Manufacturing method of phosphor pattern, photosensitive element for forming phosphor pattern, phosp

专利摘要:
A method of manufacturing a phosphor pattern having a yield of a uniform and thin film thickness having a tolerance of the phosphor pattern over the barrier rib wall surface of the substrate having irregularities such as a plasma display panel substrate and the entire inner surface surrounded by the bottom surface of the substrate. Is to provide (I) forming a photosensitive resin composition layer containing (A) phosphor and a resin layer containing (C) fine particles on a substrate having unevenness, (II) process of irradiating actinic light to the resin layer containing (C) microparticles | fine-particles, and the photosensitive resin composition layer containing (A) fluorescent substance normally, (III) removing the resin layer containing the fine particles (C) and selectively removing the photosensitive resin composition layer containing the phosphor (A) by development to form a pattern; and (IV) Process of Removing Organic Components by Firing The manufacturing method of the fluorescent substance pattern which contains each process of is related.
公开号:KR19990062901A
申请号:KR1019980053765
申请日:1998-12-08
公开日:1999-07-26
发明作者:가주야 사또우；히로유끼 다나까；다께시 노지리；세이지 다이；히로유끼 가와까미；마리꼬 시마무라；유미꼬 수기우라；나오끼 기무라
申请人:와까바야시 구니히꾀；히따찌 케미칼 컴퍼니, 리미티드；
IPC主号:

专利说明:

Manufacturing method of phosphor pattern, photosensitive element for forming phosphor pattern, phosphor pattern and back plate for plasma display panel
The present invention relates to a method for producing a phosphor pattern, a photosensitive element for forming a phosphor pattern, a phosphor pattern and a back plate for a plasma deep rib panel.
Background Art Conventionally, a plasma display panel (hereinafter referred to as PDP) that enables multicolor display is known as one of flat panel displays is provided with a light emitting body emitting light by plasma discharge.
The PDP is arranged so that the faceplate and the backplate of the flat plate made of glass are parallel to each other while facing each other, and both are maintained at regular intervals by the barrier ribs installed therebetween and discharged in the space surrounded by the faceplate, the backplate and the barrier ribs. It becomes the structure that becomes.
In such a space, a phosphor for display is applied and the phosphor emits light by ultraviolet rays generated from the enclosed gas by discharge, so that the viewer can see and recognize the light.
Conventionally, as a method of installing this phosphor, a method of applying a slurry liquid or paste in which respective color phosphors are dispersed by a printing method such as screen printing has been proposed. It is introduced in 1-124929, Unexamined-Japanese-Patent No. 1-24930, and Unexamined-Japanese-Patent No. 2-155142.
However, since the above-mentioned phosphor dispersion slurry liquid is a liquid phase, poor dispersion occurs easily due to precipitation of phosphors, and when the liquid photosensitive resistor is used in the slurry liquid, storage stability is deteriorated due to the promotion of dark reaction. Have. In addition, printing methods such as screen printing have a difficult problem in coping with large screens of PDP in the future because the printing accuracy is weak.
As a method for solving this problem, a method of using a photosensitive element (also referred to as a photosensitive film) containing a phosphor has been proposed (Japanese Patent Application Laid-Open No. 6-273925).
As a method of using the photosensitive element, the photosensitive resin layer containing the phosphor and the photosensitive resin layer containing the phosphor of the photosensitive element by the support film are embedded in the space of the substrate for PDP described above by hot pressing (lamination), and then negative. The film is exposed to active light such as ultraviolet rays by a photographic method, and then unexposed portions are removed with a developing solution such as an aqueous alkali solution, and further, unnecessary organic components of the photosensitive resin layer containing phosphors in the exposed portions by firing. To remove and form the phosphor pattern with only the necessary parts.
Since the method of using such a photosensitive element uses a photography method, it is possible to form a phosphor pattern with high precision.
However, in the conventional method of forming a photosensitive resin layer containing phosphors on the entire uneven surface of the PDP substrate described above using photosensitive elements, and then developing and firing through the feeder mask, the active light is exposed to light. Since the photocurability of the barrier rib wall portion on the inner surface of the unevenness is lower than the photocurability of the bottom surface of the substrate, the photosensitive resin layer containing the exposed body of the barrier rib wall portion is eroded at the time of development, so that it is surrounded by the barrier rib wall surface and the front surface of the substrate. It is difficult to form the phosphor pattern with good yield as a uniform thin film thickness over the recessed inner surface.
As described in claim 1 of the present invention, the present invention relates to embedding into a substrate space having irregularities such as a substrate for PDP (if it is a substrate for PDP, photosensitive resin containing phosphor on the barrier rib wall surface and the space bottom surface). It is an object of the present invention to provide a method for producing a phosphor pattern having excellent tolerance, yield of a composition layer, and a high precision and uniform tolerance of a phosphor pattern.
As described in claim 2 of the present invention, the present invention is to provide a method for producing a phosphor pattern which is more excellent in workability and environmental safety in addition to the invention effect of claim 1.
As described in claim 3 of the present invention, the present invention is to provide a method for producing a phosphor pattern which is more excellent in workability in addition to the invention effect of the claims 1 and 2.
As described in claim 4 of the present invention, the present invention further provides a film membrane (erosion of the photosensitive resin layer containing phosphor in the barrier rib wall portion) in addition to the effects of the invention described in claims 1 and 2. It is an object of the present invention to provide a method for producing a phosphor pattern excellent in suppression.
As described in claim 5 of the present invention, the present invention seeks to provide a method for producing a phosphor pattern which is more excellent in workability and light sensitivity in addition to the invention effects described in claims 1, 2, 3 and 4. will be.
As described in claim 6 of the present invention, the present invention is intended to contain edge substrates and embedding into spaces of substrates having irregularities such as PDP substrates (on a barrier rib wall surface and a space bottom surface if the substrate is a PDP substrate). It is an object of the present invention to provide a photosensitive element for forming a phosphor pattern having excellent workability and excellent yield, good yield and high tolerance of phosphor pattern having a uniform shape.
As described in claim 7 of the present invention, the present invention is to provide a photosensitive element for forming phosphor pattern which is further excellent in workability and light sensitivity in addition to the invention effect of claim 6.
As described in claim 8 of the present invention, the present invention seeks to provide a phosphor pattern excellent in luminance as a uniform shape with high precision.
As described in claim 9 of the present invention, it is an object of the present invention to provide a back plate for a plasma display panel having a phosphor pattern with excellent luminance as a uniform shape with high precision.
BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows an example of the board | substrate for PDP in which a barrier rib was formed.
2 is a schematic diagram showing an example of a substrate for PDP having barrier ribs formed thereon.
3 is a schematic diagram showing a state in which a photosensitive resin composition layer containing the (A) phosphor is formed on the uneven surface of the substrate having unevenness.
4 is a schematic diagram showing an example of each step in the method of producing a phosphor pattern.
It is a schematic diagram which shows the opening width of a recessed part.
6 is a schematic view showing a portion to be photocured.
FIG. 7: is a schematic diagram which shows the state after performing process (III) in the case of using the feed mask which has opening width larger than the opening width of a recessed part in process (II) of this invention.
Fig. 8 is a schematic diagram showing a state in which a multicolor pattern made of the photosensitive resin composition layer containing the phosphor (A) is formed.
9 is a schematic diagram showing a state in which a multi-color phosphor pattern is formed.
10 is a schematic diagram showing a state in which a layer containing no fine particles is provided and a phosphor pattern is formed.
It is a schematic diagram which shows an example of the back plate for plasma display panels of this invention.
Explanation of symbols for main parts of the drawings
1 board 2 barrier ribs
3 Lattice discharge space 4 Strip discharge space
5 uneven surface
6 (A) Photosensitive resin composition layer with phosphor
Photosensitive resin composition layer with (A) phosphor after 6 'photocuring
6'a first color pattern 6'b second color pattern
6'c Third Color Feton 7 Feed Mask
8 (C) resin layer containing fine particles
9 active light 10 opening width of the recess
Width of 11 barrier ribs 12 light curing parts
13 unnecessary part 14 phosphor pattern
14a phosphor pattern of the first color 14b phosphor pattern of the second color
14c phosphor pattern of the third color
15 Phosphor pattern eroded by barrier rib walls
16 Electrode for address 17 Protective film
18 Dielectric Layer 19 Display Electrode
20 Front Panel Substrate
The present invention provides a process for forming a photosensitive resin composition layer containing (A) phosphor and a resin layer containing (C) fine particles on a substrate having (I) unevenness,
(II) process of irradiating actinic light to the resin layer containing (C) microparticles | fine-particles, and the photosensitive resin composition layer containing (A) fluorescent substance normally,
(III) removing the resin layer containing the fine particles (C) and selectively removing the photosensitive resin composition layer containing the phosphor (A) by development to form a pattern; and
(IV) Process of Removing Organic Components by Firing
It relates to a method for producing a phosphor pattern comprising each step of.
The present invention also provides a phosphor pattern in which the process of (I) has a resin layer containing (C) fine particles on a (I '') support film and has a photosensitive resin composition layer containing (A) phosphor thereon. Preparation of the above-mentioned phosphor pattern which is a process of laminating | stacking the photosensitive element for this on the board | substrate with an unevenness | corrugation so that layer (A) mentioned above may contact easily, and forming the above-mentioned (A) layer and (C) layer on the board | substrate with unevenness | corrugation. It is about a method.
In addition, the present invention is to repeat the process of (I) to (III) to form a pattern of various colors made from a photosensitive resin composition layer containing a phosphor that develops red, green and blue color, and then the process of (IV) The present invention relates to a method for producing the above-mentioned phosphor pattern which forms a phosphor pattern of various colors.
Furthermore, the present invention relates to a method for producing the above-mentioned phosphor pattern, which forms a phosphor pattern of various colors in which red, green and blue colors are repeated by repeating the steps (I) to (IV).
In addition, the present invention provides a photosensitive resin composition layer containing (A) phosphor
(a) a film imparting polymer,
(b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group,
(c) a photoinitiator that generates free radicals by irradiation of actinic light, and
(d) phosphor
As containing
(C) The manufacturing method of the above-mentioned phosphor pattern in which the resin layer containing microparticles | fine-particles contains a thermoplastic resin.
Moreover, this invention relates to the photosensitive element for phosphor pattern formation which has a resin layer containing (C) microparticles | fine-particles, and the photosensitive resin composition layer containing (A) fluorescent substance on a support film.
In addition, the present invention provides a photosensitive resin composition layer containing (A) phosphor
(a) a film imparting polymer,
(b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group,
(c) a photoinitiator that generates free radicals by irradiation of actinic light, and
(d) phosphor
As containing
(C) The photosensitive element for phosphor pattern formation mentioned above in which the resin layer containing microparticles | fine-particles contains a thermoplastic resin.
The present invention also relates to a phosphor pattern produced by the above-described method for producing a phosphor pattern.
Moreover, this invention relates to the back plate for plasma display panels provided with the above-mentioned phosphor pattern on the substrate for plasma display panels.
In the present invention, examples of the substrate having irregularities include a substrate for plasma display panel (substrate for PDP) and the like in which a barrier rib is formed. As the substrate for PDP, for example, it is not necessary to perform a surface treatment for transparent adhesion. Examples thereof include those in which electrodes and barrier ribs are formed on substrates such as glass plates and synthetic resins. The barrier rib formation does not need to be particularly limited, and a known material may be used. For example, a rib material containing silica, a thermosetting resin, a low melting glass (lead oxide, etc.), a solvent, or the like can be used.
