacrylate, and pentaerythritol tetramethacrylate.

Examples of the photopolymerizable unsaturated compound having five ethylenically unsaturated groups include dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate and the like.

Examples of the photopolymerizable unsaturated compound having six ethylenically unsaturated groups include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and the like.

Any of these photopolymerizable unsaturated compounds having an ethylenically unsaturated group may be those capable of undergoing radical polymerization upon irradiation with light. The sexually unsaturated compounds are used alone or in combination of two or more.

Further, the thermoplastic resin layer according to the present invention.
When used in the production of a phosphor pattern, it is necessary to remove unnecessary components by baking at the time of production. Therefore, among the above (b) the photopolymerizable unsaturated compound having an ethylenically unsaturated group, Uses polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, poly (ethylene / propylene) acrylate composite, poly (ethylene / propylene) glycol dimethacrylate with good thermal decomposability Is more preferable.

As the compound having both functions of (a) the polymer having a film property and (b) the photopolymerizable unsaturated compound having an ethylenically unsaturated group, a photopolymerizable compound having an ethylenically unsaturated group in a side chain may be used. A polymeric binder can be used in place of (a) the film imparting polymer. Specifically, a vinyl copolymer having a functional group such as a carboxyl group, a hydroxyl group, an amino group, an isocyanate group, an oxirane ring, and an acid anhydride has at least one ethylenically unsaturated group, an oxirane ring, and an isocyanate group. And a photopolymerizable vinyl copolymer obtained by subjecting a compound having one functional group such as a hydroxyl group and a carboxyl group to an addition reaction.

Examples of the vinyl monomer used for synthesizing a vinyl copolymer having a functional group such as a carboxyl group, a hydroxyl group, an amino group, an oxirane ring, and an acid anhydride include acrylic acid, methacrylic acid, maleic acid, and the like. Fumaric acid, itaconic acid, cinnamic acid, 2-hydroxyethyl acrylate,
2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylamide, methacrylamide, ethyl isocyanate methacrylate, glycidyl acrylate, glycidyl methacrylate, carboxyl group such as maleic anhydride, hydroxyl group, amino group, Oxirane rings, vinyl monomers having functional groups such as acid anhydrides, and other vinyl monomers, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid n-propyl, n-propyl methacrylate, iso-propyl acrylate, is-methacrylate
o-propyl, n-butyl acrylate, n-methacrylate
-Butyl, iso-butyl acrylate, i-methacrylate
So-butyl, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, methacrylic acid Heptyl, 2-ethylhexyl acrylate, 2-methacrylic acid
Ethylhexyl, 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,
Octadecyl methacrylate, eicosyl acrylate, eicosyl methacrylate, docosyl acrylate, docosyl methacrylate, cyclopentyl acrylate, cyclopentyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, cycloheptyl acrylate, cycloheptyl methacrylate, benzyl acrylate, Benzyl methacrylate, phenyl acrylate, phenyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, methoxytriacrylate Ethylene glycol, methoxytriethylene glycol methacrylate Dimethylaminoethyl acrylate,
Dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate,
Dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, 2-fluoroethyl acrylate, 2-fluoroethyl methacrylate, 2-cyanoethyl acrylate, 2-cyanoethyl methacrylate, Styrene, α-methylstyrene, vinyltoluene, vinyl chloride, vinyl acetate, N-vinylpyrrolidone, butadiene, isoprene, chloroprene, acrylonitrile, methacrylonitrile and the like. These are used singly or in combination of two or more kinds with a vinyl monomer having a functional group such as a carboxyl group, a hydroxyl group, an amino group, an oxirane ring, and an acid anhydride as an essential component.

At least one ethylenically unsaturated group,
Examples of the compound having one functional group such as an oxirane ring, an isocyanate group, a hydroxyl group, a carboxyl group, an amino group, and an acid anhydride group include, for example, glycidyl acrylate, glycidyl methacrylate, ethyl isocyanate methacrylate, 2-hydroxyethyl acrylate 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, cinnamic acid, acrylamide, methacrylamide, maleic anhydride, etc. Is mentioned. These are used alone or in combination of two or more.

The weight average molecular weight of the photopolymerizable polymer binder having an ethylenically unsaturated group in the side chain in the present invention is:
5,000 to 300,000, preferably 2
It is more preferable to be in the range of 0000 to 150,000. When the weight average molecular weight is less than 5,000, the film formability and flexibility tend to decrease when the thermoplastic resin layer A is used. When the weight average molecular weight exceeds 300,000, various known developers described later are used. , There is a tendency that the developability at the time of development (the property that unnecessary portions can be easily removed by development) decreases.

Further, a thermoplastic resin layer containing a phosphor
Is a carboxyl group content (can be specified by an acid value (mgKOH / g)) of a photopolymerizable polymer binder having an ethylenically unsaturated group in a side chain so that the polymer can be developed by various known developers. Can be adjusted appropriately.

For example, when developing with an aqueous alkali solution such as sodium carbonate or potassium carbonate, the acid value is preferably from 90 to 260. This acid value is
If it is less than 90, the development tends to be difficult, and if it exceeds 260, the developer resistance (the property that the remaining pattern portion which is not removed by development and is not attacked by the developer) tends to decrease.

When developing using an aqueous developing solution comprising water or an aqueous alkali solution and one or more organic solvents, the acid value is preferably from 16 to 260. If the acid value is less than 16, development tends to be difficult,
If it exceeds 260, the developer resistance tends to decrease.

Further, a developer (emulsion developer) comprising water and at least one organic solvent which is insoluble in water,
When developing using an organic solvent development such as 1,1-trichloroethane, it is not necessary to contain a carboxyl group.

Examples of (c) a photoinitiator which generates free radicals upon irradiation with actinic light include aromatic ketones (benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone). (Michler's ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- (4- ( Methylthio)
Phenyl) -2-morpholinopropanone-1,2,4
-Diethylthioxanthone, 2-ethylanthraquinone, phenanthrenequinone, etc.), benzoin ether (benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, etc.), benzoin (methyl benzoin, ethyl benzoin, etc.), benzyl derivative (2-benzyl-2- Dimethylamino-1-4 (morpholinophenyl) butanone-1,2,2-dimethoxy-
1,2-diphenylethan-1-one, benzyldimethylketal, etc.), 2,4,5-triarylimidazole dimer (2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (O-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl)- 4,5-diphenylimidazole dimer, 2-
(P-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl)-
5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, etc., acridine derivatives (9-phenylacridine, 1,7-bis (9-acridinyl) heptane) Etc.). These are used alone or in combination of two or more.

The amount of the component (a) in the present invention is as follows:
The total amount of the component (a) and the component (b) is preferably 10 to 90 parts by weight based on 100 parts by weight, and more preferably 20 to 8 parts by weight.
More preferably, it is 0 parts by weight. If this blending amount is 1
If the amount is less than 0 parts by weight, when supplied in a roll form as a film for lamination, the photosensitive resin composition exudes from the roll end (hereinafter, referred to as edge fusion), which makes it difficult to draw out from the roll at the time of lamination, Further, when the extruded portion uses a PDP substrate or the like, it is partially and excessively buried in the space of the PDP substrate or the like, causing a problem such as a remarkable decrease in manufacturing yield.
When the amount exceeds 90 parts by weight, the sensitivity tends to be insufficient.

