JPH1095090A - Laminating method, laminating device, manufacture of fluorescent pattern, fluorescent pattern, and back-face plate for plasma display panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To use two kinds or more of films and laminate respective films on a base with good workability by feeding a film A from a first feed source, also feeding a film B from a second source and laminate the film A on the base, on which the film B is laminated. SOLUTION: A substrate film 5A is transferred to a first feed roll 1 for feeding a film A and a film with a thermoplastic resin layer A3 is transferred to a laminating roll 10 by a transfer roll 12, and a thermoplastic resin layer A3 having the substrate film 5a is laminated on a base 7. On the other hand, a substrate film 5B is transferred to a second feed roll 2 for feeding a film B, and a film with a thermoplastic resin layer B4 is transferred to the laminating roll 10 by the transfer roll 12, and the thermoplastic resin layer B with the substrate film 5B is laminated on the thermoplastic resin layer A3 laminated on the base 7. Respective films, therefore, can be laminated on the base with good workability by using two kinds or more of films.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a laminating method, a laminating apparatus, a method of manufacturing 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 (Japanese Patent Laid-Open No. 57-19 / 1982).
No. 7891, JP-A-57-34947, etc.).
All of the above methods are limited to laminating one type of film, and when laminating two or more types of films, two or more steps are required, and there are problems such as poor workability.

In recent years, as one of the flat panel displays, a plasma display panel (hereinafter, referred to as PDP) which enables a multicolor display by providing a phosphor which emits light by plasma discharge has been actively studied. PDP
A flat front plate and a rear plate made of glass are disposed parallel and opposite to each other, and both are held at a fixed interval by barrier ribs provided therebetween, and the front plate, the rear plate, and The structure discharges in the space surrounded by the barrier ribs. In such a space, a phosphor for display is applied, and the phosphor is caused to emit light by ultraviolet rays generated from the sealing gas by discharge, so that the light can be visually recognized by an observer.

Conventionally, as a method for providing this phosphor,
A method of applying a slurry solution or paste in which phosphors of each color are dispersed by a printing method such as screen printing has been proposed. And Japanese Patent Application Laid-Open No. 2-155142. However, since the above-mentioned phosphor dispersion slurry liquid is liquid, poor dispersion due to precipitation of the phosphor is likely to occur, and when a liquid photosensitive resist is used for the slurry liquid, it is preserved by promoting a dark reaction and the like. It has disadvantages such as poor stability. Furthermore, 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.

To solve these problems, a method using a photosensitive element containing a phosphor (also referred to as a photosensitive film) has been proposed (Japanese Patent Laid-Open No. Hei 6-267421).
And 6-273925). The method using a photosensitive element means that a photosensitive resin layer containing a phosphor of a photosensitive element composed of a support film and a photosensitive resin layer containing a phosphor is heated and pressed (laminated) to the P layer.
Embedded in the space of the DP substrate, and then imagewise exposed to active light such as ultraviolet light by a photographic method using a negative film,
After that, unexposed portions are removed with a developing solution such as an aqueous alkaline solution, and unnecessary organic components are removed by baking to form a phosphor pattern only on necessary portions. The method of using such a photosensitive element is
Since the photographic method is used, the 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 space bottom surface are laid. 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 layer thickness and shape have been studied.

[0007]

SUMMARY OF THE INVENTION The first aspect of the present invention provides a laminating method capable of laminating each film on a substrate with good workability by using two or more kinds of films. A second aspect of the present invention provides, in addition to the effects of the first aspect, a laminating method capable of laminating with good workability on a substrate having irregularities such as a PDP substrate. The third aspect of the present invention provides a laminating method capable of performing lamination with better workability in addition to the effects of the first or second aspect of the present invention.

A fourth aspect of the present invention provides, in addition to the effects of the first, second or third aspect of the present invention, a lamination method suitable for manufacturing a substrate for a printed wiring board, a color filter, and the like. The invention described in claim 5 provides, in addition to the effect of the invention described in claim 4, a lamination method suitable for manufacturing a plasma display panel, an EL substrate, and the like. The invention according to claim 6 is the invention according to claims 1, 2, 3, and 4.
Another object of the present invention is to provide a laminating method more suitable for manufacturing a plasma display panel or the like, in addition to the effects of the invention described in the fifth aspect. The invention according to claim 7 is based on claims 1, 2, 3, 4,
Another object of the present invention is to provide a laminating method which is more excellent in workability in addition to the effects of the invention described in 5 or 6.

The invention according to claims 8 and 9 is directed to a laminating apparatus capable of laminating each thermoplastic resin layer on a substrate with good workability by using two or more kinds of films having a thermoplastic resin layer. To provide. The invention according to claim 10 is a laminating apparatus that has a thermoplastic resin layer and can laminate each thermoplastic resin layer on a substrate with good workability using two or more types of films, and does not take up space. To provide. According to the eleventh aspect of the present invention, in addition to the effects of the eighth, ninth, or tenth aspect of the present invention, there is provided a laminating apparatus which is easy to prepare for starting work and has excellent maintainability. According to the twelfth aspect, in addition to the effects of the eighth, ninth, or tenth aspects,
It is another object of the present invention to provide a stacking apparatus capable of suppressing defects during stacking.

The invention according to claim 13 provides a method for manufacturing a phosphor pattern with high accuracy. The invention according to claim 14 provides a phosphor pattern formed with high precision. The invention described in claim 15 is to provide a back plate for a plasma display panel having a phosphor pattern formed with high precision.

[0011]

According to the present invention, a film A is supplied from a first supply unit, a film B is supplied from a second supply unit, a film A is provided on a substrate, and a film B is provided thereon. And a stacking method characterized by stacking. Further, the present invention relates to the lamination method, wherein the substrate is a substrate having irregularities. Further, in the present invention, the film A is a film having a thermoplastic resin layer A, and the film B is
The present invention relates to the laminating method, which is a film having a thermoplastic resin layer B.

Further, according to the present invention, the thermoplastic resin layer A comprises
(A) a photosensitive resin composition comprising: a film-imparting polymer; (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group at a terminal; and (c) a photoinitiator that generates free radicals upon irradiation with active light. The invention relates to the above-mentioned lamination method, which is a layer. The present invention also relates to the above-mentioned laminating method, wherein the thermoplastic resin layer A is further a (d) photosensitive resin composition layer containing a phosphor. The present invention also relates to the laminating method, wherein the thermoplastic resin layer B contains (e) a thermoplastic resin.

In the present invention, the film having the thermoplastic resin layer A has a support film, a thermoplastic resin layer A and a cover film, and the thermoplastic resin layer B
The present invention relates to the above-mentioned laminating method, wherein the film having the above has a support film, a thermoplastic resin layer B and a cover film.

Further, the present invention comprises first supply means for supplying the film A, second supply means for supplying the film B, and laminating means for laminating the film A on the substrate and the film B thereon. The present invention relates to a laminating apparatus comprising: The present invention also relates to a support film (5A), a thermoplastic resin layer A
Film A having (3) and cover film (6A)
And support film (5B), thermoplastic resin layer B
Film B having (4) and cover film (6B)
Is a device for laminating a thermoplastic resin layer A (3) on a substrate (7) and a thermoplastic resin layer B (4) thereon, using a first supply means for supplying the film A, B
, A means for removing the cover film ((6A) and (6B)), a means for removing the support film (5A), and the thermoplastic resin layer A (3) and the thermoplastic resin layer The present invention relates to a laminating apparatus provided with laminating means for laminating B (4).

The present invention also relates to a support film (5
A), thermoplastic resin layer A (3) and cover film (6
A) and a support film (5)
B), a thermoplastic resin layer B (4) and a cover film (6
Using a film B having B), a thermoplastic resin layer A (3) on a substrate (7) and a thermoplastic resin layer B (4) thereon
Transport means for feeding a substrate (7),
A first supply unit for supplying the film A, a second supply unit for supplying the film B, a cover film ((6A) and
(6B) Means for taking), means for feeding a film having thermoplastic resin layer A (3) or thermoplastic resin layer B (4), means for feeding support film (5A), support The present invention relates to a laminating apparatus provided with laminating means for laminating a film having a thermoplastic resin layer A (3) or a thermoplastic resin layer B (4) on a substrate (7).

The present invention also provides a transport roll (11) for feeding a substrate (7), a first supply roll (1) for feeding a film A, and a cover film winding roll (8) for winding a cover film (6A). ), A feed roll (12) for feeding a film having a support film (5A) and a thermoplastic resin layer A (3), a film having a support film (5A) and a thermoplastic resin layer A (3) to a substrate (7). A) a laminating roll (10), a feed roll (12) for feeding the support film (5A), a support film winding roll (9) for winding the support film (5A), and a second roll for supplying the film B. 2, a supply roll (2), a cover film take-up roll (8) for winding the cover film (6B), a feed roll for feeding a film having the support film (5B) and the thermoplastic resin layer B (4) ( 2) on a substrate (7) the thermoplastic resin layer A (3 laminated on), the support film (5
The present invention relates to the laminating apparatus provided with a laminating roll (10) for laminating a film having B) and a thermoplastic resin layer B (4).

The present invention also provides a transport roll (11) for feeding a substrate (7), a first feed roll (1) for feeding a film A, a feed roll (12) for feeding a film A, and a cover film (6A). Film take-up roll (8), support film (5A) and thermoplastic resin layer A
A feed roll (12) for feeding a film having (3), a second feed roll (2) for feeding a film B, a feed roll (12) for feeding a film B, and a cover film (6B)
, A cover film take-up roll (8), a support film (5B), a feed roll (12) for feeding a film having a thermoplastic resin layer B (4), and a support film (5).
A) and a film having the thermoplastic resin layer A (3), a support film (5B) and a laminating roll (13) for laminating the film having the thermoplastic resin layer B (4), and the support film (5A). Feed roll (12), support film take-up roll (9) for winding support film (5A), thermoplastic resin layer A (3), thermoplastic resin layer B
(4) A feed roll (12) for feeding a film having the support film (5B), a thermoplastic resin layer A (3), a film having the thermoplastic resin layer B (4) and the support film (5B) as a substrate. (7) Laminating roll (1
0).

The present invention also relates to (I) a film A having a thermoplastic resin layer A which is a photosensitive resin composition layer containing a phosphor on the uneven surface of a substrate having unevenness by the above-mentioned laminating method; A step of laminating a film B having a thermoplastic resin layer B to form a thermoplastic resin layer A and a thermoplastic resin layer B, (II) a step of imagewise irradiating an actinic ray, (II)
The present invention relates to a method for manufacturing a phosphor pattern including a step of (I) removing unnecessary portions by development and a step of (IV) removing unnecessary portions by firing. The present invention also relates to a phosphor pattern manufactured by the above-described method for manufacturing a phosphor pattern. Also,
The present invention relates to a plasma display panel back plate comprising the above-described phosphor pattern on a plasma display panel substrate.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The laminating method of the present invention
Is supplied from the first supply unit, the film B is supplied from the second supply unit, the film A is laminated on the substrate, and the film B is laminated thereon. The substrate in the present invention is not particularly limited, and for example, a substrate for manufacturing a printed wiring board (a copper-clad laminate, a glass epoxy substrate, a paper phenol substrate, etc.), a substrate for manufacturing a color filter (a transparent glass substrate, a plastic substrate, a metal substrate). Substrate (aluminum,
Copper, nickel, stainless steel, etc.), ceramic substrates, etc.),
Plasma display panel manufacturing substrate (PDP substrate) (A substrate such as a glass plate, a ceramic substrate, an insulated metal substrate, or a synthetic resin plate, which may have been subjected to a surface treatment for transparent bonding, A substrate on which a barrier rib is formed, a substrate for manufacturing an organic EL (a transparent glass substrate, a plastic substrate, a metal substrate (aluminum, copper,
Nickel, stainless steel, etc.), ceramic substrate, substrate on which electrodes are formed, etc., substrate for forming a phosphor layer of a field emission display (transparent glass substrate, plastic substrate, metal substrate (aluminum, copper, nickel, stainless steel, etc.), ceramic) Substrate, etc.).