In addition to the electrodes and barrier ribs, a dielectric film, an insulating film, an auxiliary electrode, a resistor, or the like may be formed on the PDP substrate as necessary.
The method of forming such a material on the substrate does not need to be particularly limited. For example, it is possible to form the electrode on the substrate by a method such as vapor deposition, sputtering, plating, coating, printing, or the like. The barrier rib can be formed by, for example, embedding. The schematic diagram of the board | substrate for PDP in which the barrier rib was formed in FIG. 1 and FIG. 2 was shown. The barrier rib usually has a height of 20 to 500 µm and a width of 20 to 200 µm.
The shape of the discharge space enclosed by the barrier rib does not need to be particularly limited, but a lattice, strip, honeycomb, triangle or oval may be used. However, as shown in FIGS. 1 and 2, a discharge in a lattice or strip is generally used. Space is formed.
1 and 2, a barrier rib 2 is formed on the substrate 1, a lattice discharge space 3 is formed in FIG. 1, and a strip discharge space 4 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 the lattice-shaped discharge space shown in FIG. 1, the length of the length and the width is 50 μm to 1 mm. According to Fig. 2, in the case of strip-shaped discharge spaces, the interval is 30 μm to 1 mm.
In the present invention, the photosensitive resin composition layer containing the (A) phosphor is not particularly limited as long as it is a layer containing the photosensitive resin composition containing phosphor as an essential component. For example, (a) a film imparting polymer, ( b) The photopolymerizable unsaturated compound which has an ethylenically unsaturated group, the photoinitiator which produces | generates a free radical by irradiation of actinic light, and the layer containing (d) fluorescent substance can be enumerated as preferable.
Photoinitiators for generating free radicals by (a) a film imparting polymer, (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group, and (c) actinic light are described in Japanese Patent Application Laid-Open No. 9-265906, respectively. You can use what you have.
In addition, since it is necessary to remove an organic component by baking at the time of manufacture of the phosphor pattern described later, (A) phosphor and binder mentioned later in the photosensitive resin composition which comprises the photosensitive resin composition layer containing fluorescent substance. The photosensitive resin composition other than the agent needs to have good thermal decomposition property. For this purpose, it is preferable that (d) photosensitive resin compositions other than a phosphor and a binder do not contain anything other than carbon, hydrogen, oxygen, and nitrogen as an element which comprises it.
(d) As the phosphor, there is no need to limit in particular, but an ordinary metal oxide having a main axis can be used.
Examples of the red light emitting phosphor include Y ₂ O ₂ S: Eu, Zn ₃ (PO ₄ ) ₂ : Mn, Y ₂ O ₃ : Eu, YVO ₄ : Eu, (Y, Gd) BO ₃ : Eu, γ-Zn ₃ (PO ₄ ) ₂ : Mn, (ZnCd) S: Ag + In ₂ O, and the like.
Examples of the green light emitting phosphor include ZnS: Cu, Zn ₂ SiO ₄ : Mn, ZnS: Cu + Zn ₂ SiO 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, Tb, BaO 6Al ₂ O ₃ : Mn and the like.
Examples of the blue light emitting phosphor include ZnS: Ag, ZnS: Ag, Al, ZnS: Ag, Ga, Al, ZnS: Ag, Cu, Ga, Cl, ZnS: Ag + In ₂ O ₃ , Ca ₂ B ₅ O ₉ Cl : Eu ²⁺ , (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ²⁺ , Sr ₁₀ (PO ₄₆ Cl ₂ : Eu ²⁺ , BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , BaMgAl ₁₄ O ₂₃ : Eu ²⁺ , BaMgAl ₁₆ O ₂₆ : Eu ²⁺ , and the like.
In the present invention, the particle diameter of the phosphor (d) is preferably about 0.1 to 20 µm, more preferably about 1 to 15 µm, and particularly preferably about 2 to 8 µm. If the particle diameter is less than 0.1 µm, the luminous efficiency tends to be lowered, and if it exceeds 20 µm, the dispersibility tends to be lowered. In addition, in this invention, it is preferable that it is spherical as a shape of (d) fluorescent substance, and the one whose surface area is smaller is preferable.
It is preferable that the total amount of (a) component and (b) component shall be 10-90 weight part as 100 weight part, and, as for the compounding quantity of (a) component, it is more preferable to set it as 20-80 weight part. When the blending amount thereof is less than 10 parts by weight, when the photosensitive resin composition containing the phosphor is cut off from the edge of the roll (hereinafter referred to as edge cushion), it is turned off from the roll when the photosensitive element is laminated. It may be difficult to pick it up, and the cut-out part may be excessively embedded in the space of the PDP substrate, causing a problem such that the manufacturing yield is remarkably lowered, and the film formability is deteriorated. If exceeded, the sensitivity tends to be insufficient.
It is preferable that the total amount of (a) component and (b) component shall be 10-90 weight part as 100 weight part, and, as for the compounding quantity of (b) component, it is more preferable to set it as 20-80 weight part. If the blending amount thereof is less than 10 parts by weight, the sensitivity of the photosensitive resin composition containing the phosphor tends to be insufficient, and if it exceeds 90 parts by weight, the photocured product tends to be fragile, and when the photosensitive element is used, the phosphor is contained. The photosensitive resin composition which comes out from the edge by flow, and shows the tendency which film formability falls.
It is preferable to set it as 0.01-30 weight part with respect to 100 weight part of total amounts of (a) component and (b) component, and, as for the compounding quantity of (c) component, it is more preferable to set it as 0.1-20 weight part. If the blending amount thereof is less than 0.01 part by weight, the sensitivity of the photosensitive resin composition containing the phosphor tends to be insufficient, and if it exceeds 30 parts by weight, the absorption of the actinic light on the exposure surface of the photosensitive resin composition containing the phosphor is increased, and The photocuring tends to be insufficient.
It is preferable that the compounding quantity of (d) component shall be 10-300 weight part with respect to 100 weight part of total amounts of (a) component and (b) component, It is more preferable to set it as 50-250 weight part, It is 70-200 weight part It is particularly preferable to. When the compounding amount thereof is less than 10 parts by weight, the luminous efficiency is lowered when light is emitted as PDP. When the amount is more than 300 parts by weight, the film formability is lowered when the photosensitive element is used, and the flexibility is lowered.
In the present invention, the photosensitive resin composition constituting the photosensitive resin composition layer containing the phosphor (A) may contain a compound having a carboxyl group in order to improve storage stability without increasing the viscosity for a long time.
Examples of the compound having a carboxyl group include saturated fatty acids, unsaturated fatty acids, aliphatic dibasic acids, aliphatic tribasic acids, aromatic tribasic acids, and the like.
Specifically, for example, formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, propionic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadeca Non-acid, stearic acid, nonadecanoic acid, arachidic acid, palmilean acid, oleic acid, elideic acid, linolenic acid, linoleic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmal Lonic acid, succinic acid, methyl succinic acid, adipic acid, methyl adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, itaconic acid, 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, ethyl malonic acid, citric acid and the like are preferable in view of the high effect of suppressing viscosity increase, and oxalic acid, malonic acid, citric acid and the like are more preferable. These acids may be used alone or in combination of two or more thereof.
It is preferable that the compounding quantity of the compound containing a carboxyl group shall be 0.01-30 weight part with respect to 100 weight part of (a) component. When this compounding quantity is less than 0.01 weight part, the effect of storage stability will fall, and when it exceeds 30 weight part, it will show the tendency for the sensitivity to become inadequate.
Moreover, in this invention, it is preferable to add a dispersing agent to the photosensitive resin composition which comprises the photosensitive resin composition layer containing (A) fluorescent substance in order to make dispersion of fluorescent substance favorable.
As the dispersant, inorganic dispersants include silica gel, bentonite, kaolinite, talc, hectorite, montmorillonite, saponite and baydelite. The organic dispersants include aliphatic acid amides, aliphatic esters, polyethylenes. An oxide type, a sulfate type anionic surfactant, a polycarboxylic acid amine salt type, a polycarboxylic acid type, a polyamide type | system | group, a high molecular weight polyether type, an acryl-type copolymer type, a special silicone type, etc. can be mentioned. These dispersants may be used alone or in combination of two or more thereof.
Although the addition amount of a dispersing agent does not need to restrict in particular, It is preferable to set it as 0.01-100 weight part with respect to 100 weight part of (a) component. If it is 0.01% or less by weight, the dispersant addition effect tends not to occur, and if it is 100 parts by weight or more, the patterning accuracy (the property obtained after the patterning of the pattern formed from the photosensitive resin composition containing the phosphor is precise and desired in shape. ) Tends to be lowered.
In addition, in this invention, it is preferable to use a binder for the photosensitive resin composition which comprises the photosensitive resin composition layer containing (A) fluorescent substance in order not to peel a fluorescent substance from the board | substrate for PDP after baking.
As a binder, low melting glass, a metal alkoxide, a silane coupling agent etc. can be mentioned, for example. These may be used alone or in combination of two or more thereof.
The amount of the binder to be used is not particularly limited, but is preferably about 0.01 to 100 parts by weight, more preferably about 0.05 to 50 parts by weight, more preferably about 0.1 to 30 parts by weight based on 100 parts by weight of the component (d). desirable. When the amount thereof is 0.01 parts by weight or less, the binding effect of the phosphor does not appear, and when 100 parts by weight or more, the luminous effect tends to decrease.
In the present invention, the photosensitive resin composition constituting the photosensitive resin composition layer containing the (A) phosphor requires a dye, a coloring agent, a plasticizer, a pigment, a polymerization inhibitor, a surface modifier, a stabilizer, an adhesion imparting agent, a thermosetting agent, and the like. It can be added depending on.
In this invention, as a resin layer containing (C) microparticles | fine-particles, the layer of what mixed microparticles | fine-particles and (B) thermoplastic resin mentioned later can be enumerated as preferable.
As microparticles | fine-particles, there should just be a substance which reflects and scatters light, and organic microparticles | fine-particles, inorganic microparticles | fine-particles, etc. can be used.
As the organic fine particles, fine particles synthesized by known methods such as suspension polymerization, emulsion polymerization and seed polymerization may be used.
As a monomer used for synthesis | combination of organic microparticles | fine-particles, the photopolymerizable unsaturated compound which has an ethylenically unsaturated group at the terminal (b) mentioned above, a styrene-type monomer (styrene, (alpha) -methylstyrene, para- t-butylstyrene, etc.), an olefin Monomers (butadiene, isoprene, chloroprene), vinyl monomers (vinyl chloride, vinyl acetate, etc.), nitrile monomers (acrylonitrile, methacrylonitrile, etc.), 1- (methacryloyloxyethoxycarbonyl ) -2- (3'-chloro-2'-hydroxypropoxycarbonyl) -benzene, m-divinylbenzene, p-divinylbenzene, urethane diacrylate compound, trivinylbenzene, etc. can be mentioned. .
In addition, a polymer, a polyether resin, a cellulose derivative, a polyamide resin, a polyvinyl acetal resin, a polyester resin, a polycarbonate resin, a polytetrafluoroethylene or an aramid fiber obtained from the monomers, or a carbon fiber The fine particles obtained by grinding in a mill such as a ball mill, a bendis mill, a jet mill, or the like can be used together.