The amount of the component (b) in the present invention is as follows:
The total amount of the component (a) and the component (b) is preferably 10 to 90 parts by weight based on 100 parts by weight, and more preferably 20 to 8 parts by weight.
More preferably, it is 0 parts by weight. If this blending amount is 1
If the amount is less than 0 parts by weight, the sensitivity of the photosensitive resin composition tends to be insufficient, and if it exceeds 90 parts by weight, the photocured product tends to be brittle, and when used as a film for lamination, The photosensitive resin composition tends to exude from the edge due to the flow, and the film-forming property tends to decrease.

The amount of the component (c) in the present invention is as follows:
The amount is preferably 0.01 to 30 parts by weight based on 100 parts by weight of the total of the components (a) and (b).
More preferably, it is 1 to 20 parts by weight. When the amount is less than 0.01 part by weight, the sensitivity of the photosensitive resin composition tends to be insufficient, and when the amount exceeds 30 parts by weight, absorption of active light on the exposed surface of the photosensitive resin composition. And the photocuring inside tends to be insufficient.

The photosensitive resin composition constituting the thermoplastic resin layer に お け る in the present invention contains known dyes, pigments, coloring agents,
Plasticizers, polymerization inhibitors, surface modifiers, stabilizers, adhesion promoters, thermosetting agents, and the like can be added as needed.

The photosensitive resin composition constituting such a thermoplastic resin layer Α can be suitably used as a resin for producing a printed wiring board, a resin for producing a color filter, and the like.

Further, the photosensitive resin composition constituting the thermoplastic resin layer 本 in the present invention contains (d) a phosphor, whereby a resin for producing a PDP substrate, a resin for producing an EL substrate, It can be used as a resin for forming a phosphor layer for an emission display.

The phosphor (d) in the present invention is not particularly limited, and a phosphor mainly composed of an ordinary metal oxide can be used.

As a red-colored phosphor, for example, Y ₂
O ₂ S: Eu, Zn ₃ (PO ₄ ) ₂ : Mn, Y ₃ O ₃ : Eu,
YVO ₄ : Eu, (Y, Gd) BO ₃ : Eu, γ-Zn ₃
(PO ₄ ) ₂ : Mn, (ZnCd) S: Ag + In ₂ O and the like.

As the phosphor emitting green color, for example, Zn
S: Cu, Zn_TwoSiO_Four: Mn, ZnS: Cu + Zn_Two
SiO_Four: Mn, Gd_TwoO_TwoS: Tb, Y_ThreeAl_FiveO₁₂: C
e, ZnS: Cu, Al, Y_TwoO_TwoS: Tb, ZnO: Z
n, ZnS: Cu, Al + In _TwoO_Three, LaPO_Four: C
e, Tb, BaO.6Al_TwoO_Three: Mn and the like.

As a blue-emitting phosphor, for example, Zn
S: Ag, ZnS: Ag, Al, ZnS: Ag, Ga,
Al, ZnS: Ag, Cu, Ga, Cl, ZnS: Ag
+ In ₂ O ₃ , Ca ₂ B ₅ O ₉ Cl: Eu ²⁺ , (Sr, C
a, Ba, Mg) ₁₀ (PO ₄ ) ₆ C ₁₂ : Eu ²⁺ , Sr ₁₀
(PO ₄ ) ₆ Cl ₁₂ : Eu ²⁺ , BaMgAl ₁₀ O ₁₇ : Eu
^{2 +} , BaMgAl ₁₄ O ₂₃ : Eu ²⁺ , BaMgAl
₁₆ O ₂₆ : Eu ^{2+ and the} like.

The particle size of the phosphor (d) in the present invention is as follows:
0.1 to 20 μm, preferably 1 to 15 μm
Is more preferable, and particularly preferably 2 to 8 μm. When the particle size is less than 0.1 μm, the luminous efficiency tends to decrease, and when it exceeds 20 μm, the dispersibility tends to decrease.

The shape of the phosphor (d) in the present invention is preferably spherical, and its surface area is preferably smaller.

The amount of the component (d) in the present invention is as follows:
The amount is preferably 10 to 400 parts by weight, more preferably 50 to 350 parts by weight, based on 100 parts by weight of the total amount of the components (a), (b) and (c).
It is particularly preferred that the amount be 0 to 300 parts by weight. If the compounding amount is less than 10 parts by weight, the luminous efficiency tends to decrease when light is emitted as PDP, and if it exceeds 400 parts by weight, the film forming property decreases when the thermoplastic resin layer A is used. Or the flexibility tends to decrease.

The photosensitive resin composition constituting the thermoplastic resin layer に お け る in the present invention may contain a compound having a carboxyl group so as not to cause viscosity increase for a long period of time and to improve storage stability. it can.

As the compound having a carboxyl group,
For example, saturated fatty acids, unsaturated fatty acids, aliphatic dibasic acids,
Examples thereof include aromatic dibasic acids, aliphatic tribasic acids, and aromatic tribasic acids.

Specifically, for example, formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, propionic acid,
Capric, undecanoic, lauric, tridecanoic, myristic, pentadecanoic, palmitic, heptadecanoic, stearic, nonadecanoic, arachidic, palmitooleic, oleic, elaidic, linolenic, linoleic, Oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, monomethyl malonate,
Monoethyl malonate, succinic acid, methylsuccinic acid, adipic acid, methyladipic acid, pimelic acid, suberic acid,
Azelaic acid, sebacic acid, maleic acid, itaconic acid,
Examples include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, citric acid, salicylic acid, pyruvic acid, malic acid and the like.

Among them, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, citric acid and the like are preferable, and oxalic acid, malonic acid, citric acid and the like are more preferable in terms of a high effect of suppressing thickening. These are used alone or in combination of two or more.

The compounding amount of the compound having a carboxyl group is preferably 0 to 30 parts by weight, more preferably 0.01 to 30 parts by weight, based on 100 parts by weight of the component (a). If the amount exceeds 30 parts by weight, the sensitivity tends to be insufficient.

In the present invention, a plasticizer can be added to the photosensitive resin composition constituting the thermoplastic resin layer に in order to improve the film properties.

A dispersant can be added to the photosensitive resin composition constituting the thermoplastic resin layer Α in the present invention in order to improve the dispersion of the phosphor.

A binder may be used in the photosensitive resin composition constituting the thermoplastic resin layer に お け る in the present invention in order to prevent the phosphor from peeling off the PDP substrate after firing.

The film A having the thermoplastic resin layer に お け る in the present invention was uniformly dissolved or dispersed by dissolving or mixing each component constituting the thermoplastic resin layer に in a solvent capable of dissolving or dispersing. A film A can be obtained by forming a solution, applying the solution on a support film, and drying.

Solvents capable of dissolving or dispersing the above components include, for example, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, tetramethylsulfone , Diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, chloroform, methylene chloride, methyl alcohol, ethyl alcohol and the like. These are used alone or in combination of two or more.

As the support film, for example, polyethylene terephthalate, polycarbonate, polyethylene, polypropylene and the like, which are chemically and thermally stable and are composed of a flexible material, are exemplified. Terephthalate and polyethylene are preferred, and polyethylene terephthalate is more preferred.

The support film is formed later by a thermoplastic resin layer.
Since it must be removable from the surface, it must not have been subjected to a surface treatment or made of a material that cannot be removed.

The thickness of the support film is 5 to 100.
μm, more preferably 10 to 80 μm, and particularly preferably 10 to 70 μm.