The substrate having irregularities in the present invention includes, for example, a substrate for a plasma display panel (substrate for PDP) on which barrier ribs are formed. P
As a substrate for DP, for example, a glass plate, a ceramic substrate,
Examples thereof include a substrate such as an insulated metal substrate or a synthetic resin plate on which electrodes and barrier ribs are formed. For forming the barrier rib, a known material can be used without any particular limitation. For example, a rib material containing silica, a thermosetting resin, a low-melting glass (such as lead oxide), a solvent, or the like can be used. Further, in addition to the electrodes and the barrier ribs, a dielectric film, an insulating film, an auxiliary electrode, a resistor, and the like may be formed on the PDP substrate as necessary. There is no particular limitation on the method for forming these on a substrate.For example, on a substrate, electrodes can be formed by a method such as vapor deposition, sputtering, plating, coating, or printing, and a printing method, a sand blast method, The barrier ribs can be formed by a method such as an embedding 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,
Although a square shape, an elliptical shape, and the like are possible, a grid-like or stripe-like discharge space is usually formed as shown in FIGS. 1 and 2, a barrier rib 15 is formed on a transparent substrate 14, and a grid-shaped discharge space 16 is formed in FIG. 1 and a stripe-shaped discharge space 17 is formed in FIG. The size of the discharge space is determined by the size and resolution of the PDP, and in the case of a grid-like discharge space as shown in FIG.
In the striped discharge space as shown in FIG.
The interval is 30 μm to 1 mm.

Film A and film B in the present invention
Although there is no particular limitation, from the viewpoint of workability and the like, the film A is preferably a film having the thermoplastic resin layer A, and the film B is preferably a film having the thermoplastic resin layer B. preferable.

The thermoplastic resin layer A in the present invention is not particularly limited as long as it is a resin having thermoplasticity. Preferred examples include a photosensitive resin composition layer containing a polymerizable unsaturated compound and (c) a photoinitiator that generates free radicals upon irradiation with active light.

As the polymer (a) for imparting film property in the present invention, a vinyl copolymer is preferable. Examples of the vinyl monomer used for the vinyl copolymer include acrylic acid, methacrylic acid, maleic acid and fumaric acid. , Itaconic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, iso-propyl acrylate, iso-propyl methacrylate, n-butyl acrylate, N-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, pentyl acrylate,
Pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate, 2-ethylhexyl acrylate, methacrylic acid 2
-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, methoxyethyl acrylate, methoxydiethylene glycol methacrylate, Methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, methacryl 2-hydroxypropyl acid, dimethylaminoethyl acrylate, dimethyl methacrylate Ethyl, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, 2-fluoroethyl acrylate, 2-fluoroethyl methacrylate, Acrylic acid 2-
Cyanoethyl, 2-cyanoethyl methacrylate, styrene, α-methylstyrene, vinyltoluene, vinyl chloride, vinyl acetate, N-vinylpyrrolidone, butadiene,
Examples include isoprene, chloroprene, acrylamide, methacrylamide, acrylonitrile, and methacrylonitrile. These are used alone or in combination of two or more.

The weight average molecular weight of the polymer (a) in the present invention is preferably from 5,000 to 300,000, more preferably from 20,000 to 150,000. This weight average molecular weight is 5,
If it is less than 000, the film forming property and flexibility tend to decrease when the photosensitive element is used.
If it exceeds 000, the developability (the property that unnecessary portions can be easily removed by development) tends to decrease. The weight average molecular weight is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

(A) The carboxyl group content (which can be specified by an acid value (mgKOH / g)) of the film-imparting polymer is appropriately determined so that the thermoplastic resin A can be developed with various known developers. Can be adjusted. For example, when developing using an aqueous alkali solution such as sodium carbonate or potassium carbonate, the acid value
It is preferably 90 to 260. This acid value is 90
If it is less than 260, development tends to be difficult, and if it exceeds 260, the resistance to developing solution (the property that the remaining pattern that is not removed by development and is not attacked by the developing solution) tends to decrease. In the case of developing using an aqueous developer composed of water or an aqueous alkali solution and one or more organic solvents, the acid value is preferably 16 to 260. When the acid value is less than 16, development tends to be difficult, and when it exceeds 260, developer resistance tends to decrease. Furthermore, when an organic solvent developer such as 1,1,1-trichloroethane or an emulsion developer is used, it does not need to contain a carboxyl group.

As the photopolymerizable unsaturated compound (b) having an ethylenically unsaturated group at the terminal in the present invention,
All those known as photopolymerizable polyfunctional monomers can be used.

For example, the following general formula (I)

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

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 alkyl group having 1 to 6 carbon atoms. And m and n each independently represent an integer of 1 to 20).

In the general formula (I), examples of the saturated or unsaturated hydrocarbon residue or heterocyclic residue which may have a substituent represented by Y include a halogen atom, a hydroxyl group and 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, the monomer having one unsaturated bond includes, for example, an ester monomer of acrylic acid or methacrylic acid (methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic 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, acrylic acid
sec-butyl, sec-butyl methacrylate, te acrylate
rt-butyl, tert-butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate,
Hexyl methacrylate, heptyl acrylate, heptyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, acrylic acid Dodecyl, 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, methacryl Cycloheptyl acid, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate, methacrylic acid Dimethylaminopropyl, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, 2-fluoroethyl acrylate, 2-fluoroethyl methacrylate, acrylic acid 2
-Cyanoethyl, 2-cyanoethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, etc.), styrene Monomer (styrene, α-methylstyrene, pt-butylstyrene, etc.), polyolefin monomer (butadiene, isoprene, chloroprene, etc.), vinyl monomer (vinyl chloride, vinyl acetate, etc.), nitrile monomer (acrylonitrile, methacrylic Lonitrile, etc.), 1- (methacryloyloxyethoxycarbonyl)
-2- (3'-chloro-2'-hydroxypropoxycarbonyl) benzene and the like.

Examples of the monomer having two unsaturated bonds include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate. Ethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, hexapropylene glycol dimethacrylate, hexapropylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, butylene glycol diacrylate, butylene glycol Jime Acrylate, 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 A diglycidyl ether Examples include acrylate, bisphenol A diglycidyl ether dimethacrylate, and urethane diacrylate compound.

Examples of the monomer having three unsaturated bonds include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, ethylene oxide-modified trimethylolpropane triacrylate, and ethylene oxide. Modified trimethylolpropane trimethacrylate, trimethylolpropane triglycidyl ether triacrylate, trimethylolpropane triglycidyl ether trimethacrylate and the like can be mentioned. Examples of the monomer having four unsaturated bonds include tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol tetraacrylate, and pentaerythritol tetramethacrylate.

Examples of the monomer having five unsaturated bonds include dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate and the like. Examples of the monomer having six unsaturated bonds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. Any of these monomers having an unsaturated bond may be those that undergo radical polymerization by light irradiation, and these monomers having an unsaturated bond may be used alone or in combination of two or more. Used in combination.

Further, the thermoplastic resin layer A in 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, so that (b) the photopolymerizable unsaturated compound having an ethylenically unsaturated group at the terminal From the inside, good thermal decomposability, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate,
Poly (ethylene / propylene) acrylate composite,
It is more preferable to use (ethylene / propylene) glycol dimethacrylate or the like.

The compound having both functions of (a) the polymer having a film property and (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group at a terminal has an ethylenically unsaturated group in a side chain. A photopolymerizable polymer binder can be used in place of the (a) 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. ,
Examples include 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 a functional group 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, iso-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, sec-butyl acrylate Spot , Sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate, 2-ethylhexyl acrylate, methacryl 2-ethylhexyl acid, octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, hexadecyl acrylate, methacryl Hexadecyl acrylate, 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, methoxydimethacrylate Propylene glycol, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylamino acrylate Propyl, dimethylaminopropyl methacrylate,
2-chloroethyl acrylate, 2-chloroethyl methacrylate, 2-fluoroethyl acrylate, 2-fluoroethyl methacrylate, 2-cyanoethyl acrylate, 2-cyanoethyl methacrylate, styrene, α-methylstyrene, vinyl toluene, 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 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. No. 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 as follows:
5,000 to 300,000, preferably 2
It is more preferable to be in the range of 0000 to 150,000. If the weight average molecular weight is less than 5,000, the film formability and flexibility of the photosensitive element tend to decrease, and if it exceeds 300,000, the developability (unnecessary portions are easily developed by development). Tend to be reduced).

Further, a thermoplastic resin layer A containing a phosphor
Has a carboxyl group content (defined by an acid value (mgKOH / g)) of a photopolymerizable polymer binder having an ethylenically unsaturated group in a side chain so that development can be performed with various known developers. It can be adjusted appropriately. For example, when developing using an aqueous alkali solution such as sodium carbonate or potassium carbonate, the acid value is preferably from 90 to 260. If the acid value is less than 90, development tends to be difficult, and if it exceeds 260, the developer resistance (the property that a portion which is not removed by development and remains as a pattern and is not attacked by the developer) decreases. Tend to. When developing using an aqueous developing solution comprising water or an aqueous alkali solution and one or more organic solvents, the acid value is 16 to 26.
It is preferably set to 0. If the acid value is less than 16,
Development tends to be difficult, and when it exceeds 260, developer resistance tends to decrease. Further, when an organic solvent developer such as 1,1,1-trichloroethane or an emulsion developer is used, it may not contain a carboxyl group.