As inorganic fine particles, microparticles | fine-particles, such as glass, a silica gel, alumina, a silicon carbide, silicon nitride, potassium titanate, and aluminum borate, can be mentioned. In addition, fine particles of a metal or a metal oxide can also be used together as inorganic fine particles.
As for the shape of microparticles | fine-particles, a spherical shape, a cone shape, a flat shape, a needle shape, and an amorphous shape are used. These microparticles | fine-particles can be used individually or in mixture of 2 or more types.
In the present invention, the size of the fine particles is preferably in the range of 0.01 μm to 100 μm, and more preferably in the range of 0.05 μm to 80 μm as the average particle diameter. When the average particle diameter thereof is less than 0.01 μm but larger than 100 μm, the efficiency of scattering light tends to be lowered. In addition, in this invention, it is essential that the largest diameter of microparticles | fine-particles is below the opening width (10 of FIG. 5) of a recessed part after forming the photosensitive resin composition layer containing (A) fluorescent substance. If the maximum diameter of the fine particles is larger than the opening width of the recesses after forming the photosensitive resin composition layer containing the (A) phosphor, the fine particles do not enter the recesses, so the efficiency of scattering light tends to decrease.
(B) The resin constituting the thermoplastic resin is not particularly limited as long as it is softened at a temperature at the time of hot pressing. For example, polyethylene, polypropylene, polymethylbenzene, polycarbonate, polyurethane, teflon, rubbers ( Butadiene rubber, styrene-butadiene rubber, silicone rubber, etc.), polyvinyl toluene, polyacrylic acid ester, polymethacrylic acid ester, copolymer of ester and vinyl acetate, copolymer of ethylene and acrylic acid ester, air of vinyl chloride and vinyl acetate Copolymer, copolymer of styrene with acrylic or methacrylic ester, copolymer of vinyltoluene with acrylic or methacrylic ester, polyvinyl alcohol-based resin (hydrolyzate of polyacrylic acid ester or polymethacrylic acid ester, Hydrolyzate of polyvinyl acetate, between ethylene and vinyl acetate Hydrolysates of polymers, hydrolysates of ethylene and acrylic esters and copolymers, hydrolysates of copolymers of vinyl chloride and vinyl acetate, hydrolysates of copolymers of styrene and acrylic esters or methacrylic esters, vinyltoluene and acrylic acid Hydrolysates of esters or copolymers with methacrylic acid esters), water-soluble salts of carboxyalkylcellulose, water-soluble cellulose esters, water-soluble salts of carboxyalkyl starch, polyvinylpyrrolidone, unsaturated carboxylic acids and unsaturated monomers copolymerizable with these The resin etc. which have a carboxyl group obtained by copolymerizing are mentioned. These can be used individually or in mixture of 2 or more types.
(B) The thermoplastic resin generates free radicals by irradiation of (e) the thermoplastic resin, (f) the photopolymerizable unsaturated compound having ethylenically unsaturated groups, and (g) the actinic light from the viewpoint of preventing mixing and improving workability. It may be composed of a photosensitive resin composition containing a photoinitiator.
(e) As a thermoplastic resin, the (a) film-providing polymer which can be used for the photosensitive resin composition which comprises the photosensitive resin composition layer containing the resin which can be used as resin which comprises the above-mentioned (B) thermoplastic resin, and (A) fluorescent substance Can be used.
(f) As the photopolymerizable unsaturated compound having an ethylenically unsaturated group, (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group which can be used in the photosensitive resin composition constituting the photosensitive resin composition layer containing the above-mentioned (A) phosphor is used. Can be.
(g) A photoinitiator that generates free radicals by irradiation of actinic light may generate free radicals by (c) actinic light irradiation which can be used in the photosensitive resin composition constituting the photosensitive resin composition layer containing the above-mentioned (A) phosphor. A photoinitiator can be used.
As for the compounding quantity of (e) component, about 10-100 weight part is preferable as a total amount of (e) component and (f) component as 100 weight part, but 20-80 weight part is more preferable. When this compounding quantity is less than 10 weight part, when it becomes a photosensitive element, the photosensitive resin composition will come out from the roll edge by flow, and it will show the tendency which film formability falls.
As for the compounding quantity of (f) component, about 0-90 weight part is preferable as a total amount of (e) component and (f) component as 100 weight part, but 20-80 weight part is more preferable. When this compounding quantity exceeds 90 weight part, when it becomes a photosensitive element, it will come out from a roll edge by flow, and it shows the tendency which film formability falls.
As for the compounding quantity in the case of mix | blending (g) component, about 0.01-30 weight part is preferable with respect to 100 weight part of total amounts of (e) component and (f) component, but about 0.1-20 weight part is more preferable. . When the blending amount is 0.01 parts by weight or less, the sensitivity tends to be insufficient, and when it exceeds 30 parts by weight, absorption of the actinic light on the exposure surface is increased and the internal light curing is insufficient.
Moreover, you may add a surface modifier and a polymerization inhibitor to (B) thermoplastic resin as needed.
In the developing step described later, the (B) thermoplastic resin can be developed using the same developing solution for the photosensitive resin composition layer containing the (A) phosphor and the (B) thermoplastic resin.
Examples of those that can be developed with the same developer include those soluble in water or an aqueous alkali solution.
Examples of the resin constituting the (B) thermoplastic resin soluble in aqueous or alkaline aqueous solution include polyvinyl alcohol-based resins (hydrolysates of polyacrylic acid esters or polymethacrylic acid esters, hydrolysates of polyvinyl acetate, ethylene and vinyl acetate). Hydrolyzate of copolymer, hydrolyzate of copolymer of ethylene and acrylic acid ester, hydrolyzate of copolymer of vinyl chloride and vinyl acetate, hydrolyzate of copolymer of styrene and acrylic acid ester or methacrylic acid ester, vinyltoluene Hydrolysates of copolymers with acrylic esters or methacrylic esters, etc.), water-soluble salts of carboxyalkylcellulose, water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinylpyrrolidone, unsaturated carboxylic acids and unsaturated copolymerizable with these CAR obtained by copolymerizing monomer The resin etc. which have a carboxyl group can be mentioned.
Examples of the resin having a carboxyl group obtained by copolymerizing an unsaturated carboxylic acid with an unsaturated monomer copolymerizable with these include, for example, unsaturated carboxylic acid (acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.) and the above-mentioned (A) phosphors. It is preferable to use the vinyl copolymer obtained by copolymerization with the vinyl monomer which can be used for the (a) film property provision polymer which can be used for the photosensitive resin composition which comprises the photosensitive resin composition layer.
The resin having a carboxyl group obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated monomer copolymerizable with these is preferably about 5,000 to 300,000, but more preferably about 20,000 to 150,000. When this weight average molecular weight is 5,000 or less, when it becomes a photosensitive element, film formability and flexibility tend to fall, and when 300,000 or more shows developability tends to fall.
The carboxyl group content of the resin having a carboxyl group obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated monomer copolymerizable with these so as to be developable by a developing solution as the (B) thermoplastic resin soluble in an aqueous alkali solution [acid value (mgKOH / g Can be defined as
For example, when developing using aqueous alkali solution, such as sodium carbonate and potassium carbonate, it is preferable to make acid value about 90-260. If the acid value is 90 or less, development tends to be difficult, and if it is 260 or more, development resistance tends to decrease.
Moreover, when developing using water or the aqueous alkali solution and the water-based developing solution which consists of 1 or more types of organic solvent, it is preferable to make acid value about 16-260. If the acid value is 16 or less, the development tends to be difficult, and if it is 260 or more, the developer resistance tends to decrease.
Furthermore, when developing using a developer (emulsion developer) consisting of water and one or more organic solvents insoluble in water or an organic solvent developer such as 1,1,1-trichloroethane, the film properties of the photosensitive resin composition The imparting polymer may not contain a carboxyl group.
Moreover, in order to make the film property of (B) thermoplastic resin favorable, a plasticizer can be added in resin which comprises said thermoplastic resin.
As a plasticizer, general formula (III)
(Wherein R ² represents a hydrogen atom or a methyl group, Y ¹ represents a saturated hydrocarbon group or a polyalkylene glycol residue which may have a hydrogen atom or a substituent, and Y ² represents a saturated hydrocarbon which may have a hydroxyl group or a substituent) Group or a polyalkylene glycol moiety, and p represents an integer of 1 to 20)
Dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl together with polyalkylene glycol such as polypropylene glycol and derivatives thereof, polyethylene glycol and derivatives thereof Phosphate and the like.
In the resin layer containing (C) microparticles | fine-particles, the compounding ratio of microparticles | fine-particles and (B) thermoplastic resin has preferable 1-500 weight part of microparticles | fine-particles with respect to 100 weight part of thermoplastic resin, but about 2-400 weight part is more preferable. , 4 to 200 parts by weight is particularly preferable. It is a tendency for the compounding quantity of microparticles | fine-particles to be less than 1 weight part, to scatter light and to reduce efficiency, and to transmit a light transmittance to 500 weight part or more.
Hereinafter, each step of the method for producing the phosphor pattern of the present invention will be described in detail.
[I] forming a photosensitive resin composition layer containing (A) phosphor and a resin layer containing (C) fine particles on substrate with (I) irregularities]
In the present invention, the step (I) comprises the steps of forming a photosensitive resin composition layer containing (A) phosphor on a substrate having (Ia) unevenness and a photosensitive resin composition layer containing (Ib) (A) phosphor. A method carried out by a step of forming a resin layer containing (C) fine particles thereon, (I ') a photosensitive resin composition layer containing a phosphor (A) and a resin layer containing (C) fine particles on a substrate having irregularities The method performed by the process of simultaneously forming a fruit, etc. can be employ | adopted.
(Ia) forming a photosensitive resin composition layer containing (A) phosphor on a substrate having unevenness, and (Ib) a resin layer containing (C) microparticles on the photosensitive resin composition layer containing (A) phosphor. The method which consists of a process to form is demonstrated.
[Step of forming photosensitive resin composition layer containing (A) phosphor on substrate having (Ia) unevenness]
FIG. 3 shows a state in which the photosensitive resin composition layer 6 containing the (A) phosphor is formed on the uneven surface 5 of the substrate 1 having unevenness in the present invention.
In the present invention, the method of forming the photosensitive resin composition layer containing the (A) phosphor on the uneven surface 5 of the substrate 1 having the unevenness is not particularly limited, but, for example, contains the solution (A) phosphor. The photosensitive resin composition is applied directly and dried to form a photosensitive resin composition layer 6 containing (A) phosphor and (A) a photosensitive resin composition having a photosensitive resin composition layer containing phosphor. And the like can be enumerated.
As a method of directly applying and drying the photosensitive resin composition containing the (A) phosphor in the solution phase to form the photosensitive resin composition layer 6 containing the (A) phosphor, for example, the photosensitive resin containing the above-mentioned (A) phosphor The method of apply | coating and drying directly on the uneven surface 5 as a solution uniformly disperse | distributed as a solvent or disperse | distributing to the solvent which can melt | dissolve or disperse each component which comprises a composition layer is mentioned.
In the direct coating method, (A) As a solvent which can melt | dissolve or disperse | distribute each component which comprises the photosensitive resin composition layer containing fluorescent substance, for example, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cell solve, ethyl Cellulsolve, gamma-butyrolactam, N-methylpyrrolidone, dimethylformamide, tetramethylsulfone, diethylene glycol dimethyl ether, diethylene glycol mobutyl ether, chloroform, methylene chloride, methyl alcohol, ethyl alcohol and the like are listed. can do. These can be used individually or in mixture of 2 or more types.