As a coating method, a known method can be used. For example, a knife coating method, a roll coating method,
Spray coating, gravure coating, bar coating,
Curtain coat method and the like can be mentioned.

The drying temperature is preferably from 60 to 130 ° C., and the drying time is preferably from 3 minutes to 1 hour.

The thickness of the thermoplastic resin layer の of the film A is
Although not particularly limited, when used for manufacturing a substrate for a printed wiring board or when used as a pixel of a color filter, the film thickness is preferably 1 to 10 μm, and 1 to 5 μm. More preferred.

When used in the manufacture of a PDP substrate, the film thickness is preferably 10 to 200 μm, more preferably 20 to 120 μm, and more preferably 20 to 120 μm.
To 80 μm, particularly preferably 30 to 80 μm
Is most preferable. When the thickness is less than 10 μm, the phosphor pattern after firing described later becomes thin, and the luminous efficiency tends to decrease.
The phosphor pattern after firing tends to be thick, and the discharge space tends to be small.

The thermoplastic resin layer の of the film A has a thickness of 100
The viscosity at ℃ is preferably from 1 to 1 × 10 ⁹ Pa · sec, more preferably from 2 to 1 × 10 ⁸ Pa · sec, and more preferably from 5 to 1 × 10 ⁷ Pa · sec. Particularly preferably, it is very preferably 10 to 1 × 10 ⁶ Pa · sec. The viscosity at 100 ° C. is 1 Pa
If it is less than sec, the viscosity at room temperature becomes too low, and when the film A is formed, the thermoplastic resin layer Α tends to bleed out from the end due to the flow, and the film formability tends to decrease. On the other hand, if it exceeds 1 × 10 ⁹ Pa · sec, the thermoplastic resin layer 層 (the photosensitive resin layer containing the phosphor) is formed on the inner surface of the concave portion of the substrate having irregularities when the substrate is used for manufacturing a PDP substrate. Tends to decrease.

On the thermoplastic resin layer の of the film A,
Further, a peelable cover film can be laminated.

As the cover film, polyethylene,
Examples thereof include polypropylene, polyethylene terephthalate, and polycarbonate. It is preferable that the adhesive force between the cover film and the thermoplastic resin layer 小 さ い be smaller than the adhesive force between the support film and the thermoplastic resin layer Α.

The film A thus obtained can be stored in a roll form.

The thermoplastic resin (e) constituting the thermoplastic resin layer B of the film B in the present invention is not particularly limited as long as it is a resin having thermoplasticity. Examples thereof include polyethylene, polypropylene, polyvinyl chloride, and the like. Polyvinyl acetate, polyvinylidene chloride, polystyrene, polyvinyl toluene, polyacrylate, polymethacrylate, copolymer of ethylene and vinyl acetate, copolymer of ethylene and acrylate, copolymer of vinyl chloride and vinyl acetate Copolymer, copolymer of styrene and acrylic or methacrylic ester, copolymer of vinyltoluene and acrylic or methacrylic ester, polyvinyl alcohol resin (hydrolysis of polyacrylic or polymethacrylic ester) Material, polyvinyl acetate Hydrolyzate of copolymer of ethylene and vinyl acetate, hydrolyzate of copolymer of ethylene and acrylic acid ester, hydrolyzate of copolymer of vinyl chloride and vinyl acetate, styrene and acrylic Hydrolysates of copolymers of acid esters or methacrylic esters, hydrolysates of copolymers of vinyl toluene with acrylic esters or methacrylic esters, etc.), water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers And water-soluble salts of carboxyalkyl starch, polyvinylpyrrolidone, and resins having a carboxyl group obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated monomer copolymerizable therewith.

Further, when the thermoplastic resin layer B is used for manufacturing a substrate for PDP, etc., the thermoplastic resin layer B can prevent color mixing, workability,
A plasticizer can be contained from the viewpoint of improving the film properties. As the plasticizer to be used, (b) polyalkylene such as photopolymerizable unsaturated compound having an ethylenically unsaturated group, polypropylene glycol represented by the general formula (II) and derivatives thereof, and polyethylene glycol and derivatives thereof Glycol derivatives, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricridyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate, and the like.

The amount of the thermoplastic resin component (e) contained in the thermoplastic resin layer B is preferably 10 to 100 parts by weight based on 100 parts by weight of the total amount of the resin component and the plasticizer component. More preferably, the content is set to 100 parts by weight. When the blending amount is less than 10 parts by weight, when the film B is used, the resin composition tends to exude from the edge due to the flow, and the film-forming property tends to be reduced.

The amount of the plasticizer component contained in the thermoplastic resin layer B is such that the total amount of the resin component and the plasticizer component is 1%.
The amount of 00 parts by weight is preferably 0 to 90 parts by weight, more preferably 0 to 80 parts by weight. If the compounding amount exceeds 90 parts by weight, when the film B is formed, there is a tendency that the film is exuded from the edge by flow, and the film formability is reduced.

Further, the thermoplastic resin layer B may contain (c) a photoinitiator which generates free radicals upon irradiation with active light.

The film B having the thermoplastic resin layer B in the present invention is formed into a uniform solution by dissolving or mixing the components constituting the thermoplastic resin layer B in a solvent which dissolves the components. On a film, it can be formed into a film by applying and drying using a known coating method such as a knife coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method, a curtain coating method and the like. it can.

Examples of the solvent for dissolving the resin constituting the thermoplastic resin layer B include water, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, γ-butyrolactone, N
-Methylpyrrolidone, dimethylformamide, tetramethylsulfone, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, chloroform, methylene chloride, methyl alcohol, ethyl alcohol and the like. These are used alone or in combination of two or more.

The thickness of the thermoplastic resin layer B in the present invention is not particularly limited. However, when the thermoplastic resin layer B is used for manufacturing a PDP substrate, the thickness is preferably 10 to 10 from the viewpoint of the embedding property of the substrate having irregularities into the inner surface of the concave portion. The thickness is preferably 200 μm, more preferably 20 to 120 μm.

Further, the thermoplastic resin layer B according to the present invention
Has a viscosity at 100 ° C. of 1 to 1 × 10 ⁹ Pa · sec.
2-1 × 10 ⁸ Pa · sec is more preferable, and 5-1 × 10 ⁷ Pa · sec is more preferable.
It is particularly preferable to set 10 to 1 × 10 ⁶ Pa · s
ec is most preferable. If the viscosity at 100 ° C. is less than 1 Pa · sec, the viscosity at room temperature becomes too low, and when a film is formed, the thermoplastic resin layer B tends to bleed out from the end due to the flow, and the film formability decreases. Tend to. If it exceeds 1 × 10 ⁹ Pa · sec, the formability of the thermoplastic resin layer の on the inner surface of a concave portion of a substrate having irregularities described later tends to decrease when used for manufacturing a PDP substrate.

Further, on the thermoplastic resin layer B, further,
A peelable cover film can be laminated.

Examples of the cover film include polyethylene, polypropylene, polyethylene terephthalate, and polycarbonate. The adhesive strength between the cover film and the thermoplastic resin layer B is higher than the adhesive strength between the support film and the thermoplastic resin layer B. Is preferably smaller.

The thermoplastic resin layer B thus formed into a film can be stored in a roll.