Examples of the photoinitiator (c) for generating free radicals upon irradiation with active light include aromatic ketones (benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone). ), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,4-diethylthioxanthone, 2-
Ethyl anthraquinone, 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-methyl-1- (4- (methylthio) phenyl)
-2-morpholinopropanone-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- Phenylimidazole 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 (9,9'- Acridinyl) heptane and the like. 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 it is less than 0 parts by weight, when the photosensitive element is supplied in the form of a roll, the photosensitive resin composition exudes from the end of the roll (hereinafter referred to as edge fusion), so that the photosensitive element is unreeled from the roll during lamination. When a PDP substrate or the like is used, the exuded portion is partially and excessively buried in the space of the PDP substrate, causing a problem such as a remarkable decrease in manufacturing yield, Formability tends to decrease,
If it exceeds 90 parts by weight, 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. If the amount is more than 90 parts by weight, the photocured product tends to become brittle. The reactive 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 A in the present invention contains a known dye, pigment, color former,
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 A 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 A 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 ₂ O ₃ : Eu, YV
O ₄ : Eu, (Y, Gd) BO ₃ : Eu, γ-Zn ₃ (PO ₄ )
2: Mn, (ZnCd) S: Ag + In ₂ O, and the like. Examples of green-colored phosphors include ZnS: C
u, Zn ₂ SiO ₄ : Mn, ZnS: Cu + Zn ₂ Si
O ₄ : Mn, Gd ₂ O ₂ S: Tb, Y ₃ Al ₅ O ₁₂ : Ce,
ZnS: Cu, Al, Y ₂ O ₂ S: Tb, ZnO: Zn,
ZnS: Cu, Al + In ₂ O ₃ , LaPO ₄ : Ce, T
_{b, BaO · 6Al 2 O 3} : Mn , and the like. Examples of the blue-emitting phosphor include ZnS: Ag and ZnS:
Ag, Al, ZnS: Ag, Ga, Al, ZnS: A
g, Cu, Ga, Cl, ZnS: Ag + In ₂ O ₃ , Ca
₂ B ₅ O ₉ Cl: Eu ²⁺ , (Sr, Ca, Ba, Mg) ₁₀ (P
O ₄ ) ₆ Cl ₂ : Eu ²⁺ , Sr ₁₀ (PO ₄ ) ₆ Cl ₁₂ : Eu ²⁺ ,
BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , BaMgAl ₁₄ O ₂₃ : E
u ²⁺ , BaMgAl ₁₆ O ₂₆ : Eu ^{2+ and the} like.

The particle size of the phosphor (d) in the present invention is:
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. Further, the shape of the phosphor (d) in the present invention is preferably spherical, and the surface area thereof is preferably smaller.

The amount of the component (d) in the present invention is as follows:
The amount is preferably from 10 to 400 parts by weight, more preferably from 50 to 350 parts by weight, based on 100 parts by weight of the total of the components (a), (b) and (c).
It is particularly preferred that the amount be 0 to 300 parts by weight. When the amount is less than 10 parts by weight, the luminous efficiency tends to decrease when light is emitted as PDP, and when the amount exceeds 400 parts by weight, the film formability decreases when the photosensitive element is used, Flexibility tends to decrease.

In the present invention, a plasticizer can be added to the photosensitive resin composition constituting the thermoplastic resin layer A in order to improve the film properties. As the plasticizer, the general formula (II)

Embedded image (Wherein, R ⁵ represents a hydrogen atom or a methyl group, Y ¹ represents a hydrogen atom, a saturated hydrocarbon group which may have a substituent or a polyalkylene glycol residue, Y ² represents a hydroxyl group, A represents a saturated hydrocarbon group or a polyalkylene glycol residue which may have a substituent;
A polyalkylene glycol derivative such as polypropylene glycol and its derivatives, polyethylene glycol and its derivatives, and dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate; Biphenyl diphenyl phosphate and the like can be mentioned.

The compounding amount of the plasticizer is preferably 0 to 90 parts by weight, more preferably 0 to 80 parts by weight, based on 100 parts by weight of the total amount of the components (a) and (b). It is particularly preferred that the amount be from 70 to 70 parts by weight. If the amount exceeds 90 parts by weight, the sensitivity of the photosensitive resin composition constituting the thermoplastic resin layer A tends to be insufficient.

The photosensitive resin composition constituting the thermoplastic resin layer A 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. Examples of the compound having a carboxyl group include saturated fatty acids, unsaturated fatty acids, aliphatic dibasic acids, 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, it is preferable to add a dispersant to the photosensitive resin composition constituting the thermoplastic resin layer A in order to improve the dispersion of the phosphor. Examples of dispersants include inorganic dispersants (silica gel, bentonite, kaolinite, talc, hectorite, montmorillonite, saponite, beidellite, etc.), and organic dispersants (aliphatic amide, aliphatic ester). , Polyethylene oxide-based, sulfate-based anion activator, polycarboxylic acid amine salt-based, polycarboxylic acid-based, polyamide-based,
Polymer polyether type, acrylic copolymer type, special silicon type, etc.). These can be used alone or in combination of two or more.

The amount of the dispersant used is not particularly limited, and is preferably 0 to 100 parts by weight, more preferably 0.01 to 100 parts by weight, per 100 parts by weight of the component (a). . If this amount exceeds 100 parts by weight, the pattern formation accuracy (the property of obtaining a pattern made of a photosensitive resin composition containing a phosphor, which is dimensionally accurate after development and has a desired shape) deteriorates. Tend to.

A binder may be used in the photosensitive resin composition constituting the thermoplastic resin layer A in the present invention in order to prevent the phosphor from peeling off the PDP substrate after firing. Examples of the binder include a low-melting glass, a metal alkoxide, and a silane coupling agent. These are used alone or in combination of two or more. The amount of the binder used is not particularly limited, and is preferably 0 to 100 parts by weight, more preferably 0 to 50 parts by weight, and more preferably 0 to 50 parts by weight, based on 100 parts by weight of the component (d). Particularly preferred is 30 parts by weight. If the amount exceeds 100 parts by weight, the luminous efficiency tends to decrease.

In the film having the thermoplastic resin layer A in the present invention, the components constituting the thermoplastic resin layer A are uniformly dissolved or dispersed by dissolving or mixing the components in a solvent that can be dissolved or dispersed. It can be obtained as a photosensitive element by forming a solution, coating and drying on a support film. As the solvent capable of dissolving or dispersing each component, 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. Since the support film must be removable from the thermoplastic resin layer A later, it must not be 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. Drying temperature is 60 ~
The temperature is preferably set to 130 ° C, and the drying time is 3 minutes to 1 minute.
Preferably, it is time.

The thickness of the thermoplastic resin layer A of the photosensitive element is not particularly limited. , Preferably 1 to 10 µm, more preferably 1 to 5 µm. Also, P
When used for the manufacture of DP substrates, the thickness is 10
２００200 μm, preferably 20-120 μm
The thickness is more preferably 20 to 80 μm, and most preferably 30 to 80 μm. When the film thickness is less than 10 μm, a phosphor pattern after firing described later becomes thin and the luminous efficiency tends to decrease. Tend.

The thermoplastic resin layer A of the photosensitive element comprises
The viscosity at 100 ° C. is preferably from 1 to 1 × 10 ⁹ Pa · sec, more preferably from 2 to 1 × 10 ⁸ Pa · sec, and from 5 to 1 × 10 ⁷ Pa · sec. Particularly preferred is 10 to 1 × 10 ⁶ Pa · sec. When the viscosity at 100 ° C. is less than 1 Pa · sec, the viscosity at room temperature becomes too low, and when the photosensitive element is used, the thermoplastic resin layer A tends to bleed from the edge due to the flow, and the film is formed. Properties tend to decrease. On the other hand, if it exceeds 1 × 10 ⁹ Pa · sec, the formability of the thermoplastic resin layer A on the inner surface of the concave portion of the substrate having irregularities tends to decrease when used for manufacturing a substrate for PDP or the like.

A releasable cover film can be further laminated on the thermoplastic resin layer A of the photosensitive element. Examples of the cover film include polyethylene, polypropylene, polyethylene terephthalate, and polycarbonate. The adhesive force between the cover film and the thermoplastic resin layer A is smaller than the adhesive force between the support film and the thermoplastic resin layer A. Preferably, it is The photosensitive element thus obtained can be stored in a roll.

The thermoplastic resin (e) constituting the thermoplastic resin layer 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 polyvinyl acetate. , Polyvinylidene chloride, polystyrene, polyvinyl toluene,
Polyacrylate, polymethacrylate,
Copolymer of ethylene and vinyl acetate, copolymer of ethylene and acrylic ester, copolymer of vinyl chloride and vinyl acetate, copolymer of styrene and acrylic ester or methacrylic ester, vinyl toluene and acrylic ester Or a copolymer with a methacrylate, a polyvinyl alcohol-based resin (a hydrolyzate of a polyacrylate or polymethacrylate, a hydrolyzate of polyvinyl acetate, a hydrolyzate of a copolymer of ethylene and vinyl acetate) , A hydrolyzate of a copolymer of ethylene and acrylate, a hydrolyzate of a copolymer of vinyl chloride and vinyl acetate, a hydrolyzate of a copolymer of styrene and acrylate or methacrylate, Hydrolysis of copolymer of vinyltoluene and acrylate or methacrylate Carboxyalkyl cellulose, water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinylpyrrolidone, unsaturated carboxylic acids and unsaturated monomers copolymerizable therewith. And a resin having a carboxyl group.

Further, when the thermoplastic resin layer B is used for manufacturing a substrate for PDP, etc.
A plasticizer can be contained from the viewpoint of improving the film properties. Examples of the plasticizer to be used include (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group at a terminal, polypropylene glycol represented by the general formula (II) and derivatives thereof, and polyethylene glycol and derivatives thereof. Alkylene glycol derivatives, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate,
Tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate, and the like. Further, the thermoplastic resin layer B may contain (c) a photoinitiator that generates free radicals upon irradiation with active light.

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. If the compounding amount is less than 10 parts by weight, when the element is used as an element, the resin composition tends to exude from the end due to the flow, or the film-forming property tends to decrease.

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 element is used, there is a tendency that the element exudes from the end due to the flow and the film-forming property is reduced.

Further, the compounding amount of the photoinitiator component (c) contained in the thermoplastic resin layer B, which generates free radicals upon irradiation with actinic light, is defined assuming that the total amount of the resin component and the plasticizer component is 100 parts by weight. Preferably it is 0 to 30 parts by weight, more preferably 0 to 20 parts by weight. When the amount is more than 30 parts by weight, the absorption of active light on the exposed surface increases, and the internal light curing tends to be insufficient.

Further, the thermoplastic resin layer B in the present invention
In the developing step described below, it is preferable that the thermoplastic resin layer A and the thermoplastic resin layer B can be developed using the same developer, because the number of steps can be reduced. Those which can be developed with the same developer include those which are soluble in water or an aqueous alkaline solution.

Examples of the resin constituting the thermoplastic resin layer B soluble in water or an aqueous alkali solution include polyvinyl alcohol resins (hydrolysates of polyacrylate or polymethacrylate, hydrolysis of polyvinyl acetate). Product, 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 acid Hydrolysates of copolymers of esters or methacrylates, hydrolysates of copolymers of vinyltoluene and acrylates or methacrylates), water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers , A water-soluble salt of carboxyalkyl starch, polyvinylpyrrolidone, unsaturated carboxylic acid and A resin having a carboxyl group obtained by copolymerizing these copolymerizable unsaturated monomers.

Examples of the resin having a carboxyl group obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated monomer copolymerizable therewith include, for example, unsaturated carboxylic acids (acrylic acid, methacrylic acid, maleic acid). , Fumaric acid, itaconic acid, etc.) and (a) a vinyl monomer which can be used for the film-imparting polymer constituting the thermoplastic resin layer A and obtained by copolymerization. Is preferred. A resin having a carboxyl group obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated monomer copolymerizable therewith has a weight average molecular weight of 5,
2,000 to 300,000, preferably 20,
It is more preferable to be 000 to 150,000. If the weight average molecular weight is less than 5,000, the film formability and flexibility of the photosensitive element tend to decrease, and if it exceeds 300,000, the developability tends to decrease.

Further, an unsaturated carboxylic acid and an unsaturated monomer copolymerizable therewith are copolymerized so that the thermoplastic resin layer B soluble in an aqueous alkali solution can be developed with various known developing solutions. Value (acid value (mg KOH / mg KOH /
g) can be adjusted as appropriate. 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. If the acid value is less than 90, development tends to be difficult, and if it exceeds 260, developer resistance tends to decrease. In the case of developing 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. When the acid value is less than 16, development tends to be difficult, and when it exceeds 260, developer resistance tends to decrease.