In the direct coating method, the coating method is, for example, doctor blade coating method, Meyer bar coating method, roll coating method, screen coating method, spinner coating method, ink jet coating method, spray coating method, immersion coating method, gravure coating. The coating method, the caten coating method, etc. can be used.
In addition, in this coating process, the material of the coating apparatus of the part which contacts the solution uniformly disperse | distributed as it melt | dissolves or mixes with the solvent which can melt | dissolve or disperse each component which comprises the above-mentioned (A) layer is non-metallic It is preferable that it is a material. In the case where the material of the contact portion thereof is a metal, the coating device in contact with this is polished by the phosphor in the solution of each component constituting the layer (A), and the polishing powder contains the photosensitive resin composition containing the phosphor (A). It tends to be incorporated as impurities in the solution of each component constituting the layer.
In the direct coating method, the drying method can be dried using a known drying method. The drying temperature is preferably about 40 to 130 ° C., and the drying time is preferably 10 to 90 minutes.
Although the thickness of the photosensitive resin composition layer containing (A) fluorescent substance after drying does not need to restrict | limit in particular, About 10-200 micrometers is preferable, About 20-120 micrometers is more preferable, About 30-80 micrometers is especially preferable. Do. If the thickness thereof is 10 μm or less, the phosphor pattern after firing described later becomes too thin and the luminous efficiency tends to be lowered. At 200 μm or more, the phosphor pattern after firing becomes thick and the luminous area of the fluorescent surface decreases, so that the luminous efficiency tends to decrease. to be.
In addition, in the method of forming on the uneven surface 5 using the photosensitive element having the photosensitive resin composition layer containing the (A) phosphor, it is necessary to prepare the photosensitive element having the photosensitive resin composition layer containing the (A) phosphor in advance. have.
The photosensitive element having the layer (A) is applied onto the support film in a uniformly dispersed solution and dried by dissolving or mixing the respective components constituting the layer (A) above in a dissolvable or dispersible solvent. Can be obtained.
In preparing the photosensitive element having the layer (A), examples of the solvent capable of dissolving or dispersing the components constituting the layer (A) described above include, for example, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellulose solution, Ethyl cellsolve, gamma-butyrolactam, N-methylpyrrolidone, dimethylformamide, tetramethylsulfone, diethylene glycol dimethyl ether, diethylene glycol mobutyl ether, chloroform, methylene chloride, methyl alcohol, ethyl alcohol, etc. Can be enumerated. These can be used individually or in mixture of 2 or more types.
The support film in the preparation of the photosensitive element having the layer (A) should be chemically and thermally stable, and further includes, for example, polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, and the like, which are configured as a soluble material. Among these, polyethylene terephthalate and polyethylene are preferable, and polyethylene terephthalate is more preferable. This support film must be removed from the (A) layer later, so that the surface treatment which becomes impossible to remove is not performed or it is not material. About 5-100 micrometers is preferable, and, as for the thickness of a support film, about 10-80 micrometers is more preferable.
A well-known method can be used as a coating method in manufacturing the photosensitive element which has the (A) layer, For example, the knife coating method, the roll coating method, the spray coating method, the gravure coating method, the bar coating method, the caten coating Can be enumerated.
In addition, in this coating process, the material of the coating apparatus of the part which contacts the solution uniformly disperse | distributed as it melt | dissolves or mixes with the solvent which can melt | dissolve or disperse each component which comprises the above-mentioned (A) layer is non-metallic It is preferable that it is a material. In the case where the material of the contact portion thereof is a metal, the coating device in contact with this is polished by the phosphor in the solution of each component constituting the layer (A), and the polishing powder contains the photosensitive resin composition containing the phosphor (A). It tends to be incorporated as impurities in the solution of each component constituting the layer.
In producing the photosensitive element having the (A) phosphor, the drying temperature is preferably about 60 to 130 ° C, and the drying time is preferably about 3 minutes to about 1 hour.
Although the thickness of the photosensitive resin composition layer which has the (A) fluorescent substance of the (A) phosphor which has the (A) fluorescent substance does not need to restrict in particular, about 10-200 micrometers is preferable, About 20-120 micrometers is more preferable, 30- Particularly preferred is about 80 μm. If the thickness thereof is 10 μm or less, the phosphor pattern after firing described later becomes too thin and the luminous efficiency tends to be lowered. At 200 μm or more, the phosphor pattern after firing becomes thick and the luminous area of the fluorescent surface decreases, so that the luminous efficiency tends to decrease. to be.
As for the photosensitive resin composition of the photosensitive element which has (A) layer, the viscosity in 100 degreeC is preferable about 1-1 * 10 <^7> Pa sec, More preferably, about 1-2-1 * 10 <^6> Pa sec, 5 ~ The degree of 1 * 10 <^5> Pa sec is especially preferable, and the grade of 10-1 * 10 <^4> Pa sec is extremely preferable. When the viscosity at 100 ° C. is 1 Pa sec or less, when the viscosity at room temperature becomes too low to form a photosensitive element, the photosensitive resin composition layer containing the (A) phosphor tends to stick out from the edge due to flow, resulting in film formation. This tends to be lowered. Moreover, when it is 1 * 10 <^7> Pa sec or more, the formation property of the photosensitive resin composition layer containing (A) fluorescent substance in the inner surface of the recessed part of the board | substrate which has an unevenness | corrugation mentioned later tends to fall.
In addition, in this invention, as a sensitivity of the photosensitive resin composition layer containing (A) fluorescent substance, in the process of irradiating actinic light normally, it is 21 steps of tablets of Hitachi Chemical Co., Ltd. product etc. The number of steps of the tablet of the photosensitive resin composition layer containing the (A) phosphor remaining when developed in the step of irradiating the active light with a predetermined amount of active light using Is preferably 1 to 21 steps, more preferably 1.5 to 18 steps, and particularly preferably 2 to 15 steps.
In the present invention, as the resolution of the photosensitive resin composition layer containing (A) phosphor, active light is irradiated with a predetermined amount of active light irradiation using a feed mask for evaluating the resolution of Hitachi Chemical Co., Ltd. product or the like. In the case of developing in the process of removing the unnecessary portion by the phenomenon described later, it is preferable that the minimum line / space of the photosensitive resin composition layer containing the remaining (A) phosphor is 1 mm / 1 mm or less, 900 μm / 900 It is more preferable that it is μm or less, and particularly preferably 800 μm / 800 μm or less.
In addition, in the present invention, the adhesiveness of the photosensitive resin composition layer containing the phosphor (A) is used to selectively generate active light at a predetermined amount of active light irradiation using a feed mask for evaluation of adhesion of Hitachi Chemical Co., Ltd. product. In the case of developing in the step of irradiating and removing unnecessary portions by the following phenomenon, it is preferable that the minimum line / space of the photosensitive resin composition layer containing the remaining (A) phosphor is 400 μm / 400 μm or less, and 350 μm / It is more preferable that it is 400 μm or less, and particularly preferably 300 μm / 400 μm or less.
Especially on the photosensitive element which has the photosensitive resin composition layer containing the (A) fluorescent substance obtained in this way, a peelable carver film can be laminated | stacked. Examples of the cover film include polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, and the like, and it is preferable that the adhesion between the cover film and the layer (A) is smaller than the adhesion between the support film and the layer (A). Do. Although the thickness of a carver film does not need to restrict | limit in particular, About 5-100 micrometers is preferable, About 10-90 micrometers is especially preferable. The photosensitive element which has the (A) layer obtained in this way can be rolled and stored in roll shape.
As a method of forming the (A) layer on the uneven surface 5 using the photosensitive element having the photosensitive resin composition layer containing the (A) phosphor, for example, the (A) layer of the photosensitive element having the (A) layer is Laminating on a substrate having irregularities and embedding (A) layer on the inner surface of the recess by heating, pressing, etc., embedding (A) layer on the inner surface of the recess by heating, pressing, etc. Can be enumerated.
As a method of laminating the (A) layer of the photosensitive element having the (A) layer on the substrate having the unevenness, and embedding the (A) layer on the inner surface of the recessed portion by heating, pressing or the like, for example, having the (A) layer When a cover film is present in the photosensitive element, the cover film is removed, and a method of heat-compression bonding as the layer (A) comes into contact with the substrate having unevenness may be mentioned.
As for the heating temperature at the time of hot pressing, about 10-130 degreeC is preferable, About 20-120 degreeC is more preferable, About 30-110 degreeC is especially preferable. When this heating temperature is 10 degrees C or less, it is a tendency for (A) layer not to fully adhere on the board | substrate with an unevenness, and it is a tendency for (A) layer to thermoset at 130 degreeC or more.
In addition, the crimping pressure at the time of hot pressing is preferably 1 × 10 ² to 1 × 10 ⁷ Pa, more preferably 5 × 10 ² to 5 × 10 ⁶ Pa, as the gauge pressure (normal pressure 1 atm is 0). , 1 × 10 ⁴ to 4 × 10 ⁶ Pa is particularly preferred. If the crimping pressure thereof is 1 × 10 ² Pa or less, the layer (A) cannot be sufficiently adhered to the substrate having the unevenness, and at 1 × 10 ⁷ Pa or more, the barrier rib of the substrate having the unevenness shows a tendency to break.
Since the above crimping pressure is the cylinder pressure of the laminator as the crimping device, it is preferable that the linear pressure is about 2. 4 to 2. 4 x 10 ⁵ N / m in terms of linear pressure, and about 12 to 1.2 x 10 ⁵ N / m. It is more preferable, and about 2.4 * 10 <^2> -2.4 * 10 <^4> N / m is especially preferable. At this crimping pressure of 2. 4 N / m or less, (A) the embedding ability into the space of the PDP substrate of layer 6 tends to decrease, and at 2. 4 × 10 ⁵ N / m or more, the barrier rib of the PDP substrate is broken. It tends to be.
Here, as a method of bringing the linear pressure to 5 x 10 ³ N / m, for example, using a laminator with a cylinder diameter of 40 mm, a substrate having a thickness of 3 mm and a length of 10 cm x 10 cm (square) is used. The cylinder pressure (normal pressure 1 atm is 0) of the laminator is 2 kgf / cm ² and the linear pressure is 5 × 10 ³ N / m. Using a laminator with a cylinder diameter of 40 mm, the thickness is 3 mm and 20 cm The method of making a laminator cylinder pressure (normal pressure 1atm is 0) into 4 kgf / cm <^2> and linear pressure of 5x10 <^3> N / m using a board | substrate of 20 cm (square) squares, etc. are mentioned.
When the photosensitive element having the layer (A) is heated as described above, it is not necessary to preheat the PDP substrate having the barrier ribs, but the (A) layer further improves the embedding on the inner surface of the recess. In the above, it is preferable to preheat the substrate having the unevenness.
Furthermore, for the same purpose, it is also possible to operate the above-mentioned crimping and hot pressing at a reduced pressure of 5 × 10 ⁴ Pa or less.
Moreover, since the embedding property to the inner surface of the recessed part of (A) layer is further improved, it is also possible to use the thing of the material with abundant flexibility, such as rubber and plastics, on the surface of the said crimping roll. In particular, the layer thickness of the flexible material is preferably about 200 to 400 µm.
In addition, from the viewpoint of further improving the embedding ability of the (A) layer on the inner surface of the recessed portion, it is also possible to heat and laminate the photosensitive element by a heating roll or the like.