The film A having the thermoplastic resin layer に お け る and the film B having the thermoplastic resin layer B in the present invention
From the viewpoint of workability and the like, it is preferable that the film A having the thermoplastic resin layer Α has a support film, a thermoplastic resin layer Α, and a cover film, and a film B having a thermoplastic resin layer B is preferable. Preferably have a support film, a thermoplastic resin layer B and a cover film.

Further, in the film A having the thermoplastic resin layer 及 び and the film B having the thermoplastic resin layer B in the present invention, the number of the thermoplastic resin layers is not necessarily one, but two or more. You may.

Next, after the thermoplastic resin layers of the film (B) and the film (B) of the present invention are partially adhered to each other via an adhesive substance, the support film of the film (2) is removed from the site where the adhesive substance is present. The method of removing will be described.

When a cover film is present on the film I and the film B, the cover film is removed, and an adhesive is applied or affixed to one or both of the thermoplastic resin layers of the film I and the film B. The entire surface of the thermoplastic resin layers of the film B and the film B are adhered to each other. The adhesive used at this time is not particularly limited,
Usually, a sheet-like adhesive such as a double-sided adhesive tape, a liquid adhesive such as an acrylic adhesive, an epoxy adhesive, or the like is used. Alternatively, after the entire surfaces of the film Α and the film B are brought into close contact with each other, a part of the interface between the thermoplastic resin layer Α and the thermoplastic resin layer B may be peeled off, and an adhesive may be applied or pasted, and then brought into close contact again. Further, the portion to be adhered with the adhesive may be either at the end of the film or inside thereof.
Next, as a method of removing the support film of the film か ら from the portion adhered through the adhesive, when the portion adhered by the adhesive is the end of the film, the support film is removed from the portion adhered as it is. The film can be removed, and when the portion adhered with the adhesive is inside the film, at least the support film is cut, and the support film can be removed from the cut portion.

The means for adhering the thermoplastic resin layers of the film フ ィ ル ム and the film B to each other is not particularly limited.
Usually, a method of press-bonding using a laminator is used. At that time, the reaction may be performed under atmospheric pressure or under reduced pressure. When the thermoplastic resin layers of the film Α and the film B are brought into close contact with each other, the heating may be performed at room temperature or by heating.
The temperature is preferably 0 to 140 ° C, more preferably 10 to 130 ° C, still more preferably 20 to 130 ° C, particularly preferably 30 to 130 ° C, and most preferably 30 to 110 ° C. . This heating temperature is
If the temperature is less than 10 ° C., the thermoplastic resin layers of the film Α and the film B tend to be unable to sufficiently adhere to each other,
When the temperature exceeds ℃, the thermoplastic resin layer Α tends to be thermoset.

When the thermoplastic resin layers of the film A and the film B are brought into close contact with each other, and it is desired to peel off the support of the film A or the film B, it is difficult to peel off only the support film. As in the present invention, the thermoplastic resin layers are only partially adhered to each other via the adhesive substance, and then the support is peeled off from the site where the adhesive substance is present, so that only the support film is easily peeled off. can do. Here, the size of the portion where the pressure-sensitive adhesive is present is not particularly limited as long as the shape and the size can be expressed by the pressure-sensitive adhesive enough to trigger the peeling of the support film. 2-1 from the end in the length direction from end to end in the width direction to which B is adhered
It is preferably 0 cm.

Hereinafter, a method for manufacturing a phosphor pattern in manufacturing a plasma display panel will be described as an example using the lamination method of the present invention. The method for producing a phosphor pattern according to the present invention comprises: (I) a film A having a photosensitive resin composition layer containing a phosphor as a thermoplastic resin layer 支持 on a support film; and a thermoplastic resin layer on the support film. (B) peeling off the support film of the film か ら from the site where the adhesive substance is present, after the thermoplastic resin layers of the film B having B are partially adhered to each other via the adhesive substance; III) a step of laminating a film having the thermoplastic resin layer B and the thermoplastic resin layer に on the obtained support film so that the thermoplastic resin layer Α is in close contact with the substrate on the uneven surface of the uneven substrate; (IV) a step of peeling the thermoplastic resin layer B from the laminated film, (V) a step of imagewise irradiating the photosensitive resin composition layer containing the phosphor with actinic rays, and (VI) developing the phosphor by development. Feeling to contain A step and (VII) removing unnecessary components from the pattern by baking the steps of forming a phosphor pattern is removed to form a pattern unnecessary portions from sexual resin composition layer.

Hereinafter, each step of the method for manufacturing a phosphor pattern will be described with reference to the drawings. FIGS. 3 to 7 are schematic views showing each step of the method for manufacturing a phosphor pattern.

[(I) The heat of a film A having a photosensitive resin composition layer containing a phosphor as a thermoplastic resin layer 上 on a support film and a film B having a thermoplastic resin layer B on a support film (II) A step of peeling the support film of the film か ら from a portion where the sticky substance 9 is present after the plastic resin layers are partially adhered to each other via the sticky substance] on the support film (5) The thermoplastic resin of a film A having a photosensitive resin composition layer containing a phosphor as a thermoplastic resin layer (6) and a film B having a thermoplastic resin layer B (8) on a support film (7) FIG. 3 (I) shows a state in which the support film (5) of the film Α is removed from a portion where the adhesive substance (9) is present after the layers are brought into close contact with each other only through the adhesive substance (9). ) And FIG. 3 (II). .

[(III) A film having a thermoplastic resin layer B and a thermoplastic resin layer 上 on a support film, and a photosensitive resin composition layer containing a phosphor (thermoplastic Step of laminating resin layer Α) so as to be in close contact with the substrate] PDP on which barrier ribs (11) are formed
On the surface of the transparent substrate (10) (substrate having irregularities) for
The thermoplastic resin layer Α (photosensitive resin composition layer containing a phosphor) (6) and the thermoplastic resin layer B (8) are bonded to the thermoplastic resin layer Α (6) using a pressure roll (12). FIG. 4 (II) shows a state in which the layers are laminated so as to be in close contact with each other, and FIG. 4 (III) shows a state in which the layers are laminated.

[(IV) Step of peeling thermoplastic resin layer B] FIG. 4 (I) shows a state in which the thermoplastic resin layer (8) and the support film (7) have been peeled from the thermoplastic resin layer Α (6).
V).

[(V) Step of irradiating actinic rays imagewise]
FIG. 5 (V) shows a state where the actinic ray (13) is irradiated imagewise.

In the step (V), the actinic ray (13)
Is imagewise irradiated on the thermoplastic resin layer Α (6) in the state shown in FIG. 5 (V) by applying a photomask (1) such as a negative film, a negative glass, a positive film, a positive glass, or the like.
The actinic ray (13) can be radiated imagewise via 4). Further, an actinic ray may be irradiated between the thermoplastic resin layer A (6) and the photomask via a protective film.

As the actinic ray (13), a known actinic light source can be used, and examples thereof include light generated from a carbon arc, a mercury vapor arc, a xenon arc, and others.

Since the sensitivity of the photoinitiator is usually maximal in the ultraviolet range, the active light source in that case should be one which effectively emits ultraviolet rays. When the photoinitiator is sensitive to visible light, for example, 9,10-phenanthrenequinone or the like, visible light is used as the active light (13), and the light source is as described above. Other than the above, a flood light bulb for photography, a sun lamp, and the like can be used.