The film having the thermoplastic resin layer B according to the present invention is formed into a uniform solution by dissolving or mixing the components constituting the thermoplastic resin layer B in a solvent capable of dissolving the same. It can be formed into a film by coating and drying on 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, and a curtain coating method. . As a solvent for dissolving the resin constituting the thermoplastic resin layer B, for example, water, toluene,
Acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, γ-butyl lactone, N-methylpyrrolidone, dimethylformamide, tetramethyl sulfone, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, chloroform, methylene chloride, methyl alcohol,
Ethyl alcohol and the like can be mentioned. 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. To 200 μm, more preferably 20 to 100 μm. The thermoplastic resin layer B in the present invention preferably has a viscosity at 100 ° C. of 1 to 1 × 10 ⁹ Pa · sec.
１1 × 10 ⁸ Pa · sec, more preferably 5-1
× 10 ⁷ Pa · sec is particularly preferable, and 10 to 1 ×
It is most preferably 10 ⁶ Pa · sec. This 100
If the viscosity at 0 ° C. is less than 1 Pa · sec, the viscosity at room temperature becomes too low to form a film. Tend. Also, if it exceeds 1 × 10 ⁹ Pa · sec, when it is used for manufacturing a PDP substrate,
There is a tendency that the formability of the thermoplastic resin layer A on the inner surface of the concave portion of the substrate having irregularities is reduced.

Further, a releasable cover film can be further laminated on the thermoplastic resin layer B in the present invention. As the cover film, polyethylene,
Examples thereof include polypropylene, polyethylene terephthalate, and polycarbonate, and it is preferable that the adhesive strength between the cover film and the thermoplastic resin layer B is smaller than the adhesive strength between the support film and the thermoplastic resin layer B. The thermoplastic resin layer B thus formed in a film shape is
It can be stored in a roll.

In the present invention, the film having the thermoplastic resin layer A and the film having the thermoplastic resin layer B are preferably a film having the thermoplastic resin layer A as a support film and a thermoplastic resin layer in view of workability. A and a film having a cover film are preferable, and a film having a thermoplastic resin layer B is preferably a film having a support film, a thermoplastic resin layer B and a cover film. Further, the film having the thermoplastic resin layer A and the film having the thermoplastic resin layer B in the present invention,
Each thermoplastic resin layer does not necessarily have to be a single layer, and may be two or more layers.

In the laminating method of the present invention, the film A is supplied from the first supply unit, the film B is supplied from the second supply unit, and the film A is laminated on the substrate and the film B is laminated thereon. It is necessary to use such a method, for example, a method using the laminating apparatus of the present invention described below.

The laminating apparatus of the present invention comprises a first supplying means for supplying the film A, a second supplying means for supplying the film B, and a laminating means for laminating the film A on the substrate and the film B thereon. It is provided. Further, the laminating apparatus of the present invention comprises a support film (5A), a thermoplastic resin layer A
Film A having (3) and cover film (6A)
And support film (5B), thermoplastic resin layer B
Film B having (4) and cover film (6B)
Is a device for laminating a thermoplastic resin layer A (3) on a substrate (7) and a thermoplastic resin layer B (4) thereon, using a first supply means for supplying the film A, B
, A means for removing the cover film ((6A) and (6B)), a means for removing the support film (5A), and the thermoplastic resin layer A (3) and the thermoplastic resin layer It is provided with a laminating means for laminating B (4).

Further, the laminating apparatus of the present invention comprises a conveying means for feeding the substrate (7), a first feeding means for feeding the film A,
The second supply means for supplying the film B, the means for removing the cover film ((6A) and (6B)), and sending the film having the thermoplastic resin layer A (3) or the thermoplastic resin layer B (4). Means for feeding the support film (5A), means for removing the support film (5A),
A laminating means for laminating a film having a thermoplastic resin layer A (3) or a thermoplastic resin layer B (4) on a substrate (7) is provided. Specific examples of the above-described laminating apparatus of the present invention include the laminating apparatuses shown in FIGS.

Hereinafter, the laminating apparatus of the present invention will be described with reference to FIGS. 3 and 4. 3 and 4 are schematic views showing an example of the laminating apparatus of the present invention. The laminating apparatus in FIG. 3 includes a transport roll (11) for feeding a substrate (7), a first supply roll (1) for feeding a film A, a cover film winding roll (8) for winding a cover film (6A), A feed roll (12) for feeding a film having a support film (5A) and a thermoplastic resin layer A (3), a support film (5A)
Roll (10) for laminating the film having the thermoplastic resin layer A (3) on the substrate (7), a feed roll (12) for feeding the support film (5A), and winding the support film (5A) Support film take-up roll (9), second supply roll (2) for supplying film B, cover film take-up roll (8) for winding cover film (6B), support film (5B) and thermoplastic Resin layer B
A support film (5B) and a thermoplastic resin layer B are provided on a feed roll (12) for feeding a film having (4) and a thermoplastic resin layer A (3) laminated on a substrate (7).
Laminating roll (10) for laminating a film having (4)
Is provided.

The support film (5A) and the thermoplastic resin layer A are placed on the first supply roll (1) for supplying the film A.
(3) A roll-shaped film A having a cover film (6A) is installed, and a cover film take-up roll (8)
Then, while winding up the cover film (6A), the film having the support film (5A) and the thermoplastic resin layer A (3) is fed by the feed roll (12) to the laminate roll (10).
And a thermoplastic resin layer A (3) having a support film (5A) is laminated on the substrate (7). The substrate (7) on which the thermoplastic resin layer A (3) is laminated is fed by a transport roll (11), and the support film (5A) on the thermoplastic resin layer A (3) is fed by a feed roll (12). Then, it was sent to the support film take-up roll (9), was taken up by the support film take-up roll (9), and only the thermoplastic resin layer A (3) was laminated on the substrate (7). State.

On the other hand, a roll-shaped film B having a support film (5B), a thermoplastic resin layer B (4) and a cover film (6B) is set on a second supply roll (2) for supplying the film B. Then, while winding the cover film (6B) with the cover film winding roll (8), the film having the support film (5B) and the thermoplastic resin layer B (4) is laminated with the feed roll (12). It is sent to a roll (10), and a thermoplastic resin layer B (4) having a support film (5B) is laminated on a thermoplastic resin layer A (3) laminated on a substrate (7). FIG. 3 also shows a partially enlarged view of the lamination process.

The pressing pressure of the laminating roll (10) for laminating the thermoplastic resin layer A (3) having the support film (5A) is 1 × 10 ² gauge pressure (normal pressure 1 atm is 0).
１1 × 10 ⁷ Pa, preferably 5 × 10 ² -5 ×
It is more preferably 10 ⁶ Pa, and 1 × 10 ⁴ to 1 × 1
It is particularly preferred to 0 ⁶ Pa. This pressure is the cylinder pressure of the laminator and can be converted to linear pressure.
Preferably, the linear pressure is 50 to 1 × 10 ⁵ N / m,
It is more preferably from 2.5 × 10 ^{2 to} 5 × 10 ⁴ N / m, and particularly preferably from 5 × 10 ² to 4 × 10 ⁴ N / m. When the pressure is less than 50 N / m, the thermoplastic resin layer A (3) tends to be unable to adhere sufficiently to the substrate (7). When the pressure exceeds 1 × 10 ⁵ N / m, the substrate (7) Tend to be destroyed. Here, as a method of setting the linear pressure to 5 × 10 ³ N / m, for example, using a laminator having a cylinder diameter of 40 mmφ, a thickness of 3 mm, a length of 10 cm × a width of 10 cm (square)
Using the laminator cylinder pressure (normal pressure 1 at)
m is 0) to 2 kgf / cm ² so that the linear pressure is 5 × 10 ³ N / m. A method in which the linear pressure is set to 5 × 10 ³ N / m by using a (square) substrate and setting the cylinder pressure of the laminator (normal pressure 1 atm is 0) to 4 kgf / cm ^2. .

A laminating roll (10) for laminating a thermoplastic resin layer A (3) having a support film (5A)
In order to improve the adhesion of the thermoplastic resin layer A (3) to the substrate (7), a heat-pressing roll may be used, and heating may be performed. The heating temperature when heating is involved is 10 to 14
The temperature is preferably 0 ° C, more preferably 10 to 130 ° C, still more preferably 20 to 130 ° C, particularly preferably 30 to 130 ° C, and 30 to 130 ° C.
It is most preferable to set the temperature to 110 ° C. If the heating temperature is lower than 10 ° C., the thermoplastic resin layer A (3) tends to be unable to sufficiently adhere to the substrate (7). Tends to harden. If the thermoplastic resin layer A (3) is heated as described above, it is not necessary to pre-heat the substrate (7),
From the viewpoint of further improving the adhesion of the thermoplastic resin layer A (3) to the substrate (7), it is preferable to perform a pre-heat treatment on the substrate (7).

The material of the laminating roll (10) for laminating the thermoplastic resin layer A (3) having the support film (5A) is not particularly limited. From the viewpoint of further improving the adhesion to ()), it is preferable that the surface of the roll is made of a material having high flexibility such as rubber and plastic. Note that the thickness of the layer made of a material having high flexibility is preferably 200 to 400 μm.

The pressing pressure of the laminating roll (10) for laminating the thermoplastic resin layer B (4) having the support film (5B) is 1 × 10 ⁴ gauge pressure (normal pressure 1 atm is 0).
１1 × 10 ⁷ Pa, preferably 2 × 10 ⁴ -5 ×
It is more preferably 10 ⁶ Pa, and 4 × 10 ⁴ to 1 × 1
It is particularly preferred to 0 ⁶ Pa. This pressure is the cylinder pressure of the laminator and can be converted to linear pressure.
Preferably, the linear pressure is 5 to 1 × 10 ⁵ N / m.
It is more preferably 5 × 10 ^{2 to} 5 × 10 ⁴ N / m,
It is particularly preferred to be 1 × 10 ² to 4 × 10 ⁴ N / m.
If the pressure is less than 50 N / m, the thermoplastic resin layer B
(4), tend not to be sufficiently close contact on the thermoplastic resin layer A (3), exceeds 1 × 10 ⁵ N / m, the substrate (7)
Tend to be destroyed.

A laminating roll (10) for laminating a thermoplastic resin layer B (4) having a support film (5B)
Is the thermoplastic resin layer A (3) of the thermoplastic resin layer B (4)
From the viewpoint of improving the adhesion to
Heating can also be involved. The heating temperature when accompanied by heating is preferably 10 to 140 ° C., and 10 to 13 ° C.
° C, more preferably 20 to 130 ° C, particularly preferably 30 to 130 ° C, most preferably 30 to 110 ° C. If the heating temperature is less than 10 ° C., the thermoplastic resin layer B (4) tends to be unable to sufficiently adhere to the thermoplastic resin layer A (3), and if it exceeds 140 ° C., the thermoplastic resin layer A ( 3) and the thermoplastic resin layer B (4) tend to be thermoset.