Moreover, after lamination is completed in this way, it is also possible to heat for 1 to 120 minutes in the range of 30-150 degreeC. In doing so, a support film can be removed as needed.
[Ib] Process of Forming Resin Layer Containing (C) Particles on Photosensitive Resin Composition Layer Containing (A) Phosphor]
The state which formed the resin layer containing (C) microparticles | fine-particles on the photosensitive resin composition layer containing (A) fluorescent substance is shown in FIG. 4 (I).
Although the method of forming a resin layer containing (C) microparticles | fine-particles on the photosensitive resin composition layer containing (A) fluorescent substance formed by the process of (Ia) mentioned above does not need to be specifically limited, The process of (Ia) mentioned above In the process of (Ia) described above using a film having a resin layer containing (C) microparticles and a method of forming a resin layer containing (C) microparticles by directly applying and drying the layer (A) formed by The method of forming on the (A) layer formed by this etc. can be mentioned.
As a method of directly applying and drying the photosensitive resin composition layer containing the (A) phosphor formed by the above-mentioned step (Ia) and drying it, for example, each component constituting the resin layer containing the above-mentioned (C) fine particles As a solution uniformly dispersed by dissolving or dispersing in a solvent capable of dissolving or degrading, there may be mentioned a method of directly applying on the layer (A) formed by the above-described step (Ia) and drying to form. As a solvent which can melt | dissolve or decompose each component which comprises the above-mentioned resin layer containing (C) microparticles | fine-particles, For example, water, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellulose solver, ethyl cellulose solver, gamma- Butyrolactam, N-methylpyrrolidone, dimethylformamide, tetramethylsulfone, diethylene glycol dimethyl ether, diethylene glycol mobutyl ether, chloroform, methylene chloride, methyl alcohol, ethyl alcohol and the like. These can be used individually or in mixture of 2 or more types.
Application method and drying conditions in forming by directly applying and drying the solution constituting the resin layer containing the fine particles (C) on the photosensitive resin composition layer containing the (A) phosphor formed by the above-described process (Ia) Silver can be made in the same way as when forming the photosensitive resin composition layer containing the (A) fluorescent substance of (Ia) process.
In addition, the layer (C) which consists of several layers can be formed by overlapping and apply | coating the solution which comprises the resin layer containing (C) microparticles | fine-particles. In particular, in forming the layer (C) from several layers, at least one of the layers preferably contains fine particles, and the other layers do not necessarily need to contain fine particles.
Moreover, in the method of mixing each component which comprises the resin layer containing (C) microparticles mentioned above, forming it in a film form and using it, it is formed on the (A) layer formed by the above-mentioned (Ia) process, As a method of forming the resin layer containing (C) microparticles | fine-particles into a film form, the knife nose on a support film as a uniform fine particle dispersion as it melt | dissolves and mixes each component which comprises the above-mentioned (C) layer in a solvent. It can form into a film shape by apply | coating and drying using well-known methods, such as a coating method, the roll coating method, the spray coating method, the gravure coating method, the bar coating method, and the caten coating method.
Moreover, also when forming the resin layer containing (C) microparticles | fine-particles, it has a (C) layer which consists of several layers by overlapping and apply | coating the solution which comprises the resin layer containing (C) microparticles | fine-particles differently. It can be formed into a film. In particular, in forming the layer (C) which consists of several layers, it is good to contain microparticles | fine-particles in at least 1 layer among several layers, and it is not necessary to necessarily contain microparticles | fine-particles in another layer.
(C) Although the thickness of the resin layer containing microparticles | fine-particles does not need to limit in particular, about 10-200 micrometers is preferable in consideration of the embedding property etc. in the recessed part inner surface of the board | substrate which has an unevenness | corrugation, and is about 20-100 micrometers More preferred.
As for the (B) thermoplastic resin used for the resin layer containing (C) microparticles | fine-particles, the viscosity in 100 degreeC has the preferable thing of 1-1 * 10 <^7> Pa sec, and the degree of 2-1 * 10 <^6> Pa sec is more preferable. Preferably, the degree of ^5-1 * 10 <^5> Pa sec is especially preferable, and the grade of 10-1 * 10 <^4> Pa sec is extremely preferable. When the viscosity at 100 ° C. is 1 Pa sec or less, when the viscosity at room temperature becomes too low to form a film, the (B) thermoplastic resin tends to come off from the edge due to flow, and the film formability tends to be lowered. Moreover, when it is 1 * 10 <^7> Pa sec or more, the formation property of the photosensitive resin composition layer containing (A) fluorescent substance in the inner surface of the recessed part of the board | substrate which has an unevenness | corrugation mentioned later tends to fall.
Moreover, the cover film which can be peeled further can be laminated | stacked on the resin layer containing (C) microparticles | fine-particles. Examples of the cover film include polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, and the like. The cover film contains the cover film and the (C) microparticles rather than the adhesion between the support film and the resin layer containing the (C) microparticles. The adhesive force with the resin layer is at least good. Although the thickness of a carver film does not need to restrict | limit especially, about 5-100 micrometers is preferable, and about 10-90 micrometers is more preferable.
Thus, the resin layer containing the (C) microparticles | fine-particles formed in the film form can be rolled and stored in roll shape.
(A) The resin layer containing the fine particles (A) is well embedded in the inner surface of the substrate having the unevenness used as the embedding layer to strengthen the embedding of the photosensitive resin composition layer containing the phosphor on the substrate. As a method of forming the layer, for example, a photosensitive resin composition layer containing the (A) phosphor of the above-mentioned photosensitive element is formed on a substrate having unevenness, and the embedding layer is heat-compressed in a state where the (C) layer is disposed thereon. Methods and the like can be enumerated.
(C) in a state in which a (A) layer of the photosensitive element having the photosensitive resin composition layer containing the above-mentioned (A) phosphor is formed on a substrate having unevenness and the resin layer containing (C) fine particles is disposed thereon. As a method of heating and crimping the layer, for example, after forming the (A) layer of the photosensitive element having the above-mentioned (A) layer, if the support film is present on the (A) layer, after removing the support film ( A resin layer containing (C) microparticles | fine-particles (after a cover film is removed, if there exists a cover film) on A) layer, and the method of heat-compression with a heating roll etc. can be mentioned.
In this case, an intermediate layer made of polyethylene, polypropylene, polycarbonate, polytetraphthalate, polyethylene terephthalate, or the like may be disposed between the layer (A) and the layer (C), followed by heat compression using a heating roll or the like. You may use an intermediate | middle layer overlapping one layer or two or more layers.
As for the heating temperature at the time of hot pressing, about 10-130 degreeC is preferable, About 20-120 degreeC is more preferable, About 30-110 degreeC is especially preferable. When this heating temperature is 10 degrees C or less, the embedding property to the inner surface of the recessed part of the board | substrate with which (A) layer has an unevenness tends to fall, and it is a tendency for (A) layer to thermoset at 130 degreeC or more.
In addition, the crimping pressure at the time of hot pressing is preferably 1 × 10 ⁴ to 1 × 10 ⁷ Pa, more preferably 2 × 10 ⁴ to 5 × 10 ⁶ Pa as the gauge pressure (normal pressure 1 atm is 0). , 4 × 10 ⁴ to 1 × 10 ⁶ Pa is particularly preferable. This thereof contact pressure 1 × 10 ⁴ Pa or less and the tendency for the filling performance of the recess inner surface of the substrate having the unevenness of the layer (A) decreases, 1 × 10 In ⁷ Pa or more irregularities of the substrate having a concave-convex (with barrier ribs including ) Tends to break down.
Since the crimping pressure at the time of hot pressing is the cylinder pressure of the laminator, it is preferable that it is about 2. 4 x 10 ² to 2. 4 x 10 ⁵ N / m in terms of linear pressure in terms of linear pressure, and it is preferably 4.8 x 10 ² to 1.2 x The thing of about 10 ⁵ N / m is more preferable, and the thing of about 9.6 * 10 <^2> -2.4 * 10 <^4> N / m is especially preferable. This is prone to compression pressure is 2. 4 × 10 ² is reduced to pieces of the area of the substrate of the PDP in the below N / m (A) layer 6, 2. 4 × 10 ⁵ N / m or more of the substrate for PDP Barrier ribs tend to break.
When the resin layer containing (C) microparticles is heated as mentioned above, it is not necessary to preheat-process the board | substrate with the unevenness | corrugation which laminated | stacked (A) layer, but the embedding property to the inner surface of the recessed part of (A) layer further improved. It is preferable to preheat-process the board | substrate which has the unevenness | corrugation which laminated | stacked the (A) layer from a viewpoint to make.
At this time, the preheating temperature is preferably in the range of 30 to 150 ° C, and the preheating time is preferably 0.5 to 20 minutes.
Moreover, it is also possible to use the thing of the material with abundant flexibility, such as rubber | gum, plastics, in the surface of the said crimping roll from a viewpoint of further improving the embedding to the inner surface of the recessed part of (A) layer. In particular, the layer thickness of the flexible material is preferably about 200 to 400 µm.
Furthermore, for the same purpose, the above-mentioned crimping and heating crimping operations may be performed at a reduced pressure of 5 × 10 ⁴ Pa or less.
Moreover, after lamination is completed, it is also possible to heat for 1 to 120 minutes in 30-150 degreeC. At this time, when a support film exists on the layer (C), the support film may be removed as necessary.
In the layer (A), this phenomenon occurs when (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group or (c) a photoinitiator that generates free radicals by irradiation with active light is likely to cause migration in the (C) layer. In order to suppress this, after lamination is completed, the board | substrate which has an unevenness | corrugation can also be cooled (usually -30-150 degreeC).
In the present invention, the step (I) is a step of simultaneously forming a photosensitive resin composition layer containing (A) phosphor and a resin layer containing (C) fine particles on a substrate having (I ') unevenness. This can be done in a way.
[A step of simultaneously forming a photosensitive resin composition layer containing (A) phosphor and a resin layer containing (C) fine particles on a substrate having (I ') unevenness]
As a method of simultaneously forming the layer (A) and the layer (C), the substrate (A) has irregularities using the photosensitive element having the layer (A) described above and the film having the layer (C) described above. The method of laminating | stacking two layers at the same time by contact | contacting a surface at the same time (when three or more exist in the case of an intermediate | middle layer at the same time) by heat compression was mentioned.
The conditions for the heat press bonding when the two layers are laminated by heating and pressing at the same time can be used.
Moreover, the photosensitive resin which has the resin layer containing (C) microparticles | fine-particles in the above-mentioned (I '') support film, and contains (A) fluorescent substance on it as a method of simultaneously forming (A) layer and (C) layer. The layer (A) and the layer (C) described above are laminated on the substrate having the unevenness by forming the photosensitive element for forming the phosphor pattern having the composition layer on the substrate having the unevenness. The method of laminating | stacking by heat pressing at the same time (3 or more at the same time, if there is an intermediate layer) can be mentioned.
(I '') A photosensitive element for forming a phosphor pattern having a resin layer containing (C) fine particles on a support film and having a photosensitive resin composition layer containing (A) phosphor thereon is described above on a substrate having irregularities. Simultaneously forming the above-mentioned (A) layer and (C) layer on a substrate having unevenness by lamination of one (A) layer]
In the process of (I ''), it is necessary to produce the photosensitive element for molding for phosphor pattern in which the resin layer containing (C) fine particles and the photosensitive resin composition containing (A) phosphor are integrated.