The actinic ray (13) in the present invention includes a parallel ray and a scattered ray.
Either scattered light may be used, or both may be used in one step, or both may be used separately in two stages. If both are used separately in two stages, either may be performed first.

[(VI) Step of Removing Unwanted Parts by Development] FIG. 5 (VI) shows a state where the unnecessary parts are removed by development. In FIG. 5 (VI), reference numeral 6 'denotes a photosensitive resin composition layer containing a phosphor after photocuring.

In FIG. 5 (VI), as a developing method, if a protective film is present on the thermoplastic resin layer A, the protective film is removed, and then a known method such as an aqueous alkali solution, an aqueous developer, an organic solvent or the like is used. A method of performing development using a developing solution by a known method such as spraying, rocking immersion, brushing, and scrubbing to remove unnecessary portions is used.

The developing time and the developing temperature in the step (VI) can be appropriately adjusted so that unnecessary portions can be removed. The development time is the minimum development time of the photosensitive resin composition layer containing the phosphor (thermoplastic resin layer （) (6) (the photosensitive resin composition layer containing the phosphor (thermoplastic resin layer （) (6). ) Is embedded in the inner surface of the concave portion of the PDP substrate,
(The shortest time during which the photosensitive resin composition layer containing the phosphor (the thermoplastic resin layer Α) (6) is removed by development)
Preferably, the developing time is 1 to 10 times.
The temperature is preferably set to 0 to 60 ° C.

If the development time is less than the minimum development time, the undeveloped portion tends to occur. If the development time exceeds 10 times the minimum development time, the photosensitive resin composition layer containing the phosphor (the thermoplastic resin layer) Ii) There is a tendency that the necessary part of (6) is removed. When the developing temperature is lower than 10 ° C., the developability tends to decrease, and when the developing temperature exceeds 60 ° C., the developer resistance tends to decrease.

Examples of the base of the aqueous alkali solution include alkali hydroxides (such as hydroxides of lithium, sodium or potassium), alkali carbonates (such as carbonates or bicarbonates of lithium, sodium or potassium), and alkali metal phosphates (such as carbonates or bicarbonates). Potassium phosphate, sodium phosphate, etc.), alkali metal pyrophosphate (sodium pyrophosphate, potassium pyrophosphate, etc.), tetramethylammonium hydroxide, triethanolamine, etc., among which sodium carbonate, tetramethylammonium hydroxide And the like are preferred.

The pH of the aqueous alkaline solution used for development is 9
To 11, and the temperature is preferably set to a layer of a photosensitive resin composition containing a phosphor (a thermoplastic resin layer Α).
It can be adjusted according to the developability of (6).

A surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating the development, and the like can be mixed in the aqueous alkali solution.

Examples of the aqueous developer include those comprising water or an aqueous alkali solution and one or more organic solvents.

Here, as the base of the aqueous alkali solution,
Other than the above substances, for example, borax, sodium metasilicate, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,
3-propanediol, 1,3-diaminopropanol-2-morpholine, tetramethylammonium hydroxide and the like.

The pH of the aqueous developer is preferably from 8 to 12, more preferably from 9 to 10.

Examples of the organic solvent include acetone alcohol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol. Monobutyl ether and the like. These can be used alone or 2
Used in combination of more than one type.

The concentration of the organic solvent is usually 2 to 90% by weight.
The temperature can be adjusted according to the developing property.

Further, a small amount of a surfactant, an antifoaming agent or the like can be mixed in the aqueous developer.

The organic solvent developer used alone includes, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyrolactone and the like. These organic solvents are used to prevent ignition.
Water may be added in the range of 1 to 20% by weight.

In this manner, the photosensitive resin composition layer (thermoplastic resin layer Α) (6) (unnecessary portion) containing the phosphor formed on the inner surface of the concave portion except for the inner surface of the concave portion is removed. Forms a photosensitive resin composition layer 6 'containing a phosphor after photocuring.

After the development, ultraviolet irradiation or heating using a high-pressure mercury lamp or the like may be performed for the purpose of improving the adhesion and chemical resistance of the phosphor-containing photoresist on the inner surface of the concave portion of the PDP substrate. .

At this time, the irradiation amount of the ultraviolet ray is usually 5 to 5.
It is preferably 10,000 mJ / cm ² ,
More preferably, 5,000 mJ / cm ² ,
It is particularly preferable that the concentration be 0 to 3,000 mJ / cm ² .

The temperature during heating is preferably from 60 to 180 ° C., and more preferably from 100 to 180 ° C. Further, the heating time is preferably set to 15 to 90 minutes.

Irradiation and heating of these ultraviolet rays may be performed separately from irradiation and heating, and either one may be performed first.

[(VII) Step of Removing Unwanted Components by Firing] FIG. 5 (VII) shows a state in which the phosphor pattern has been formed after the unnecessary components have been removed by firing. FIG.
In (VII), 14 is a phosphor pattern.

In FIG. 5 (VII), the firing method is not particularly limited, and a known firing method may be used to remove unnecessary components other than the phosphor and the binder to form a phosphor pattern. it can.

At this time, the maximum firing temperature is 350-80.
The temperature is preferably set to 0 ° C, more preferably 400 to 600 ° C. Further, the firing time at the highest firing temperature is preferably from 3 to 120 minutes, more preferably from 5 to 90 minutes.

At this time, the heating temperature is 0.5 to 50 ° C. /
Min., More preferably 1 to 45 ° C./min. In addition, before reaching the maximum firing temperature, 35
A step of maintaining the temperature between 0 ° C. and 450 ° C. can be provided, and the holding time is preferably 5 to 100 minutes.

According to the method of manufacturing a phosphor pattern of the present invention, the above steps (I) to (VI) are repeated for each color so that the number of steps can be reduced. After forming a multicolor pattern composed of a photosensitive resin composition layer containing a phosphor to be formed, it is preferable to perform the step (VII) to form a multicolor phosphor pattern.

In the method for producing a phosphor pattern of the present invention, a photosensitive resin composition layer (thermoplastic resin layer Α) (6) containing a phosphor containing each of the phosphors that emit red, blue, and green independently. ) Can be performed in any order for each of the colors red, blue and green.

The steps (I) to (VI) in the method for producing a phosphor pattern of the present invention are repeated for each color to form a photosensitive resin composition layer containing a phosphor that emits red, green and blue light. FIG. 6 shows a state in which a multicolor pattern including is formed. In FIG. 6, 6'a is a first color pattern,
6'b is a second color pattern, and 6'c is a third color pattern.

FIG. 7 shows a state where a multicolor phosphor pattern is formed by performing the step (VII) in the phosphor pattern manufacturing method of the present invention. In FIG. 7, 15a is a first color phosphor pattern, 15b is a second color phosphor pattern, and 15c is a third color phosphor pattern.

The back plate for a plasma display panel of the present invention is obtained by combining the phosphor pattern obtained as described above with
It is provided on a plasma display panel substrate.

The back plate for a plasma display panel will be described below with reference to FIG. In addition, FIG.
FIG. 9 is a schematic view showing an example of a plasma display panel (PDP). In FIG.
11 is a barrier rib, 20 is a stripe discharge space, 15
Is a phosphor pattern, 16 is an address electrode, 17 is a protective film, 18 is a dielectric layer, 19 is a display electrode, and 20 is a front plate substrate.