When the substrate (7) is a substrate for a PDP having irregularities, it is necessary to adhere the thermoplastic resin layer A (3) on the irregular surface of the irregular substrate. Since the thermoplastic resin layer B (4) plays a role of an embedding layer, the heating of the laminating roll (10) for laminating the thermoplastic resin layer B (4) is an essential condition. FIG.
FIG. 5 is a schematic view showing an uneven surface of a substrate having unevenness. In FIG. 5, (18) on the uneven surface is shown by hatching.

The material of the laminating roll (10) for laminating the thermoplastic resin layer B (4) having the support film (5B) is not particularly limited, but the thermoplastic resin of the thermoplastic resin layer B (4) is From the viewpoint of improving the adhesion to the layer A (3), it is preferable that the surface of the roll be made of a material having a high flexibility such as rubber or plastic. Note that the thickness of the layer made of a material having high flexibility is preferably 200 to 400 μm. The transfer speed of the substrate (7) is 0.0
It is preferably set to 1 to 10 m / min, and 0.02 to 5 m
/ Min, more preferably 0.1 to 2 m / min.

The laminating apparatus shown in FIG. 4 includes a transport roll (11) for feeding a substrate (7), a first feed roll (1) for feeding a film A, a feed roll (12) for feeding a film A, and a cover film (6A). ), A cover film winding roll (8), a support film (5A) and a thermoplastic resin layer A
A feed roll (12) for feeding a film having (3), a second feed roll (2) for feeding a film B, a feed roll (12) for feeding a film B, and a cover film (6B)
, A cover film take-up roll (8), a support film (5B), a feed roll (12) for feeding a film having a thermoplastic resin layer B (4), and a support film (5).
A) and a film having the thermoplastic resin layer A (3), a support film (5B) and a laminating roll (13) for laminating the film having the thermoplastic resin layer B (4), and the support film (5A). Feed roll (12), support film take-up roll (9) for winding support film (5A), thermoplastic resin layer A (3), thermoplastic resin layer B
(4) A feed roll (12) for feeding a film having the support film (5B), a thermoplastic resin layer A (3), a film having the thermoplastic resin layer B (4) and the support film (5B) as a substrate. (7) Laminating roll (1
0).

A first supply roll (1) for supplying the film A is provided with the support film (5A) and the thermoplastic resin layer A.
(3) A roll-shaped film A having the cover film (6A) is set, and the cover film (6A) is fed to the cover film winding roll (8) by the feed roll (12), and the cover film winding roll ( In 8), while winding up the cover film (6A), the film having the support film (5A) and the thermoplastic resin layer A (3) is sent to the joining roll (13) by the feed roll (12). on the other hand,
A roll-shaped film B having a support film (5B), a thermoplastic resin layer B (4) and a cover film (6B) is placed on a second supply roll (2) for supplying the film B, and a feed roll ( 12) In the cover film (6B)
To the cover film take-up roll (8), and while the cover film (6B) is taken up by the cover film take-up roll (8), a film having the support film (5B) and the thermoplastic resin layer B (4) Is sent to a matching roll (13) by a feed roll (12).

A film having a support film (5A) and a thermoplastic resin layer A (3) and a support film (5B)
And a film having the thermoplastic resin layer B (4) is adhered by an assembling roll (13) to form a feed roll (12).
Then, the support film (5A) is sent to the support film take-up roll (9), and the support film take-up roll (9)
While the support film (5A) is being wound, a film having the thermoplastic resin layer A (3), the thermoplastic resin layer B (4) and the support film (5B) is laminated on a feed roll (12) using a laminate roll ( Send to 10). The substrate (7) is transported by the transport rolls (11) while being laminated on the substrate (7) by the laminating rolls (10) on the substrate (7) and the thermoplastic resin layer B (4) and the support. A film having the film (5B) is laminated. A partially enlarged view of the lamination process is also shown in FIG.

The pressing pressure of the laminating roll (10) for laminating a film having the thermoplastic resin layer A (3), the thermoplastic resin layer B (4) and the support film (5B) is a gauge pressure (normal pressure 1 atm). 0) and 1 × 10 ⁴ -1 × 10 ⁷ Pa
The pressure is preferably set to 2 × 10 ^{4 to} 5 × 10 ⁶ Pa, more preferably 4 × 10 ⁴ to 1 × 10 ⁶ Pa. This pressure is the cylinder pressure of the laminator and can be converted to a linear pressure.
× 10 ⁵ N / m, preferably 2.5 × 10 ^{2 to} 5
It is more preferably set to × 10 ⁴ N / m, and 1 × 10 ² to 4
It is particularly preferred to be × 10 ⁴ N / m. If the pressure is less than 50 N / m, the thermoplastic resin layer A (3) and the thermoplastic resin layer B (4) tend not to be sufficiently adhered to the substrate (7), and 1 × 10 ⁵ N / m If it exceeds m, the substrate (7) tends to be broken.

The laminating roll (10) for laminating a film having the thermoplastic resin layer A (3), the thermoplastic resin layer B (4) and the support film (5B) is a thermoplastic resin layer A (3). And the substrate (7) of the thermoplastic resin layer B (4)
From the viewpoint of improving the adhesion to
Heating can also be involved. When heating is performed, the heating temperature is preferably 0 to 130 ° C, and 10 to 130 ° C.
° C, more preferably 10 to 120 ° C, further preferably 20 to 120 ° C, particularly preferably 20 to 110 ° C.
Most preferably, it is 0 to 110 ° C. If the heating temperature is lower than 0 ° C., the thermoplastic resin layer A (3) and the thermoplastic resin layer B (4) tend to be unable to sufficiently adhere to the substrate (7). Plastic resin layer A
(3) and the thermoplastic resin layer B (4) tend to be thermoset.

When the substrate (7) is a substrate for a PDP having irregularities, it is necessary to adhere the thermoplastic resin layer A (3) on the irregular surface of the irregular substrate. Since the thermoplastic resin layer B (4) plays a role of an embedding layer, the above-described heating of the laminated roll (10) is an essential condition. Further, if the thermoplastic resin layer A (3) and the thermoplastic resin layer B (4) are heated as described above, it is not necessary to pre-heat the substrate (7), but the thermoplastic resin layer A (3) is not necessary. ) And the thermoplastic resin layer B (4) are preferably pre-heat-treated from the viewpoint of further improving the adhesion to the substrate (7).

The material of the laminating roll (10) for laminating the film having the thermoplastic resin layer A (3), the thermoplastic resin layer B (4) and the support film (5B) is not particularly limited. In order to improve the adhesion of the thermoplastic resin layer A (3) and the thermoplastic resin layer B (4) to the substrate (7), the surface of the roll should be made of a material having a high flexibility such as rubber or plastic. It is preferred to use. Note that the thickness of the layer made of a material having high flexibility is preferably 200 to 400 μm. The transfer speed of the substrate (7) is
0.01 to 10 m / min, preferably 0.02 to 10 m / min.
To 5 m / min, more preferably 0.1 to 2 m / min.
It is particularly preferable to set it to minutes.

[0096] Moreover, lamination method of the present invention, 5 × 10 ⁴ Pa
It may be performed under the following reduced pressure, and the laminating apparatus of the present invention can be decompressed, and the laminating apparatus of the present invention can be used under a reduced pressure of 5 × 10 ⁴ Pa or less.

[0097]

The laminating apparatus of the present invention is capable of laminating two or more kinds of films having a thermoplastic resin layer with only one apparatus, and has good workability. By adjusting the pressing pressure, heating temperature and the like of the laminating roll (10) in the laminating apparatus of the present invention, the adhesion of the thermoplastic resin layer to the substrate (7) can be satisfactorily laminated, and the workability is also good. Also, P
Even in a substrate having irregularities such as a DP substrate, the thermoplastic resin layer can be laminated on the inner surface of the concave portion with good embedding property. By using the laminating apparatus of the present invention, lamination can be performed with only one apparatus, so that the space of the apparatus can be saved. Further, the laminating apparatus of FIG. 3 according to the present invention has a simple structure, is easy to prepare for the start of work, and has excellent maintainability. Further, in the laminating apparatus of FIG. 4 according to the present invention, two or more types of thermoplastic resin layers can be formed on the substrate in one lamination, so that defects during lamination can be suppressed.

The laminating method and the laminating apparatus of the present invention are suitable for laminating two or more kinds of films with good workability, and require the production of a color filter, the production of a plasma display panel, and the production of an EL substrate, which require a multilayer lamination. It can be effectively used for manufacturing a substrate for forming a field emission display phosphor layer, and is more suitable for manufacturing a plasma display panel using a substrate having a relatively large unevenness.

Hereinafter, as an example using the laminating method of the present invention and the laminating apparatus of the present invention, a method of manufacturing a phosphor pattern in manufacturing a plasma display panel will be described. According to the method for producing a phosphor pattern of the present invention, (I) forming a photosensitive resin composition layer (thermoplastic resin layer A) containing a phosphor and a thermoplastic resin layer B on an uneven surface of a substrate having unevenness. (II) irradiating actinic rays imagewise, (II)
It has the following steps: I) a step of removing unnecessary portions by development, and (IV) a step of removing unnecessary portions by firing.

Hereinafter, each step of the method for manufacturing a phosphor pattern will be described with reference to FIG. FIG. 6 is a schematic view showing each step of the method for manufacturing a phosphor pattern. [(I) Step of Forming Photosensitive Resin Composition Layer (Thermoplastic Resin Layer A) and Thermoplastic Resin Layer B Containing Phosphor on Irregular Surface of Substrate Having Irregularities] Barrier rib (15) is formed The photosensitive resin composition layer containing a phosphor (thermoplastic resin layer A) is formed on the uneven surface of the transparent substrate for PDP (14) (substrate having unevenness) by using the laminating method and the laminating apparatus of the present invention. FIG. 6I shows a state where (3) and the thermoplastic resin layer B (4) are formed.

[(II) Step of irradiating actinic rays imagewise]
FIG. 6 (II) shows a state where the actinic ray (20) is irradiated imagewise. In the step of FIG. 6 (II), actinic rays (20)
Is imagewise irradiated on the thermoplastic resin layer B (4) in the state shown in FIG. 6 (I) by adding a photomask (1) such as a negative film, a negative glass, a positive film,
The actinic ray (20) can be radiated imagewise via 9). At this time, when the support film (5B) is present on the thermoplastic resin layer B (4), even if the support film (5B) is laminated and the actinic ray (20) is irradiated imagewise. Alternatively, after removing the support film (5B), the actinic ray (20) may be irradiated imagewise. At this time, when the thermoplastic resin layer B (4) has photosensitivity, the thermoplastic resin layer B (4) is formed of a photosensitive resin composition layer containing a phosphor (thermoplastic resin layer). Layer A)
(3) At the same time, photo-curing is performed.

As the actinic ray (20), 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 the like. Since the sensitivity of the photoinitiator is usually maximal in the ultraviolet region, the active light source in that case should be one that effectively emits ultraviolet light. When the photoinitiator is sensitive to visible light, for example, 9,10-phenanthrenequinone or the like, visible light is used as active light (20), 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 (20) may be a parallel ray, a scattered ray, or the like. Either a parallel ray or a scattered ray may be used. They may be used separately in stages.
If both are used separately in two stages, either may be performed first.