The photosensitive element for phosphor pattern formation incorporating the layer (C) and the layer (A) is formed on the support film by forming the layer (A) in the same manner as described above, and then forming the layer (C) on the layer (A) with the above-mentioned method. Forming in the same shape, (A) layer and (C) layer separately formed in the same shape as the above-mentioned method, if a carver film is present in each film, after peeling off the carver film (A) layer And (C) can be obtained by a method of stretching the layers together.
In the use of the photosensitive element for forming the phosphor pattern in which the layer (C) and the layer (A) are integrated, the heat pressing conditions can be used when the two layers are laminated while heating and pressing at the same time.
Thus, the photosensitive resin composition layer containing fluorescent substance (A) is formed uniformly in the inner surface of the recessed part of the board | substrate with an unevenness | corrugation, and the resin layer containing (C) microparticles can be formed on it.
Hereinafter, the manufacturing method of the phosphor pattern of the present invention will be described in detail with reference to FIG. 4. In particular, Fig. 4 is a schematic diagram showing an example of each step of the method for producing the phosphor pattern of the present invention.
The photosensitive resin composition layer 6 containing (A) phosphor and the resin layer 8 containing (C) microparticles | fine-particles were formed on the uneven | corrugated surface of the PDP board | substrate 1 (substrate with an unevenness | corrugation) in which the barrier rib 2 was formed. The process of (I) is completed] is shown in FIG.
[II] Irradiating actinic light to the resin layer containing (C) microparticles | fine-particles and the photosensitive resin composition layer containing (A) fluorescent substance normally;
(II) The state of the process of irradiating actinic light 9 through the feed mask to the resin layer 8 containing (C) microparticles | fine-particles, and the photosensitive resin composition layer 6 containing (A) fluorescent substance is shown to FIG. 4 (II). Indicated.
In this process, the feed mask 7 can use what has a narrow active light transmission width from the active light transmission width wider than the opening width of a recessed part. In particular, in this step, the opening width 10 of the recessed portion and the width 11 of the barrier rib are shown in FIG. 5. In particular, FIG. 6 is a schematic diagram showing a portion 12 to be photocured.
In this step, the width of the active light transmission width satisfying the barrier rib width 11 on the right and left sides of the opening width 10 of the recessed portion (when the barrier rib width 11 is 70 μm, the width of 140 μm wider than the aperture width 10 of the recessed portion) A width of 120 µm narrower than the opening width 10 of the recess is preferable, and a width that satisfies 50% of the barrier rib width 11 on the right and left sides of the opening width 10 of the recess (when the barrier rib width 11 is 70 µm, the opening width of the recess is defined). More preferably, the width is 70 µm wider than 10) to the opening width of the recessed portion 100 µm narrower than 10, and particularly preferably the width 1 µm to 90 µm narrower than the aperture width 10 of the recessed portion.
If the active light width is wider than the width satisfying the left and right barrier rib widths 11 to the opening width 10 of the recessed part, the photosensitive part tends to be photocured to a part other than the inner surface of the recessed part to be photocured. It tends to remain. In addition, the photocuring of the photosensitive resin composition layer 6 containing the (A) phosphor formed on the inner surface of the recess tends to be insufficient in a narrow width exceeding 120 µm than the opening width 10 of the recess. (A) Layer 6 formed on the inner surface of the recess is a tendency to decrease the development resistance (property that the portion of the pattern which is not removed by the development does not invade by development) is formed. It shows a tendency to remove to the required part of.
Here, the active light transmission width of the recess opening width 10 indicates the active light transmission width when the recess opening width 10 is 150 µm and the width 11 of the barrier rib is 70 µm. Therefore, when the dimension of recess part opening width 10 changes, the range of the actinic light transmission width narrower than the said recess part opening width 10 is determined according to this variation rate.
In addition, in order to increase the scattering efficiency of the light, the light scattering material sheet may be exposed between the light source and the feed mask 7.
The light scattering material sheet can be used insofar as it can refract or scatter the actinic light.
Specific examples of the light scattering material sheet include a quilting film having irregularities on the surface of the film, an embossed film, a sand mat film, a cloud glass, a glass with a shape, and a film or glass that transmits general active light. May be polished with sand paper or the like to form a cloud glass, glass is treated with hydrogen fluoride or the like, concave or convex on the surface, or a film containing fine particles and subjected to light scattering. These may be used independently and may be used overlapping 2 or more sheets.
The light scattering material sheet is light scattering only on one side, light scattering on both sides, light scattering on the surface and backside differently, light scattering on the inside, light scattering on the inside and only one side, inside The light scattering treatment may be used on both sides of the light, and the light scattering treatment may be different from the inside and the front and back surface. Active light can be irradiated on either side of the front and back for light scattering treatment of only one surface and light scattering treatment of different surface and back surface.
The light transmittance of the light scattering material sheet is preferably 3 to 100% transmitted, more preferably 10 to 100% transmission, compared to the case where no light scattering material sheet is used in the wavelength range of 230 nm to 450 nm. It is especially preferable to permeate-100%, and it is most preferable to permeate | transmit 50-100%. When the light transmission amount of the light scattering material sheet is less than 3%, the exposure time is relatively long, and work efficiency tends to be lowered.
The thickness of the light scattering material sheet may be any thickness as long as the light transmittance transmits 3 to 100% as compared with the case where no light scattering material sheet is used in the wavelength range of 230 nm to 450 nm. The position at the time of using the light scattering material sheet may be any height as long as the position is between the resin layer 8 containing the (C) fine particles and the active light source 9.
In Fig. 4 (II), as a method of irradiating the active light source 9 as an image, for example, water containing the photosensitive resin composition layer 6 and (C) fine particles containing the (A) phosphor in the state of Fig. 4 (I) can be obtained. And a method of irradiating actinic light 9 through a feed mask such as negative film, negative glass, polycarbonate, polyglass, etc. on the layer 8 and the like.
In the present step, as the active light 9, a known active light source can be used, for example, a carbon arc, a mercury vapor arc, a xenon arc, or the like can be listed.
Since the sensitivity of a photoinitiator is usually the maximum in an ultraviolet range, the active light source in that case should radiate an ultraviolet-ray effectively. In addition, since the photoinitiator is sensitive to visible light, for example, in the case of 9,10-phenanthrenequinone or the like, visible light is used as the active light 9, and in addition to the above-mentioned light source, a photographic bulb or a solar lamp may also be used. Can be. In the present invention, the active light 9 may include parallel light, scattered light, and the like, and any of parallel light and scattered light may be used, or both may be used in one process. You may use it separately as a step. In particular, when both sides are used separately in two steps, any one may be used first.
In addition, in this process, the irradiation amount of the actinic ray 9 does not need to be particularly limited, but is preferably about 5 to 10000 mJ / cm ² , more preferably about 7 to 8000 mJ / cm ² , and more preferably about 10 to 5000. Particularly preferred is about mJ / cm ² . If the irradiation amount of this actinic ray 9 is 5 mJ / cm ² or less, the photocuring of the photosensitive resin composition layer 6 containing the (A) phosphor formed on the inner surface of the recess is insufficient, and in the phenomenon described later, it is formed on the inner surface of the recess. (A) It is a tendency for the developing solution resistance of the layer 6 (the property which the part which becomes the pattern which remains even if removed by development does not invade by development) to fall. Moreover, when the irradiation amount of the actinic light 9 is 10000 mJ / cm <^2> or more, it is a tendency to photocure to parts other than the inner surface of the recessed part which photocured, and it shows the tendency which an unnecessary part remains after image development, as mentioned later.
[III] A step of forming a pattern by removing the resin layer containing (C) microparticles and selectively removing the photosensitive resin composition layer containing (A) phosphor by development.
The state which removed the unnecessary part by the phenomenon is shown to FIG. 4 (III). In FIG. 4 (III), 6 'is a photosensitive resin composition layer containing the (A) fluorescent substance after photocuring.
In this process, as a method of removing the resin layer containing (C) microparticles | fine-particles, for example, an adhesive tape is adhere | attached on a support film, or a support film and a layer (C) are physically used, for example using a brown-shaped tool, etc. (In addition, when an intermediate | middle layer exists, the intermediate | middle layer also), the method of peeling from the photosensitive resin composition layer containing (A) fluorescent substance, etc. can be mentioned.
In addition, as a method of removing the layer (C), a method of peeling the support film and the layer (C) (in the case of the intermediate layer, if an intermediate layer is present) using a force such as static electricity or suction for the purpose of improving workability, etc. Can be used.
In addition, immediately after peeling a support film and (C) layer (Moreover, an intermediate | middle layer, if an intermediate | middle layer exists), a support film and (C) layer after peeling (intermediate layer, if an intermediate | middle layer exists, etc.) immediately after peeling. Can be wound up).
In this step, the developing method for selectively removing the photosensitive resin composition layer containing the (A) phosphor by development is, for example, the support film on the resin layer containing the (C) fine particles after the state of Fig. 4 (II). If present, the support film and the layer (C) (moreover, if an intermediate layer is present) are peeled off from the layer (A) and then sprayed using a known developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. Developing by known methods such as rocking dipping, flashing, scrubbing and the like, and removing unnecessary portions of the layer (A), after the state of FIG. 4 (II), on the resin layer containing the fine particles (C) If present, the support film is removed, and development is carried out by known methods such as spraying, shaking, immersion, flashing, and scrubbing using a known developer such as an alkaline aqueous solution, an aqueous developer, and an organic solvent. And (C) can be exemplified a method of removing the unnecessary portions of the layer and the layer (A).
Further, as a method of removing the unnecessary portions of the layer (C) and the layer (A), (C) using layer 6, which does not dissolve layer 6, an aqueous alkali solution, an aqueous semisolvent, an aqueous semisolvent, an organic solvent, or the like, ) After removing the layer 8 by dissolution, the developer may be used to remove the unnecessary portion of (A) layer 6, and (A) the unnecessary portion of layer 6 and (C) layer 8 use the same developer. In this case, the developer can be used to remove the unnecessary portion of (A) layer 6 and the unnecessary portion of (C) layer 8 in one step.
In addition, as a method of removing (A) layer 6 and (C) layer 8, it can carry out individually or in one process by dry development, respectively.
In particular, in the present invention, in the step of (III), the resin layer containing the photosensitive resin composition layer 6 and (C) fine particles containing the (A) phosphor other than the inner surface of the recess formed by the step of (II) described above. 8 is an unnecessary part and should be removed by the phenomenon. Moreover, the developing time and the developing temperature at this time can be adjusted as appropriate to remove the unnecessary portion.
The development time is the minimum development time of the photosensitive resin composition layer 6 containing (A) phosphor [the fastest time after (A) layer is embedded in the inner surface of the recess of the PDP substrate, and the (A) layer is removed by development] 1-10 times the time is preferable, and developing temperature is about 10-60 degreeC is preferable.
If the developing time is less than or equal to the minimum developing time, the developing residue tends to be generated. If the developing time exceeds 10 times the minimum developing time, it tends to be removed to the required portion of layer (A). Moreover, developability tends to fall at 10 degrees C or less, and develop resistance falls at 60 degreeC or more.
Examples of the base of the aqueous alkali solution used for development include alkali hydroxide (hydroxide of lithium, sodium or potassium), alkali carbonate (such as carbonate or bicarbonate of lithium, sodium or potassium), alkali metal phosphate (such as potassium phosphate and sodium phosphate), alkali metal Pyrophosphate (sodium pyrophosphate, potassium pyrophosphate, etc.), tetramethyl ammonium hydroxide, triethanolamine, etc. are mentioned, Among these, sodium carbonate, tetramethyl ammonium hydroxide, etc. are mentioned to be preferable.