In FIG. 8, the lower portion including the transparent substrate 10, the barrier ribs 11, the phosphor patterns 15, and the addressing electrodes 16 is the back plate for the PDP, and the protective film 17, the dielectric layer 18, the display electrodes 19, and the front plate. The upper portion including the substrate 20 is a PDP front plate.

PDPs can be classified into AC (AC) type PDPs, DC (DC) type PDPs, and the like according to the voltage application method. The schematic diagram of FIG. 8 shown as an example is an AC type PDP.

[0159]

The present invention will be described below with reference to examples.

Production method 1 [Preparation of solution (a) of film-imparting polymer] In a flask equipped with a stirrer, a reflux condenser, an inert gas inlet and a thermometer, the solvent (1) shown in Table 1 was added. Charge and raise the temperature to 80 ° C in a nitrogen gas atmosphere, and raise the reaction temperature to 80 ° C
(2) shown in Table 1 was dropped uniformly over 4 hours. After dropping, continue stirring at 80 ° C. ± 2 ° C. for 6 hours,
Weight average molecular weight of 80,000, acid value of 130 mg KO
An H / g solution (a) of a film-imparting polymer (solid content: 45.5% by weight) was obtained.

[0161]

[Table 1] Production Example 2 [(A) Preparation of solution (Α-1) for thermoplastic resin layer］] The materials shown in Table 2 were mixed for 15 minutes using a raikai machine.
A solution (Α-1) for the thermoplastic resin layer 調製 was prepared.

[0162]

[Table 2] Production Example 3 [Preparation of Photosensitive Element (i) (Film A)] The solution (A-1) for the thermoplastic resin layer (photosensitive resin composition layer) obtained in Production Example 2 was 12 cm in width and 12 cm in thickness. Uniformly applied on a 50 μm polyethylene terephthalate film,
The solvent was removed by drying with a hot air convection dryer at 110 ° C. for 10 minutes to form a thermoplastic resin layer Α. The thickness of the obtained thermoplastic resin layer ４０ was 40 μm.

Then, a polyethylene film having a width of 12 cm and a thickness of 25 μm was further laminated on the thermoplastic resin layer と し て as a cover film to produce a photosensitive element (i).

The edge fusion property of the obtained photosensitive element (i) was evaluated by the following method, and the results are shown in Table 5.

[Edge Fusion Property] The photosensitive element (i) having a length of 90 m wound up in a roll shape was stored at a temperature of 23 ° C. and a humidity of 60% Rh, and the photosensitive resin composition layer was placed from the side of the roll. The state of oozing was visually evaluated over a period of six months. The evaluation criteria are as follows. ：: good edge fusion property (no exudation of the photosensitive resin composition layer even in 6 months) ×: poor edge fusion property (exudation of the photosensitive resin composition layer in 6 months) Production Example 4 [Preparation of photosensitive element (ii)] The materials shown in Table 3 were mixed for 15 minutes using a raikai machine to prepare a solution (A-2) for a thermoplastic resin layer Α. .

[0166]

[Table 3] Next, in Production Example 3, except that the solution (A-1) for the thermoplastic resin layer に was replaced with the solution (A-2) for the thermoplastic resin layer 、, the photosensitive element ( ii) was prepared. In addition, the photosensitive element (ii)
The thickness of the thermoplastic resin layer was 40 μm.

The edge fusion property of the obtained photosensitive element (ii) was evaluated in the same manner as in Production Example 3, and the results are shown in Table 5.

Production Example 5 [Preparation of photosensitive element (iii)] The materials shown in Table 4 were mixed for 15 minutes using a raikai machine to prepare a solution (A-3) for a thermoplastic resin layer Α.

[0169]

[Table 4] Next, in Production Example 3, except that the solution (A-1) for the thermoplastic resin layer に was replaced with the solution (A-3) for the thermoplastic resin layer 感光, the photosensitive element ( iii) was prepared. Incidentally, the photosensitive element (ii)
The thickness of the thermoplastic resin layer の of i) was 40 μm.

The edge fusion property of the obtained photosensitive element (iii) was evaluated in the same manner as in Production Example 3.
Table 5 shows the results.

[0171]

[Table 5] From the results in Table 5, the edge fusion properties of the photosensitive elements manufactured in Production Examples 3 to 5 were good.

Production Example 6 [Preparation of Film (B-1) Having Thermoplastic Resin Layer B] A resin solution composed of the materials shown in Table 6 was applied to a film having a width of 12 cm.
The resin was uniformly coated on a 20 μm-thick polyethylene terephthalate film and dried with a hot air convection dryer at 80 to 110 ° C. for 10 minutes to remove the solvent, thereby forming a thermoplastic resin layer B. The thickness of the obtained thermoplastic resin layer B after drying is 45
μm.

[0173]

[Table 6] Next, on the thermoplastic resin layer B, a width of 12 cm and a thickness of 2 cm
A 5 μm polyethylene film was laminated as a cover film to prepare a film (B-1) having a thermoplastic resin layer B, which was composed of a support film, a thermoplastic resin layer B, and a cover film.

Example 1 [Preparation of Red Phosphor Pattern] [(I) A photosensitive resin composition layer containing a phosphor on a support film (a thermoplastic resin layer) )) And the thermoplastic resin layers of the film B having the thermoplastic resin layer B on the support film are brought into close contact with each other only partially via an adhesive substance.
(II) A film of the support film of 7 films is peeled off from the site where the adhesive substance is present, and (III) a film having the thermoplastic resin layer B and the thermoplastic resin layer on the support film is replaced with the thermoplastic resin layer. Step of laminating the photosensitive element (i) having the thermoplastic resin layer 得 and the film (B-1) having the thermoplastic resin layer B obtained in Production Example 3 by peeling off the polyethylene film. While a double-sided pressure-sensitive adhesive tape having a width of 12 cm × 4 cm was arranged on the interface at the head, the laminating temperature was 60 ° C., the laminating speed was 0.5 m / min, and the pressure (cylinder pressure) was 5 × 10 ⁴ Pa (this The linear pressure at the time is 1.0 × 10 ³ N / m)
The thermoplastic resins were brought into close contact with each other.

Next, the polyethylene terephthalate film on the surface of the photosensitive element (i) was peeled off from the portion on which the double-sided adhesive tape was disposed, and a substrate for PDP having irregularities (10 cm × 10 cm × 3 mm, striped barrier ribs, The laminating temperature is 120 ° C., the laminating speed is 0.5 m / min, and the crimping pressure (cylinder pressure) is 4 × 10 5 on the side where the barrier ribs having an opening width of 150 μm, a barrier rib width of 70 μm and a barrier rib height of 150 μm) are formed. The substrate was laminated at ⁵ Pa (the linear pressure at this time was 9.8 × 10 ³ N / m because a substrate having a width of 10 cm was used).
A thermoplastic resin layer Α and a thermoplastic resin layer B were embedded in the inner surface of the concave portion.

[(IV) Step of peeling off thermoplastic resin layer B] Next, the thermoplastic resin layer B was removed together with the polyethylene terephthalate film (B-1) having the thermoplastic resin layer B.

The substrate on which only the thermoplastic resin layer was laminated was cut in a direction perpendicular to the stripe direction, the cut surface was observed with an electron microscope, and the phosphor layer (laminated on the inner surface of the concave portion of the substrate). As a result of confirming the thermoplastic resin layer A) formability, it was found that a uniform and good phosphor layer was formed.