[(III) Step of Removing Unwanted Parts by Development] FIG. 6 (III) shows a state where the unnecessary parts are removed by development. In FIG. 6 (III), reference numeral 3 'denotes a photosensitive resin composition layer containing a phosphor after photocuring. FIG.
In (III), as a developing method, for example, FIG.
After the state of I), if the support film (5B) is present on the thermoplastic resin layer B (4), after removing the support film (5B), a known aqueous solution such as an alkaline aqueous solution, an aqueous developer, or an organic solvent is used. Using a developer, spray, rocking dipping, brushing,
A method in which development is performed by a known method such as scraping to remove unnecessary portions, and the like can be given.

When removing unnecessary portions, first, a photosensitive resin composition layer containing a phosphor (thermoplastic resin layer A)
An unnecessary portion of the thermoplastic resin layer B (4) is removed by dissolving using (3) water, an alkali aqueous solution, a semi-solvent aqueous solution, a semi-solvent alkaline aqueous solution, an organic solvent, or the like, and then using a developer. Unnecessary portions of the phosphor-containing photosensitive resin composition layer (thermoplastic resin layer A) (3) may be removed, and the phosphor-containing photosensitive resin composition layer (thermoplastic resin layer) A) (3) and thermoplastic resin layer B (4)
Are those which can be developed using the same developer, the unnecessary portion of the photosensitive resin composition layer containing the phosphor (thermoplastic resin layer A) (3) can be prepared using the developer. Unnecessary portions of the thermoplastic resin layer B (4) can be removed in one step. Further, as a method of removing unnecessary portions of the photosensitive resin composition layer (thermoplastic resin layer A) (3) containing a phosphor and unnecessary portions of the thermoplastic resin layer B (4), dry development is performed, respectively. It can be performed alone or in one step.

In the step (III), the (I)
The photosensitive resin composition layer containing the phosphor (the thermoplastic resin layer A) other than the inner surface of the recess formed by the step I)
(3) and thermoplastic resin layer B (4) (thermoplastic resin layer B)
When (4) has photosensitivity, the thermoplastic resin layer B (4) other than the inner surface of the concave portion is an unnecessary portion, which needs to be removed by development. FIG. 7 is a schematic diagram showing the inner surface of the concave portion.
2) is indicated by hatching.

The developing time and the developing temperature in the step (III) can be appropriately adjusted so that unnecessary portions can be removed. The development time is determined by the minimum development time of the photosensitive resin composition layer containing the phosphor (the thermoplastic resin layer A) (3) (the photosensitive resin composition layer containing the phosphor (the thermoplastic resin layer A) (3) ) 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 A) (3) 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 (thermoplastic resin layer A) ( There is a tendency that the necessary part of 3) is removed. When the developing temperature is 10
When the temperature is lower than 0 ° C, the developability tends to decrease. When the 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 pyrophosphates (sodium pyrophosphate, potassium pyrophosphate, etc.), tetramethylammonium hydroxide, triethanolamine, etc., among which sodium carbonate, tetramethylammonium hydroxide And the like are preferred. PH of aqueous alkaline solution used for development
Is preferably 9 to 11, and the temperature is determined by the developability of the photosensitive resin composition layer (thermoplastic resin layer A) (3) and the thermoplastic resin layer B (4) containing the phosphor. Can be adjusted to suit. In addition, 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 alkaline aqueous solution, in addition to 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 triacetone 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. These can be used alone or 2
Used in combination of more than one type. The concentration of the organic solvent is usually in the range of 2 to 90% by weight, and the temperature can be adjusted according to the developability. Also,
A small amount of a surfactant, an antifoaming agent or the like can be mixed in the aqueous developer. Examples of the organic solvent developer used alone include, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyrolactone, and the like. Water may be added to these organic solvents in the range of 1 to 20% by weight to prevent ignition.

Thus, the photosensitive resin composition layer (thermoplastic resin layer A) (3) (unnecessary part) (phosphoric resin layer B (4)) containing the phosphor formed on other than the inner surface of the concave portion is formed. When the photosensitive resin composition has photosensitivity, the thermoplastic resin layer B (4) other than the inner surface of the concave portion is removed by development, and the photosensitive resin composition layer containing the photocured phosphor is formed on the inner surface of the concave portion. 3 ′ (when the thermoplastic resin layer B (4) has photosensitivity, the photo-cured thermoplastic resin layer B is also included).

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 ultraviolet rays is generally preferably be 5~10000mJ / cm ^2, more preferably to 7~5000mJ / cm ^2, and particularly preferably to 10~3000mJ / cm ^2. Further, the temperature during heating is preferably from 60 to 180 ° C, 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 may be performed first.

[(IV) Step of Removing Unwanted Components by Firing] FIG. 6 (IV) shows a state in which the phosphor pattern has been formed after the unnecessary components have been removed by firing. FIG. 6 (IV)
, 21 is a phosphor pattern. In FIG. 6 (IV), the firing method is not particularly limited, and a known firing method can be used to remove unnecessary components other than the phosphor and the binder, thereby forming a phosphor pattern. At this time, the maximum firing temperature is preferably from 350 to 800 ° C, more preferably from 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 rate is preferably 0.5 to 50 ° C./min, more preferably 1 to 45 ° C./min. Also, before reaching the maximum firing temperature,
A step of holding the temperature between 450 ° C. can be provided, and the holding time is preferably 5 to 100 minutes.

According to the method for producing a phosphor pattern of the present invention, the above steps (I) to (III) are repeated for each color to produce red, green and blue in view of the fact that the number of steps can be reduced. After forming a multicolor pattern composed of the photosensitive resin composition layer containing the phosphor to be formed, it is preferable to perform the step (IV) to form a multicolor phosphor pattern. In the method for producing a phosphor pattern according to the present invention, the photosensitive resin composition layer (thermoplastic resin layer A) (3) containing a phosphor containing each of the phosphors that emit red, blue, and green colors alone,
The red, blue and green colors can be performed in any order.

The steps (I) to (III) 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. 8 shows a state in which a multicolor pattern including is formed. In FIG. 8, 3′a is a pattern of the first color,
3'b is a second color pattern and 3'c is a third color pattern. FIG. 9 shows a state in which the step (IV) in the method for producing a phosphor pattern of the present invention has been performed to form a multicolor phosphor pattern. In FIG. 9, 21a is a first color phosphor pattern, 21b is a second color phosphor pattern, and 21c is a third color phosphor pattern.

Further, the method for producing a phosphor pattern of the present invention can be applied to a method for suppressing film loss of a photosensitive resin composition layer (thermoplastic resin layer A) (3) containing a phosphor formed on the inner surface of a recess. From the viewpoint, (I) in the method for producing the phosphor pattern
It is preferable to repeat the steps (IV) to (IV) for each color to form a multicolor phosphor pattern that emits red, green, and blue light.

The back plate for a plasma display panel of the present invention comprises the fluorescent pattern obtained as described above on a substrate for a plasma display panel. The back plate for a plasma display panel will be described below with reference to FIG. FIG. 10 is a schematic view showing an example of a plasma display panel (PDP). In FIG. 10, 14 is a transparent substrate, 15 is a barrier rib, 17 is a striped discharge space, 21 is a phosphor pattern, and 23 is an address. Electrode, 24 is a protective film, 25
Is a dielectric layer, 26 is a display electrode, and 27 is a front plate substrate. In FIG. 10, the transparent substrate 14, the barrier rib 1
5, the lower part including the phosphor pattern 21 and the addressing electrode 23 is the back plate for PDP, and the protective film 24, the dielectric layer 2
5. The upper portion including the display electrode 26 and the front plate substrate 27 is the PDP front plate. PDPs can be classified into AC (alternating current) type PDPs, DC (direct current) type PDPs, and the like according to a voltage application method. The schematic diagram of FIG. 10 shown as an example is an AC type PDP.

[0117]

The present invention will be described below with reference to examples. Production Example 1 [Preparation of Film-Promoting Polymer (a) Solution] A flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer was charged with the contents shown in Table 1, and was charged under a nitrogen gas atmosphere.
The temperature was raised to 0 ° C, and the reaction temperature was kept at 80 ° C ± 2 ° C, and the contents shown in Table 1 were dropped uniformly over 4 hours. After the dropwise addition, stirring was continued for 6 hours at 80 ° C. ± 2 ° C., and a solution (45.5% by weight of solid content) of the polymer (a) having a weight average molecular weight of 80,000 and an acid value of 130 mg KOH / g was added. Obtained.

[0118]

[Table 1]

Production Example 2 [Preparation of Solution (A-1) for Thermoplastic Resin Layer A] The materials shown in Table 2 were mixed for 15 minutes using a Raikai machine to obtain a solution (A-1) for thermoplastic resin layer A. ) Was prepared.

[0120]

[Table 2]

Production Example 3 [Preparation of Solution for Thermoplastic Resin Layer A (A-2)] The materials shown in Table 3 were mixed for 15 minutes using a Raikai machine to obtain a solution for thermoplastic resin layer A (A-2). ) Was prepared.

[0122]

[Table 3]

Production Example 4 [Preparation of Photosensitive Element (i)] The solution (A-1) for the thermoplastic resin layer A obtained in Production Example 2 was uniformly spread on a polyethylene terephthalate film having a thickness of 50 μm. The resin was applied and dried for 10 minutes with a hot air convection dryer at 110 ° C. to remove the solvent, thereby forming a thermoplastic resin layer A. The thickness of the obtained thermoplastic resin layer A was 60 μm. Next, a polyethylene film having a thickness of 25 μm was further laminated on the thermoplastic resin layer A 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 6. [Edge fusion property] The photosensitive element (i) having a length of 90 m wound up in a roll shape is stored at a temperature of 23 ° C and a humidity of 60% Rh, and the state of exudation of the photosensitive layer from the roll side surface is shown below. Evaluation was made visually for 6 months. The evaluation criteria are as follows. ：: Good edge fusion property (no exudation of photosensitive layer even in 6 months) ×: Poor edge fusion property (thing exuded of photosensitive layer in 6 months)

Production Example 5 [Preparation of photosensitive element (ii)]
Solution for thermoplastic resin layer A obtained in Production Example 2 (A-1)
With the solution for thermoplastic resin layer A obtained in Production Example 3 (A-
A photosensitive element (ii) was produced in the same manner as in Production Example 4, except that 2) was used. In addition, the thickness of the thermoplastic resin layer A of the photosensitive element (ii) was 40 μm. The edge fusion property of the obtained photosensitive element (ii) was evaluated in the same manner as in Production Example 4, and the results are shown in Table 6.

Production Example 6 [Preparation of Photosensitive Element (iii)] The materials shown in Table 4 were mixed for 15 minutes using a raikai machine to prepare a solution for thermoplastic resin layer A (A-3).

[0127]

[Table 4]

Next, in Production Example 4, the solution for thermoplastic resin layer A (A-1) was replaced with the solution for thermoplastic resin layer A (A-
A photosensitive element (iii) was produced in the same manner as in Production Example 4 except that 3) was used. The thickness of the thermoplastic resin layer A of the photosensitive element (iii) was 40 μm. The edge fusion property of the obtained photosensitive element (iii) was evaluated in the same manner as in Production Example 4, and the results were shown in Table 6.
It was shown to.

Production Example 7 [Preparation of photosensitive element (iv)]
Mix for 15 minutes using a Raikai machine, and add thermoplastic resin layer A
A solution for use (A-4) was prepared.