PH of the alkali aqueous solution used for image development is about 9-11, and the temperature is adjusted in addition to the developability of the photosensitive resin composition layer 6 containing (A) fluorescent substance, and the resin layer 8 containing (C) microparticles | fine-particles. Can be.
In addition, a small amount of organic solvent can be mixed in the aqueous alkali solution to promote the surfactant, the antifoaming agent and the development.
Examples of the aqueous developer include those formed from water or an aqueous alkali solution and one or more organic solvents.
Here, as the base of the aqueous alkali solution, in addition to the substances described above, for example, borax, sodium metasilicate, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxy-methyl-1,3-propanediol, 1 , 3-diaminopropanol-2, morpholine, and the like.
As for pH of an aqueous developing solution, about 8-12 are preferable, More preferably, it is the range of 9-10.
As the organic solvent, for example, acetone, ethyl acetate, alkoxy ethanol having 1 to 4 carbon atoms, alkoxy ethanol, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene Glycol monobutyl ether and the like. These organic solvents may be used alone or in combination of two or more thereof.
As an aqueous developer consisting of water and one or more organic solvents (emulsion solution when the organic solvent is not dissolved in water), the organic solvent is, for example, acetone alcohol (2-ketopropyl alcohol, acetone, ethyl acetate, 1 to 1 carbon atom). Alkoxy ethanol, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, dipropylene glycol with up to 4 alkoxy groups Monopropylene ether, 3-methyl-3-methoxybutylacrylate, 1, 1, 1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, Gamma-butyrolactam, etc. These may be used alone or in combination of two or more thereof.
The concentration of the organic solvent is usually in the range of 2 to 90% by weight, and the temperature can be adjusted in accordance with developability.
Moreover, a small amount of surfactant, an antifoamer, etc. can be mixed in an aqueous developing solution.
As an organic solvent developer used alone, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methylisobutyl ketone, gamma-butyrolactam And the like. You may add water to these organic solvents in the range of 1-20 weight% in order to prevent flammability.
In addition, known developer such as water, aqueous alkali solution, aqueous developer (made of water and at least one organic solvent or alkaline aqueous solution and at least one organic solvent), organic solvent and the like, except for alkali metal ions from the viewpoint of preventing phosphor degradation during development It is preferable not to contain a metal ion or a halogen ion.
In addition, in order to prevent deterioration of the developer and the phosphor, the base of the alkali aqueous solution remaining in the photosensitive resin composition layer 6 'containing the (A) phosphor after photocuring is sprayed or shaken by using an organic acid or an inorganic acid or such an aqueous acid solution. The acid treatment (neutralization treatment) can be carried out by known methods such as flashing, scrubbing and the like.
Examples of the acid include organic acids and inorganic acids such as saturated fatty acid, unsaturated fatty acid, aliphatic dibasic acid, aromatic dibasic acid, aliphatic tribasic acid and aromatic tribasic acid.
Specific organic acids include, for example, formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, propionic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, Stearic acid, nonadecanoic acid, arachinic acid, palmilean acid, oleic acid, eryidic acid, linolenic acid, linoleic acid, hydroxyl, malonic acid, methylmalonic acid, ethylmalonic acid, monomethylmalonic acid, monoethylmalonic acid, Succinic acid, methyl succinic acid, adipic acid, methyl adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, citric acid, salicylic acid, pi Rubinic acid, malic acid, etc. can be mentioned.
Among these, considering that the neutralizing effect is high, formic acid, hydroxyl, malonic acid, citric acid and the like can be listed as preferred.
The pH of the acid aqueous solution used for the acid treatment is preferably about 2 to 6, and the pH and temperature of the acid aqueous solution are the acid resistance of the photosensitive resin composition 6 'containing the phosphor after photocuring and the substrate for the PDP (substrate having irregularities) ( Durability that does not deteriorate with acid) can be adjusted. Furthermore, after the acid treatment (neutralization treatment), a washing step can be performed.
As such, the photosensitive resin composition layer (unnecessary portion) containing the (A) phosphor formed in addition to the recessed inner surface is removed by development, and the photosensitive resin composition layer 6 'containing the (A) phosphor after photocuring is removed on the inner surface of the recessed portion. A) It has photosensitivity on a layer, and when the (C) layer 8 exists, the resin layer containing the (C) microparticles | fine-particles after photocuring is formed.
Furthermore, in the above-described step (II), in the case of using the feed mask 7 having an opening width wider than the opening width of the recessed portion, the light irradiation portion of (A) layer 6 formed in addition to the recessed inner surface is the present process [(III) The process tends to be in the state shown in FIG. 7. In this case, the photosensitive resin composition layer 6 '(unnecessary portion) containing the (A) phosphor remaining after photocuring in addition to the recess inner surface can be completely removed by polishing or the like.
In particular, FIG. 7 is a schematic diagram showing a state after performing step (III) in the case of using the feed mask 7 having an opening width wider than that of the recessed portion in the step (II) of the present invention. 13 is an unnecessary part (where completely removed by polishing or the like).
In addition, when the adhesive tape is used for the above-mentioned unnecessary portion instead of the above-described polishing, only the unnecessary portion may be physically removed by peeling it off.
In addition, in consideration of such a case, after forming a multi-colored pattern consisting of a photosensitive resin composition layer containing phosphors that develop red, green, and blue colors described below, iron oxide, chromium oxide, and copper oxide are formed on the upper portion of the recess before the baking process described later. The black inorganic material paste containing black inorganic pigments, such as low melting-point glass pleats, etc. can be apply | coated or printed, or baking may be performed after forming a black strip using the photosensitive element containing a black inorganic material.
After development, ultraviolet irradiation or heating can be performed by a high-pressure mercury lamp or the like for the purpose of improving the adhesion and chemical resistance of the photoresist containing phosphors on the inner surface of the recessed part on the PDP substrate.
The irradiation amount of ultraviolet rays at this time is 0.2-10 J / cm <^2> normally, and can also heat in irradiation. Moreover, about 60-180 degreeC is preferable and, as for a heating temperature, about 100-180 degreeC is more preferable. Moreover, as for heating time, about 15 to 90 minutes are preferable. Irradiation and heating of such ultraviolet rays may be performed separately from irradiation and heating, and any of them may be performed first.
[Process for Removing Organic Components by (IV) Firing]
The state which formed the phosphor pattern after removing the organic component by baking is shown in FIG. 4 (IV). Furthermore, in Fig. 4 (IV), 12 is phosphor pattern.
In this step, the firing method does not need to be particularly limited, but a known firing method can be used to remove organic components other than the phosphor and the binder to form a phosphor pattern.
At this time, the baking temperature is preferably about 350 to 800 ° C, and more preferably about 400 to 600 ° C. In addition, the firing time is preferably about 3 to 120 minutes, more preferably about 5 to 90 minutes.
At this time, the temperature increase rate is preferably about 0.5 to 50 ° C / minute, and more preferably about 1 to 45 ° C / minute. In addition, it is possible to install the strip by maintaining the temperature between 350 to 450 ° C before reaching the maximum firing temperature, and the holding time is preferably about 5 to 100 minutes.
In the present invention, the method for producing the phosphor pattern is performed in order to reduce the number of steps, and in the present invention described above, the steps (I) to (III) are repeated in one color sheet to red, green and blue colors. It is preferable to form the multi-color phosphor pattern which performed the process of (IV) after forming the multi-color pattern which consists of the photosensitive resin composition layer containing fluorescent substance to develop.
In the present invention, the photosensitive resin composition layer 6 containing the phosphor (A) containing each phosphor colored in red, green, and blue alone may be performed in any order in each of the colors of red, green, and blue. It is possible.
In the present invention, a state in which a phosphor pattern containing a photosensitive resin composition layer containing the (A) phosphor colored in red, green and blue is formed by repeating each of the steps (I) to (III) in the first color. Is shown in FIG. 8. In Fig. 8, 6'a is a first color pattern, 6'b is a second color pattern, and 6'c is a third color pattern.
9 shows a state in which a multi-color phosphor pattern is formed, where 14a is a fluorescent pattern of the first color, 14b is a phosphor pattern of the second color, and 14c is a phosphor pattern of the third color.
In addition, the method for producing the phosphor pattern of the present invention includes (I) to (IV) in the present invention described above in consideration of suppression of erosion of the film (erosion of the photosensitive resin layer containing phosphors on the barrier rib wall portion). It is preferable to form a multi-color phosphor pattern that is colored in red, green and blue by repeating each step of the first color sheet.
The back plate for the plasma display panel of the present invention is provided with the fluorescent pattern of the present invention obtained as described above on the substrate for the plasma display panel.
Plasma displane of the invention; The size of the panel for the panel is not particularly limited, but a size of 25 inches or more is preferable diagonally, more preferably 30 inches or more diagonally, and particularly preferably 35 inches or more diagonally.
Hereinafter, the back plate for the plasma display panel will be described with reference to FIG. 11. In particular, FIG. 11 is a schematic diagram showing an example of a plasma display panel (PDP). In Fig. 11, 1 is a substrate, 2 is a barrier rib, 4 is a strip discharge space, 14 is a phosphor pattern, 16 is an address electrode, 17 is a protective film, 18 is a dielectric layer, 19 is a display electrode, and 20 is a front panel. Substrate.
In Fig. 11, the lower part containing the substrate 1, the barrier rib 2, the phosphor pattern 14, and the address electrode 16 is on the back plate for the PDP, and the upper part containing the protective film 17, the dielectric layer 18, the display electrode 19 and the front plate 20. Is the front panel for PDP.
PDPs can be classified into AC (AC) type PDPs, DC (DC) type PDPs, and the like from the voltage application method. The schematic diagram of FIG. 11 shown as an example is an AC type PDP.
In particular, the method for producing the photosensitive element and the phosphor pattern of the present invention can also be applied to self-luminous displays such as cathode ray tube (CRT), field emission display (FED), electroluminescence display (ELD) and the like. .
Example
Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
Manufacture example 1
[Production of Film Imparting Polymer (a)]
In the flask equipped with the stirrer, the reflux cooler, the inert gas inlet, and the thermometer, the ① shown in Table 1 was prepared, the temperature was raised to 80 ° C. in a nitrogen gas atmosphere, and the reaction temperature was maintained at 80 ° C. ± 2 ° C. Was added dropwise uniformly over 4 hours.
After dripping (2), stirring was continued at 80 degreeC +/- 2 degreeC for 6 hours, and the weight average molecular weight 80,000 and the acid value obtained the film property provision polymer (a) of 130 mg KOH / g.
materialCompounding amount (part by weight) ①Ethylene Glycol Monomethyl Ether70 toluene50 ②Methacrylate20 Methyl methacrylate55 Ethyl acrylate15 n-butyl methacrylate10 2,2'-azobis (isobutyronitrile)0.5
Manufacture example 2
[A] Preparation of photosensitive element (A-1) which has photosensitive resin composition layer containing fluorescent substance
The materials shown in Table 2 were mixed and mixed for 15 minutes using a Leica group to prepare a photosensitive resin composition containing a phosphor.
materialCompounding amount (part by weight) Film imparting polymer (a) obtained in Production Example 167 Tetraethylene Glycol Dimethacrylate [Photopolymerizable monomer made by Shin-Jungchon Chemical Industry Co., Ltd., product name NK ester 4G]33 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-12 (Y, Gd) BO ₃ : Eu140 Binder (Low Melting Point Glass)3 Methyl ethyl ketone30
The obtained solution was uniformly applied onto a 20 μm-thick polyethylene terephthalate film and dried in a hot air convection dryer at 80 to 110 ° C. for 10 minutes to remove the solvent, thereby forming a photosensitive resin composition layer containing phosphor (A). The thickness after drying of the obtained (A) layer was 60 micrometers.