[(V) Step of irradiating actinic rays imagewise]
Next, a test photomask was brought into close contact with the thermoplastic resin layer Α, and an active light beam was imagewise irradiated at 500 mJ / cm ² using an HMW-590 type exposure machine manufactured by Oak Manufacturing Co., Ltd.

[(VI) Step of Removing Unwanted Parts by Developing] Then, after irradiating with actinic rays, the mixture was allowed to stand at room temperature for 1 hour, and then spray-developed at 30 ° C. for 120 seconds using a 1% by weight aqueous sodium carbonate solution. .

After the development, the film was dried at 80 ° C. for 10 minutes, and 3 J / cm 2 was applied using a Toshiba ultraviolet irradiation device manufactured by Toshiba Electric Materials Co., Ltd.
The sample was irradiated with ultraviolet light of No. ² and further heated in a dryer at 150 ° C. for 1 hour.

[(VII) Step of Removing Unwanted Content by Firing] Next, heat treatment (firing) is performed at 500 ° C. for 30 minutes to remove unnecessary resin components, and a red phosphor is formed on the inner surface of the concave portion of the PDP substrate. A pattern was formed.

The cross section of the obtained red phosphor pattern was visually observed with a stereoscopic microscope and an SEM, and the state of formation of the red phosphor pattern was evaluated. As a result, the red phosphor layer was formed on the inner surface of the recess of the PDP substrate (barrier rib). (Wall surface and substrate surface).

Example 2 [Preparation of Blue Phosphor Pattern] [(I) A photosensitive resin composition layer containing a phosphor on a support film (thermoplastic resin layer) )) And the thermoplastic resin layers of the film B having the thermoplastic resin layer B on the support film are brought into close contact with each other only partially via an adhesive substance.
(II) The support film of the film Α is peeled off from the portion where the adhesive substance is present, and (III) a film having the thermoplastic resin layer B and the thermoplastic resin layer に on the support film is formed of a thermoplastic resin layer Α. Step of laminating so as to be in close contact with the substrate] The photosensitive element (ii) having the thermoplastic resin layer 得 obtained in Production Example 4 and the film (B-1) having the thermoplastic resin layer B are peeled off while removing the polyethylene film. Laminating temperature is 60 ° C., laminating speed is 0.5 m / min, and pressing pressure (cylinder pressure) is 5 × 10, with the same double-sided adhesive tape as in Example 1 disposed on the interface at the head.
^The thermoplastic resins were brought into close contact with each other at ⁴ Pa (the linear pressure at this time was 1.0 × 10 ³ N / m).

Next, while peeling off the polyethylene terephthalate film on the surface of the photosensitive element (ii) from the portion where the double-sided adhesive tape was disposed, a PDP substrate having the same irregularities as in Example 1 (stripe-shaped barrier ribs, Opening width 150μm, barrier rib width 70μ
m, the laminating temperature is 120 ° C., the laminating speed is 0.5 m / min, and the pressing pressure (cylinder pressure) is 4 × 10
The substrate was laminated at ⁵ Pa (the linear pressure at this time was 9.8 × 10 ³ N / m because a substrate having a width of 10 cm was used), and the thermoplastic resin layer Α and the thermoplastic resin layer B were embedded in the inner surface of the concave portion.

[(IV) Step of peeling off thermoplastic resin layer B] Then, a film having thermoplastic resin layer B (B-
The thermoplastic resin layer B was removed together with the polyethylene terephthalate film of 1).

The substrate on which only the thermoplastic resin layer Α is laminated is cut in a direction perpendicular to the stripe direction.
The cut surface was observed with an electron microscope to confirm the phosphor layer forming properties. As a result, it was found that a uniform and good phosphor layer was formed.

[(V) Step of irradiating actinic rays imagewise]
Next, a test photomask was brought into close contact with the thermoplastic resin layer Α, and an active light beam was imagewise irradiated at 500 mJ / cm ² using an HMW-590 type exposure machine manufactured by Oak Manufacturing Co., Ltd.

[(VI) Step of Removing Unwanted Parts by Development] Then, after irradiation with actinic rays, the mixture was left at room temperature for 1 hour, and then spray-developed at 30 ° C. for 120 seconds using a 1% by weight aqueous sodium carbonate solution. .

After the development, the film was dried at 80 ° C. for 10 minutes, and was irradiated with 3 J / cm using a Toshiba ultraviolet irradiation device manufactured by Toshiba Electric Materials Co., Ltd.
The sample was irradiated with ultraviolet light of No. ² and further heated in a dryer at 150 ° C. for 1 hour.

[(VII) Step of Removing Unwanted Content by Firing] Next, heat treatment (firing) is performed at 500 ° C. for 30 minutes to remove unnecessary resin components, and a blue phosphor is formed on the inner surface of the concave portion of the PDP substrate. A pattern was formed.

The cross section of the obtained blue phosphor pattern was visually observed with a stereoscopic microscope and an SEM, and the formation state of the blue phosphor pattern was evaluated. As a result, the blue phosphor layer was formed on the inner surface of the concave portion of the PDP substrate (barrier rib). (Wall surface and substrate surface).

Example 3 [Preparation of Green Phosphor Pattern] [(I) A photosensitive resin composition layer containing a phosphor on a support film (thermoplastic resin layer) )) And the thermoplastic resin layers of the film B having the thermoplastic resin layer B on the support film are brought into close contact with each other only partially via an adhesive substance.
(II) The support film of the film Α is removed from the portion where the adhesive substance is present, and (III) a film having the thermoplastic resin layer B and the thermoplastic resin layer に on the support film is a thermoplastic resin layer Α. Step of laminating so as to be in close contact with the substrate] The photosensitive element (iii) having the thermoplastic resin layer 得 obtained in Production Example 5 and the film (B-1) having the thermoplastic resin layer B are peeled off while removing the polyethylene film. In the state where the same double-sided adhesive tape as in Example 1 was disposed on the interface at the head, the laminating temperature was 60 ° C., the laminating speed was 0.5 m / min, and the pressure (cylinder pressure) was 5 × 1.
0 ⁴ Pa (linear pressure of at this time 1.0 × 10 ³ N / m) was adhered to the thermoplastic resin to each other by.

Next, while peeling off the polyethylene terephthalate film on the surface of the photosensitive element (iii) from the portion where the double-sided adhesive tape was disposed, a PDP substrate having the same irregularities as in Example 1 (stripe-shaped barrier ribs, Opening width 150μm, barrier rib width 70μ
m, the laminating temperature is 120 ° C., the laminating speed is 0.5 m / min, and the pressing pressure (cylinder pressure) is 4 × 1 on the side on which the barrier rib having a barrier rib height of 150 μm is formed.
0 ⁵ Pa (for using a substrate of width 10 cm, the linear pressure at this time 9.8 × 10 ³ N / m) was laminated with, embedded thermoplastic resin layer Α and the thermoplastic resin layer B in the recess inner surface.

[(IV) Step of peeling off thermoplastic resin layer B] Next, the thermoplastic resin layer B was removed together with the polyethylene terephthalate film (B-1) having the thermoplastic resin layer B.

The remaining substrate on which only the thermoplastic resin layer Α was laminated was cut in a direction perpendicular to the stripe direction.
The cut surface was observed with an electron microscope to confirm the phosphor layer forming properties. As a result, it was found that a uniform and good phosphor layer was formed.