[0130]

[Table 5]

Next, in Production Example 4, the solution (A-1) for the thermoplastic resin layer A was replaced with the solution (A-
A photosensitive element (iv) was produced in the same manner as in Production Example 4, except that 4) was used. Incidentally, the thickness of the thermoplastic resin layer A of the photosensitive element (iv) was 40 μm. The edge fusion property of the obtained photosensitive element (iv) was evaluated in the same manner as in Production Example 4, and the results are shown in Table 6.

[0132]

[Table 6]

From the results shown in Table 6, the edge fusion properties of the photosensitive elements produced in Production Examples 4 to 7 were good.

Production Example 8 [Preparation of Film (B-1) Having Thermoplastic Resin Layer B] A resin solution composed of the materials shown in Table 7 was uniformly applied on a polyethylene terephthalate film having a thickness of 20 μm. Drying was performed for 10 minutes with a hot air convection dryer at 110 ° C. to remove distilled water, thereby forming a thermoplastic resin layer B.
The thickness of the obtained thermoplastic resin layer B after drying is 70 μm.
Met.

[0135]

[Table 7]

Then, a polyethylene film having a thickness of 25 μm is laminated as a cover film on the thermoplastic resin layer B to form a thermoplastic resin layer B comprising a support film, the thermoplastic resin layer B and the cover film. Film (B-1) was produced.

Production Example 9 [Preparation of Film (B-2) Having Thermoplastic Resin Layer B] A resin solution composed of the materials shown in Table 7 was uniformly applied on a polyethylene terephthalate film having a thickness of 20 μm. Drying was performed for 10 minutes with a hot air convection dryer at １１０110 ° C. to remove the solvent, thereby forming a thermoplastic resin layer B. The thickness of the obtained thermoplastic resin layer B after drying was 45 μm.

[0138]

[Table 8]

Next, a 25 μm-thick polyethylene film is laminated as a cover film on the thermoplastic resin layer B to form a thermoplastic resin layer B composed of a support film, a thermoplastic resin layer B and a cover film. Film (B-2) was produced.

[Lamination of Photosensitive Element Having Thermoplastic Resin Layer A and Film Having Thermoplastic Resin Layer B] Example 1 PDP substrate having irregularities (striped barrier ribs, opening width between barrier ribs 150 μm, barrier ribs The photosensitive element (i) having the thermoplastic resin layer A obtained in Production Example 4 on the side on which the barrier rib having a width of 70 μm and a barrier rib height of 150 μm) was formed using the laminating apparatus of the present invention shown in FIG. While peeling off the polyethylene film of the above, the laminating temperature is 60 ° C. and the laminating speed is 0.
5m / min, crimping pressure (cylinder pressure) 5 × 10 ⁴ Pa
(Because a substrate having a width of 10 cm was used, the linear pressure at this time was 1.
2 × 10 ³ N / m), the polyethylene terephthalate film on the surface of the photosensitive element (i) that is not in contact with the barrier rib is peeled off, and a film having a thermoplastic resin layer B on the thermoplastic resin layer A (B- While peeling off the polyethylene film of 1), the laminating temperature was 120 ° C., the laminating speed was 0.5 m / min, and the pressing pressure (cylinder pressure) was 4 × 10 ⁵ Pa (a 10 cm wide substrate was used. Was laminated at 9.8 × 10 ³ N / m), and the thermoplastic resin layer A and the thermoplastic resin layer B were embedded in the inner surface of the concave portion.

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

Example 2 Using the laminating apparatus of the present invention shown in FIG. 4, the photosensitive element (ii) having the thermoplastic resin layer A obtained in Production Example 5
And the film (B-2) having the thermoplastic resin layer B, while peeling off each polyethylene film, the laminating temperature is 20 ° C., the laminating speed is 0.5 m / min, and the pressing pressure (cylinder pressure) is 5 × 10 ⁴ Pa ( Since a film having a width of 10 cm was used, the linear pressure at this time was 1.2 × 10 ³ N /
m), and peeling off the polyethylene terephthalate film on the surface of the photosensitive element (ii) that is not in contact with the thermoplastic resin layer B, while forming a PDP substrate having irregularities (striped barrier ribs, opening width 150 between barrier ribs).
μm, barrier rib width 70 μm, barrier rib height 15
On the side where the barrier ribs (0 μm) were formed, the laminating temperature was 120 ° C., the laminating speed was 0.5 m / min, and the pressing pressure (cylinder pressure) was 4 × 10 ⁵ Pa (because a 10 cm wide substrate was used, The layers were laminated at a linear pressure of 9.8 × 10 ³ N / m), and the thermoplastic resin layer A and the thermoplastic resin layer B were embedded in the inner surface of the recess.

The substrate on which the thermoplastic resin layer A and the thermoplastic resin layer B were laminated was cut in a direction perpendicular to the stripe direction, and the cut surface was observed with an electron microscope to check the phosphor layer forming property. As a result, it was found that a uniform and good phosphor layer was formed.

Example 3 Using the laminating apparatus of the present invention shown in FIG. 4, the photosensitive element (ii) having the thermoplastic resin layer A obtained in Production Example 6 was prepared.
i) and a film (B-2) having a thermoplastic resin layer B
While peeling each polyethylene film, lamination temperature is 20 ° C, lamination speed is 0.5m / min,
Crimping pressure (cylinder pressure) is 5 × 10 ⁴ Pa (width 10c)
m, the linear pressure at this time was 1.2 ×
10 ³ N / m), and peeling off the polyethylene terephthalate film on the surface of the photosensitive element (iii) that is not in contact with the thermoplastic resin layer B, and forming a PDP substrate having irregularities (stripe-shaped barrier ribs, The laminating temperature is 120 ° C. and the laminating speed is 0.5 m / m on the side on which the barrier rib having an opening width of 150 μm, a barrier rib width of 70 μm, and a barrier rib height of 150 μm) is formed.
Min, the pressure (cylinder pressure) is 4 × 10 ⁵ Pa (width 10c)
Since the substrate of m was used, the linear pressure at this time was 9.8 × 10 ³
N / m), and a thermoplastic resin layer A and a thermoplastic resin layer B were embedded in the recess inner surface.

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

Example 4 Using the laminating apparatus of the present invention shown in FIG. 4, the photosensitive element (iv) having the thermoplastic resin layer A obtained in Production Example 7
And the film (B-2) having the thermoplastic resin layer B, while peeling off each polyethylene film, the laminating temperature is 20 ° C., the laminating speed is 0.5 m / min, and the pressing pressure (cylinder pressure) is 5 × 10 ⁴ Pa ( Since a film having a width of 10 cm was used, the linear pressure at this time was 1.2 × 10 ³ N /
m), and peeling off the polyethylene terephthalate film on the surface of the photosensitive element (iv) which is not in contact with the thermoplastic resin layer B, and forming a PDP substrate having irregularities (striped barrier ribs, opening width 150 between barrier ribs).
μm, barrier rib width 70 μm, barrier rib height 15
On the side where the barrier ribs (0 μm) were formed, the laminating temperature was 120 ° C., the laminating speed was 0.5 m / min, and the pressing pressure (cylinder pressure) was 4 × 10 ⁵ Pa (because a 10 cm wide substrate was used, The layers were laminated at a linear pressure of 9.8 × 10 ³ N / m), and the thermoplastic resin layer A and the thermoplastic resin layer B were embedded in the inner surface of the recess.

The substrate on which the thermoplastic resin layer A and the thermoplastic resin layer B were laminated was cut in a direction perpendicular to the stripe direction, and the cut surface was observed with an electron microscope to check the phosphor layer forming property. As a result, it was found that a uniform and good phosphor layer was formed.

Example 5 [Preparation of Red Phosphor Pattern] [(I) A photosensitive resin composition layer containing a red phosphor (thermoplastic resin layer A) and a thermoplastic resin were formed on an uneven surface of a substrate having unevenness. Step of Forming Resin Layer B] In the same manner as in Example 2, a thermoplastic resin layer A and a thermoplastic resin layer B were laminated on a substrate using a photosensitive element (ii) and a film (B-2). [(II) Step of irradiating actinic rays imagewise] Next, the thermoplastic resin layer B is peeled off together with the polyethylene terephthalate film, and a test photomask is brought into close contact with the thermoplastic resin layer A. Using an HMW-590 type exposure machine manufactured by Oak Manufacturing Co., an actinic ray was imagewise irradiated at 500 mJ / cm ² .

[(III) 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, irradiated with 3 J / cm ² of ultraviolet light using a Toshiba UV irradiation device manufactured by Toshiba Electric Materials Co., Ltd., and further heated at 150 ° C. for 1 hour in a dryer. . [(IV) Step of Removing Unwanted Parts by Firing]
Heat treatment (baking) was performed at 00 ° C. for 30 minutes to remove unnecessary resin components, and a red phosphor pattern was formed on the inner surface of the concave portion of the PDP substrate.

The cross section of the obtained red phosphor pattern was visually observed with a stereoscopic microscope and an SEM to evaluate the formation state of the blue phosphor pattern. As a result, the red phosphor layer was (Wall surface and substrate surface).

Example 6 [Preparation of Blue Phosphor Pattern] [(I) A photosensitive resin composition layer containing a blue phosphor (thermoplastic resin layer A) and a thermoplastic resin were formed on an uneven surface of a substrate having unevenness. Step of Forming Resin Layer B] In the same manner as in Example 2, photosensitive element (iii) and film (B-2)
A thermoplastic resin layer A and a thermoplastic resin layer B
Were laminated. [(II) Step of irradiating actinic rays imagewise] Next, the thermoplastic resin layer B is peeled off together with the polyethylene terephthalate film, and a test photomask is brought into close contact with the thermoplastic resin layer A. Using an HMW-590 type exposure machine manufactured by Oak Manufacturing Co., an actinic ray was imagewise irradiated at 500 mJ / cm ² .

[(III) Step of Removing Unwanted Parts by Development] Then, after irradiating with actinic rays, the mixture was allowed to stand at room temperature for 1 hour, and then subjected to spray development 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, irradiated with 3 J / cm ² of ultraviolet light using a Toshiba UV irradiation device manufactured by Toshiba Electric Materials Co., Ltd., and further heated at 150 ° C. for 1 hour in a dryer. . [(IV) Step of Removing Unwanted Parts by Firing]
Heat treatment (baking) was performed at 00 ° C. for 30 minutes to remove unnecessary resin components, and a blue phosphor pattern was formed on the inner surface of the concave portion of the PDP substrate.

The cross section of the obtained blue phosphor pattern was visually observed with a stereoscopic microscope and an SEM to evaluate the formation state of the blue phosphor pattern. As a result, the blue phosphor layer was (Wall surface and substrate surface).

Example 7 [Preparation of Green Phosphor Pattern] [(I) A photosensitive resin composition layer containing a green phosphor (thermoplastic resin layer A) and a thermoplastic resin were formed on an uneven surface of a substrate having unevenness. Step of Forming Resin Layer B] In the same manner as in Example 2, a thermoplastic resin layer A and a thermoplastic resin layer B were laminated on a substrate using the photosensitive element (iv) and the film (B-2). [(II) Step of irradiating actinic rays imagewise] Next, the thermoplastic resin layer B is peeled off together with the polyethylene terephthalate film, and a test photomask is brought into close contact with the thermoplastic resin layer A. Using an HMW-590 type exposure machine manufactured by Oak Manufacturing Co., an actinic ray was imagewise irradiated at 500 mJ / cm ² .

[(III) Step of Removing Unwanted Parts by Development] Then, after irradiating with actinic rays, the mixture was allowed to stand at room temperature for 1 hour, and then subjected to spray development 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, irradiated with 3 J / cm ² of ultraviolet light using a Toshiba UV irradiation device manufactured by Toshiba Electric Materials Co., Ltd., and further heated at 150 ° C. for 1 hour in a dryer. . [(IV) Step of Removing Unwanted Parts by Firing]
Heat treatment (baking) was performed at 00 ° C. for 30 minutes to remove unnecessary resin components, and a green phosphor pattern was formed on the inner surface of the concave portion of the PDP substrate.

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

From the above results, by manufacturing a phosphor pattern using the laminating method and the laminating apparatus of the present invention,
A good phosphor pattern can be manufactured.

Example 8 [Formation of Three-Color Pattern] (I) to (II) in Example 5
Using a substrate on which a photosensitive resin composition layer containing a phosphor that emits the first color red, which was obtained by performing the step I), was formed using the substrates of Test Examples 2 (I) to (III). The same process is performed to form a photosensitive resin composition layer containing a phosphor that emits a second color blue, and then (I) to (I) of Test Example 3
By performing the same process as in (III), a photosensitive resin composition layer containing a phosphor emitting a third color green was formed to form a multicolor pattern. Next, using the obtained multicolor pattern, the process (IV) in Example 5 was performed to produce a PDP back plate on which a multicolor phosphor pattern was formed.

The 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).

[0160]

According to the laminating method according to the first aspect, two or more kinds of films can be used and each film can be laminated on a substrate with good workability. The laminating method according to the second aspect has the effects of the first aspect, and further has a PDP.
It can be laminated with good workability on a substrate having irregularities such as a substrate for use. The laminating method according to the third aspect has the effects of the invention according to the first or second aspect, and is more excellent in workability. The laminating method according to the fourth aspect has the effects of the invention according to the first, second, or third aspect, and is suitable for manufacturing a substrate for a printed wiring board, a color filter, and the like. The lamination method according to the fifth aspect has the effects of the invention according to the fourth aspect, and is suitable for manufacturing a plasma display panel, an EL substrate, and the like. The lamination method according to claim 6 is a method according to claims 1, 2, 3, and 4.
Or the effect of the invention described in 5 is exhibited, which is more suitable for manufacturing a plasma display panel or the like. The laminating method according to the seventh aspect has the effects of the invention according to the first, second, third, fourth, fifth or sixth aspect and is more excellent in workability.

In the laminating apparatus according to the eighth and ninth aspects, each thermoplastic resin layer can be laminated on a substrate with good workability by using two or more kinds of films having a thermoplastic resin layer. The laminating apparatus according to claim 10, wherein two or more types of films having a thermoplastic resin layer are used, and each thermoplastic resin layer can be laminated on a substrate with good workability, and a space-saving laminating apparatus. It is. The laminating apparatus according to the eleventh aspect has the effects of the invention according to the eighth, ninth, or tenth aspect, and is easy to prepare for starting work, and is excellent in maintainability. The laminating apparatus according to claim 12,
According to the eighth, ninth, or tenth aspect of the present invention, it is possible to further suppress defects during lamination.

The method of manufacturing a phosphor pattern according to the thirteenth aspect is capable of manufacturing a highly accurate phosphor pattern.
The phosphor pattern according to claim 14 is formed with high accuracy and has excellent uniformity. A back plate for a plasma display panel according to a fifteenth aspect has a 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 is a schematic view showing an example of the laminating apparatus of the present invention.

FIG. 4 is a schematic view showing an example of the laminating apparatus of the present invention.

FIG. 5 is a schematic diagram showing an uneven surface of a substrate having unevenness.

FIG. 6 is a schematic view showing an example of each step of a method for manufacturing a phosphor pattern.

FIG. 7 is a schematic view showing an inner surface of a concave portion.

FIG. 8 is a schematic view showing a state in which a multicolor pattern composed of a photosensitive resin composition layer containing a phosphor is formed.

FIG. 9 is a schematic diagram showing a state in which a multicolor phosphor pattern is formed.

FIG. 10 is a schematic diagram showing an example of a back plate for a plasma display panel.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... 1st supply roll 2 ... 2nd supply roll 3 ... Thermoplastic resin layer A3 ... Photosensitive resin composition layer containing a fluorescent substance (thermoplastic resin layer A) 3 '... Phosphor after photocuring 3'a: pattern of the first color 3'b: pattern of the second color 3'c: pattern of the third color 4: thermoplastic resin layer B 5A: support film 5B: support film 6A ... cover film 6B ... cover film 7 ... substrate 8 ... cover film take-up roll 9 ... support film take-up roll 10 ... laminating roll 11 ... transport roll 12 ... feed roll 13 ... aligning roll 14 ... transparent substrate 15 ... barrier rib 16 ... Lattice discharge space 17 ... Stripe discharge space 18 ... On the uneven surface 19 ... Photomask 20 ... Active light 21 ... Phosphor pattern 21a ... Fluorescent body pattern 21b: Phosphor pattern of second color 21c: Phosphor pattern of third color 22: Inner surface of concave portion 23: Address electrode 24: Protective film 25: Dielectric layer 26: Display electrode 27: Front plate substrate

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroyuki Tanaka 4-13-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside the Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. (72) Inventor Yumiko Wada 4-13 Higashimachi, Hitachi City, Ibaraki Prefecture 1 Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. (72) Inventor Kazuya Sato 4-13-1, Higashicho, Hitachi City, Ibaraki Prefecture Within Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. (72) Inventor Naoki Kimura Hitachi, Ibaraki Prefecture 4-13-1, Higashicho, Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. (72) Inventor Kiyoyoshi Tanno 4-1-1, Higashicho, Hitachi, Ibaraki Pref., Semiconductor & Liquid Crystal Materials Division, Hitachi Chemical Co., Ltd. (72) Inventor Hajime Kadomaru 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside the Hitachi Chemical Co., Ltd.Yamazaki Plant

Claims (15)

[Claims] 1. A film A is supplied from a first supply unit,
A laminating method, comprising: supplying a film B from a second supply unit, and laminating a film A on a substrate and a film B thereon. 2. The method according to claim 1, wherein the substrate is a substrate having irregularities. 3. The lamination method according to claim 1, wherein the film A is a film having the thermoplastic resin layer A, and the film B is a film having the thermoplastic resin layer B. 4. A thermoplastic resin layer A comprising: (a) a film-imparting polymer; (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group at its terminal; and (c) free radicals by irradiation with active light. The lamination method according to claim 3, wherein the layer is a photosensitive resin composition layer containing a photoinitiator to be generated. 5. The thermoplastic resin layer A comprises a component (a),
5. The lamination method according to claim 4, wherein the photosensitive resin composition layer contains component (b) and component (c) and further contains (d) a phosphor. 6. The laminating method according to claim 3, wherein the thermoplastic resin layer B contains (e) a thermoplastic resin. 7. A film having a thermoplastic resin layer A,
5. A film having a support film, a thermoplastic resin layer A and a cover film, wherein the film having a thermoplastic resin layer B has a support film, a thermoplastic resin layer B and a cover film. 7. The lamination method according to 5 or 6. 8. A first supply means for supplying a film A,
A laminating apparatus comprising: a second supplying means for supplying the film B; and a laminating means for laminating the film A on the substrate and the film B thereon. 9. A film A having a support film (5A), a thermoplastic resin layer A (3) and a cover film (6A), a support film (5B), and a thermoplastic resin layer B.
Film B having (4) and cover film (6B)
Is a device for laminating a thermoplastic resin layer A (3) on a substrate (7) and a thermoplastic resin layer B (4) thereon, using a first supply means for supplying the film A, B
, A means for removing the cover film ((6A) and (6B)), a means for removing the support film (5A), and the thermoplastic resin layer A (3) and the thermoplastic resin layer A laminating apparatus provided with laminating means for laminating B (4). 10. A film A having a support film (5A), a thermoplastic resin layer A (3) and a cover film (6A) and a support film (5B), a thermoplastic resin layer B (4) and a cover film ( Using a film B having 6B), a thermoplastic resin layer A (3) on a substrate (7),
An apparatus for laminating a thermoplastic resin layer B (4) thereon, comprising a conveying means for feeding the substrate (7), a first feeding means for feeding the film A, a second feeding means for feeding the film B, A means for removing the cover film ((6A) and (6B)), a means for feeding a film having the thermoplastic resin layer A (3) or the thermoplastic resin layer B (4), and the support film (5A) Means for feeding, support film (5
A laminating apparatus provided with means for taking A), laminating means for laminating a film having a thermoplastic resin layer A (3) or a thermoplastic resin layer B (4) on a substrate (7). 11. A transport roll (1) for feeding a substrate (7).
1) a first supply roll (1) for supplying the film A,
A cover film take-up roll (8) for taking up the cover film (6A), a feed roll (1) for feeding a film having the support film (5A) and the thermoplastic resin layer A (3).
2), support film (5A) and thermoplastic resin layer A
A laminating roll (10) for laminating a film having (3) on a substrate (7), a feed roll (12) for feeding a support film (5A), and a support film take-up roll for winding the support film (5A) (9) Second supplying film B
Supply roll (2), cover film take-up roll (8) for winding up cover film (6B), support film (5)
B) and a feed roll (12) for feeding a film having a thermoplastic resin layer B (4), a support film (5B) and a thermoplastic resin layer A (3) laminated on a substrate (7). The laminating apparatus according to claim 8, 9 or 10, further comprising a laminating roll (10) for laminating a film having the thermoplastic resin layer B (4). 12. A transport roll (1) for feeding a substrate (7).
1) a first supply roll (1) for supplying the film A,
A feed roll (12) for feeding the film A, a cover film winding roll (8) for winding the cover film (6A), a feed roll for feeding a film having the support film (5A) and the thermoplastic resin layer A (3) ( 12), a second supply roll (2) for feeding the film B, a feed roll (12) for feeding the film B, a cover film winding roll (8) for winding the cover film (6B), and a support film (5).
B) and a feed roll (12) for feeding a film having a thermoplastic resin layer B (4), a support film (5A), a film having a thermoplastic resin layer A (3) and a support film (5B), and a thermoplastic resin Laminating roll (13) for laminating a film having resin layer B (4), feed roll (12) for feeding support film (5A), support film take-up roll (9) for winding support film (5A) A roll (12) for feeding a film having a thermoplastic resin layer A (3), a thermoplastic resin layer B (4) and a support film (5B), a thermoplastic resin layer A (3), a thermoplastic resin layer B The laminating apparatus according to claim 8, 9 or 10, further comprising a laminating roll (10) for laminating the film having (4) and the support film (5B) on the substrate (7). 13. A film A comprising a thermoplastic resin layer A which is a photosensitive resin composition layer containing a phosphor by the laminating method according to claim 1, and Laminating a film B having a thermoplastic resin layer B to form a thermoplastic resin layer A and a thermoplastic resin layer B, (II) irradiating an actinic ray imagewise, (III)
A method for producing a phosphor pattern, comprising a step of removing unnecessary portions by development and a step of (IV) removing unnecessary portions by firing. 14. A phosphor pattern produced by the method for producing a phosphor pattern according to claim 13. 15. A back plate for a plasma display panel comprising the phosphor pattern according to claim 14 on a substrate for a plasma display panel.