[(V) Step of irradiating actinic rays imagewise]
Next, a test photomask was brought into close contact with the thermoplastic resin layer Α, and an active light beam was imagewise irradiated at 500 mJ / cm ² using an HMW-590 type exposure machine manufactured by Oak Manufacturing Co., Ltd.

[(VI) Step of Removing Unwanted Parts by Development] Then, after irradiation with actinic rays, the mixture was allowed to stand at room temperature for 1 hour, and then spray-developed at 30 ° C. for 120 seconds using a 1% by weight aqueous sodium carbonate solution. .

After the development, the film was dried at 80 ° C. for 10 minutes, and 3 J / cm 2 was applied using a Toshiba ultraviolet irradiation device manufactured by Toshiba Electric Materials Co., Ltd.
The sample was irradiated with ultraviolet light of No. ² and further heated in a dryer at 150 ° C. for 1 hour.

[(VII) Step of Removing Unwanted Content by Firing] Next, a heat treatment (firing) is performed at 500 ° C. for 30 minutes to remove unnecessary resin components, and a green phosphor is formed on the inner surface of the concave portion of the PDP substrate. A pattern was formed.

The cross section of the obtained green phosphor pattern was visually observed by a stereoscopic microscope and an SEM, and the formation state of the green phosphor pattern was evaluated. As a result, the green phosphor layer was formed on the inner surface of the concave portion of the PDP substrate (barrier rib). (Wall surface and substrate surface).

From the above results, a good phosphor pattern can be produced by producing a phosphor pattern using the lamination method of the present invention.

Embodiment 4 [Formation of Three-Color Pattern] Next, (I) in Embodiment 1
(I) to (VI) of Example 2 using the substrate on which the photosensitive resin composition layer containing the phosphor emitting the first color red, which was obtained by performing the steps (VI) to (VI), was formed. ) To form a photosensitive resin composition layer containing a phosphor that emits the second color blue, and then perform the same steps as in (I) to (VI) of Example 3. Then, a photosensitive resin composition layer containing a phosphor emitting the third green color was formed to form a multicolor pattern.

Next, using the obtained multicolor pattern,
The step (VII) in Example 1 was performed to manufacture a PDP back plate on which a multicolor phosphor pattern was formed.

A cross section of the obtained multicolor phosphor pattern is
As a result of visually observing with a stereoscopic microscope and an SEM and evaluating the formation state of the multicolor phosphor pattern, the multicolor phosphor pattern emitting red, blue and green was found to be in the space of the back plate for PDP (barrier rib wall surface and (On the bottom surface of the cell).

[0205]

According to the laminating method of the present invention, a thermoplastic resin layer of each film can be laminated on a substrate with good workability by using two or more kinds of films having a thermoplastic resin layer. It can be suitably used for lamination on a substrate having irregularities such as.

According to the method for producing a phosphor pattern of the present invention, a highly accurate phosphor pattern can be produced.

The phosphor pattern of the present invention is formed with high precision, and the back plate for a plasma display panel of the present invention is provided with the phosphor pattern formed with high precision.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a PDP substrate on which barrier ribs are formed.

FIG. 2 is a schematic view showing an example of a PDP substrate on which barrier ribs are formed.

FIG. 3 shows (I) to (F) of the method for producing a phosphor pattern of the present invention.
It is the schematic diagram which showed one aspect of the process of (II).

FIG. 4 shows a method (III) for producing a phosphor pattern of the present invention.
It is the schematic diagram which showed one aspect of the process of (IV).

FIG. 5 shows (V) to (F) of the method for producing a phosphor pattern of the present invention.
It is the schematic diagram which showed one aspect of the process of (VII).

FIG. 6 is a schematic diagram showing a state in which a multicolor pattern formed of a photosensitive resin composition layer containing a phosphor is formed.

FIG. 7 is a schematic diagram showing a state in which a multicolor phosphor pattern is formed.

FIG. 8 is a schematic view showing an example of a back plate for a plasma display panel of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 PDP board 2 Barrier rib 3 Lattice discharge space 4 Stripe discharge space 5 Support film 6 Thermoplastic resin layer A 6 'Photosensitive resin layer containing phosphor 6'a First color pattern 6'b Second color Pattern 6′c Third color pattern 7 Support film 8 Thermoplastic resin layer B 9 Adhesive substance 10 Transparent substrate for PDP 11 Barrier rib 12 Phosphor pattern 13 Active ray 14 Photomask 15 Phosphor pattern 15a First color phosphor pattern 15b Second color phosphor pattern 15c Third color phosphor pattern 16 Address electrode 17 Protective film 18 Dielectric layer 19 Display electrode 20 Front plate substrate

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI H04N 5/66 101 H04N 5/66 101A (72) Inventor Kazuya Sato 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Within Ibaraki Research Laboratory, Industrial Co., Ltd. (72) Inventor Tsuyoshi Nojiri 4-3-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside the Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. No. Hitachi Chemical Co., Ltd.Ibaraki Research Laboratory (72) Inventor Seiji Tai 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd.

Claims (8)

[Claims] 1. A thermoplastic resin layer of a film having a thermoplastic resin layer on a support film and a thermoplastic resin layer of a film having a thermoplastic resin layer on a support film are partially bonded with an adhesive substance therebetween. After being adhered, peel the support film of film Α from the site where the adhesive substance is present,
A laminating method comprising laminating a film having a thermoplastic resin layer B and a thermoplastic resin layer に on the obtained support film so that the thermoplastic resin layer 密 着 adheres to the substrate. 2. The substrate according to claim 1, wherein the substrate has irregularities.
The lamination method according to the above. 3. The thermoplastic resin layer Α has (a) a film-imparting polymer, (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group, and (c) free radicals generated by irradiation with active light. The lamination method according to claim 1 or 2, wherein the layer is a photosensitive resin composition layer containing a photoinitiator and (d) a phosphor. 4. The laminating method according to claim 1, wherein the thermoplastic resin layer B is a thermoplastic resin layer containing a plasticizer component. 5. A film having a thermoplastic resin layer on a support film, comprising a support film, a thermoplastic resin layer and a cover film, wherein a thermoplastic resin layer B is formed on the support film. The lamination method according to claim 1, wherein the film B has a support film, a thermoplastic resin layer B, and a cover film. 6. A film A having a photosensitive resin composition layer containing a phosphor as a thermoplastic resin layer 上 on a support film and a film B having a thermoplastic resin layer B on a support film. (II) a step of peeling the support film of the film Α from a portion where the adhesive substance is present, after the thermoplastic resin layers are partially adhered to each other via the adhesive substance, and (III) the obtained support. A step of laminating a film having a thermoplastic resin layer B and a thermoplastic resin layer 上 on a base film so that the thermoplastic resin layer 密 着 adheres to the substrate on the uneven surface of the substrate having irregularities, (IV) a laminated film Peeling the thermoplastic resin layer B from the resin, (V) irradiating the photosensitive resin composition layer containing the phosphor imagewise with actinic rays, and (VI) photosensitive resin composition containing the phosphor by development. From the physical layer Preparation of a phosphor pattern having the steps of forming a step and (VII) phosphor pattern by removing unnecessary components from the pattern by baking to form a part to remove the pattern. 7. A phosphor pattern produced by the method for producing a phosphor pattern according to claim 6. 8. A back plate for a plasma display panel comprising the phosphor pattern according to claim 7 on a substrate for a plasma display panel.