Next, a 25 μm-thick polyethylene film was stretched on a layer (A) with a Carver film to prepare a photosensitive element (A-1) having a photosensitive resin composition layer containing the (A) phosphor.
Manufacture example 3
[A] Preparation of Photosensitive Element (A-2) Having Photosensitive Resin Composition Layer Containing Phosphor]
A photosensitive resin composition layer containing the (A) phosphor was formed in the same manner as in Production Example 2 except that the material shown in Table 2 was used instead of the material shown in Table 2. The thickness after drying of the obtained (A) layer was 60 micrometers.
materialCompounding amount (part by weight) Film imparting polymer (a) obtained in Production Example 167 Polypropylene glycol dimethacrylate (average number of propylene oxide 12)33 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1One (Y, Gd) BO ₃ : Eu140 Methyl ethyl ketone30
Next, the photosensitive element (A-2) which has the photosensitive resin composition layer containing fluorescent substance (A) similarly to manufacture example 2 was produced.
Manufacture example 4
[A] Preparation of Photosensitive Element (A-3) Having Photosensitive Resin Composition Layer Containing Phosphor]
A photosensitive resin composition layer containing the phosphor (A) was formed in the same manner as in Production Example 2 except that the material shown in Table 4 was used in place of the material shown in Table 2. After drying the obtained (A) layer, the thickness was 60 µm.
materialCompounding amount (part by weight) Polymethyl methacrylate67 Tetraethylene Glycol Dimethacrylate [Photopolymerizable Monomer by Shin-Nakamura Chemical Co., Ltd., brand name NK ester 4G]33 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1One (Y, Gd) BO ₃ : Eu140 Methyl ethyl ketone30
Next, the photosensitive element (A-3) which has the photosensitive resin composition layer containing fluorescent substance (A) similarly to manufacture example 2 was produced.
Manufacture example 5
[Production of Resin Composition (B-1) Containing (C) Fine Particles]
The resin solution made from the materials shown in Table 5 was mixed until uniformly dispersed to prepare a resin composition (B-1) containing fine particles (C).
materialCompounding amount (part by weight) Polyvinyl Alcohol [Kurare Co., Ltd., PVA 205, hydrolysis rate = 80%]17.3 Alumina particles (average particle size 3 μm)17.3 Distilled water28
Manufacture example 6
[Production of (C) Resin Composition Containing Fine Particles (B-2)]
The resin solution made of the material shown in Table 6 was uniformly coated on a 20 μm-thick polyethylene terephthalate film and dried in a hot air convection dryer at 80 to 110 ° C. for 10 minutes to remove the solvent and containing (C) fine particles. A resin composition layer was formed. The thickness after drying of the obtained (C) layer was 43 μm.
materialCompounding amount (part by weight) Film imparting polymer (a) obtained in Production Example 165 Triethylene Glycol Diacetate35 Polystyrene particles (average particle diameter 6 μm)70 Methyl ethyl ketone30
Subsequently, a polyethylene film having a thickness of 25 μm was stretched on each other with a Carver film on the layer (C) to produce a film (B-2) having a resin layer containing the particles (C).
Manufacture example 7
(C) Preparation of Resin Composition (B-3) Containing Fine Particles]
Instead of the material shown in Table 6, except having used the material shown in Table 7, it carried out similarly to the manufacture example 6, and formed the layer of the resin composition containing (C) microparticles | fine-particles. The thickness after drying of the obtained (C) layer was 50 µm.
materialCompounding amount (part by weight) Polymethyl methacrylate70 Triethylene Glycol Diacetate30 Polytetrafluoroethylene fine particles (average particle diameter 1 μm)120 Methyl ethyl ketone30
Next, similarly to the manufacture example 6, the film (B-3) which has a resin layer containing (C) microparticles | fine-particles was produced.
Manufacturing Example 8
[Production of Film (B-4) Having Resin Layer Containing (C) Fine Particles]
A resin composition layer containing (C) fine particles was formed in the same manner as in Production Example 6 except that the material shown in Table 8 was used instead of the material shown in Table 6. The thickness after drying of the obtained (C) layer was 50 µm.
materialCompounding amount (part by weight) Copolymer of ethylene and ethylene acrylate [Evaplex EEA 709, Mitsui DuPont Co., Ltd.]100 Organic particles (average particle size 3.1 μm)15 toluene300
Next, similarly to the manufacture example 6, the film (B-4) which has a resin layer containing (C) microparticles | fine-particles was produced.
Manufacturing Example 9
[Production of Film (B-5) Having Resin Layer Containing (C) Fine Particles]
Instead of the material shown in Table 6, except having used the material shown in Table 9, it carried out similarly to the manufacture example 6, and the resin composition layer containing (C) microparticles was formed. The thickness after drying of the obtained (C) layer was 50 µm.
materialCompounding amount (part by weight) Ethylene and Ethylene Acrylate Copolymer [Evaplex EEA 709, Mitsui DuPont Co., Ltd.]100 Glass particles (average particle size 2. 3 μm)20 Polypropylene glycol dimethacrylate (average number of propylene oxide 12)4 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-10. 4 toluene300
Next, similarly to the manufacture example 6, the film (B-5) which has a resin layer containing (C) microparticles | fine-particles was produced.
Manufacturing Example 10
[Production of Film (E-1) Having Photosensitive Resin Composition Layer Containing (A) Phosphor and Resin Layer Containing (C) Fine Particles]
The cover film of the film (B-5) which has the resin composition layer containing (C) microparticles | fine-particles obtained in manufacture example 9 was peeled off, and the fluorescent substance which consists of the material shown in Table 3 on the resin composition layer containing (C) microparticles | fine-particles is contained. The photosensitive resin composition solution was uniformly coated and dried in a hot air convection dryer at 80 to 110 ° C. for 10 minutes to remove the solvent, thereby forming a photosensitive resin composition layer containing the phosphor. The thickness after drying of the obtained (A) layer was 60 micrometers.
Next, on the photosensitive resin composition layer containing (A) phosphor, a 25 μm-thick polyethylene film was stretched together as a cover film, and the resin layer containing (A) photosensitive resin composition layer containing phosphor and (C) fine particles. The film (E-1) which has was produced.
Manufacturing Example 11
[Production of Film (E-2) Having Photosensitive Resin Composition Layer Containing (A) Phosphor and Resin Layer Containing (C) Fine Particles]
The resin solution made of the material shown in Table 10 was uniformly coated on a 20 μm thick polyethylene terephthalate film, dried in a hot air convection dryer at 80 to 110 ° C. for 10 minutes to remove the solvent, and (C) containing fine particles. A resin composition layer was formed. The thickness after drying of the obtained (C) layer was 50 µm.
materialCompounding amount (part by weight) Ethylene and Ethylene Acrylate Copolymer [Evaplex EEA 709, Mitsui DuPont Co., Ltd.]100 Glass particles (average particle size: 3.1 μm)15 toluene334
Next, (C) a 20 μm-thick polyethylene film was stretched together with the intermediate layer on the resin layer containing the fine particles, and the photosensitive resin composition solution containing the phosphor made from the materials shown in Table 3 was uniformly applied on the polyethylene film. , Dried for 10 minutes in a hot air convection dryer at 80 to 110 ℃ to remove the solvent to form a photosensitive resin composition layer containing the (A) phosphor. The thickness after drying of the obtained (A) layer was 50 micrometers.
Subsequently, a 20 μm-thick polyethylene film was tensioned with each other as a cover film on the photosensitive resin composition layer containing (A) phosphor, and the resin layer containing (A) photosensitive resin composition layer containing phosphor and (C) fine particles was prepared. Eggplant produced a film (E-2).
Comparative Production Example 1
[Production of Resin Composition (B'-1) Containing No Fine Particles (C ')]
The resin solution made from the materials shown in Table 11 was mixed until uniform, and a resin composition (B'-1) containing no (C ') fine particles was prepared.
materialCompounding amount (part by weight) Polyvinyl Alcohol [Kurare Co., Ltd., PVA 205, hydrolysis rate = 80%]17.3 Distilled water28
Comparative Production Example 2
[Preparation of film (B'-2) having a resin layer containing no (C ') fine particles]
In place of the material shown in Table 6, except for using the material shown in Table 12, and in the same manner as in Preparation Example 6, to form a resin composition layer containing no (C ') fine particles. The thickness after drying of the obtained (C ′) layer was 43 μm.
materialCompounding amount (part by weight) Film imparting polymer (a) obtained in Production Example 165 Triethylene Glycol Diacetate35 Methyl ethyl ketone30
Next, the film (B'-2) which has a resin layer which does not contain (C ') microparticles | fine-particles was produced similarly to manufacture example 6.
Comparative Production Example 3
[Production of Film (B'-3) with Resin Layer without (C ') Particles]
A resin composition layer containing no (C ′) fine particles was formed in the same manner as in Production Example 7 except that the material shown in Table 7 was used and the material shown in Table 13 was used. The thickness after drying of the obtained (C ′) layer was 50 μm.
materialCompounding amount (part by weight) Polymethyl methacrylate60 Triethylene Glycol Diacetate40 Methyl ethyl ketone30
Next, similarly to the manufacture example 6, the film (B'-3) which has a resin layer containing no (C ') microparticles | fine-particles was produced.
Comparative Production Example 4
[Preparation of film (B'-4) having a resin layer containing no (C ') fine particles]
Instead of the material shown in Table 8, except having used the material shown in Table 14, it carried out similarly to manufacture example 8, and the resin composition layer which does not contain the (C ') microparticles | fine-particles was formed. The thickness after drying of the obtained (C ′) layer was 50 μm.
materialCompounding amount (part by weight) Ethylene and Ethylene Acrylate Copolymer [Evaplex EEA 709, Mitsui DuPont Co., Ltd.]100 toluene300
Next, the film (B'-4) which has a resin layer containing no (C ') microparticles | fine-particles was produced similarly to manufacture example 6.
Comparative Production Example 5
[Preparation of film (B'-5) having a resin layer containing no (C ') fine particles]
Instead of the material shown in Table 9, except having used the material shown in Table 15, it carried out similarly to the manufacture example 9, and the resin composition layer containing no (C ') microparticles was formed. The thickness after drying of the obtained (C ′) layer was 50 μm.
materialCompounding amount (part by weight) Ethylene and Ethylene Acrylate Copolymer [Evaplex EEA 709, Mitsui DuPont Co., Ltd.]100 Polypropylene glycol dimethacrylate (average number of propylene oxide 12)4 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-10. 4 toluene300
Next, similarly to the manufacture example 6, the film (B'-5) which has a resin layer containing no (C ') microparticles | fine-particles was produced.
Comparative Production Example 6
[Production of Film (E'-1) with Photosensitive Resin Composition Layer Containing (A) Phosphor and Resin Layer without Containing (C ') Particles]
Film (B'-5) which does not contain the (C ') microparticles | fine-particles obtained by comparative manufacture example 5 instead of the film (B-5) with the resin layer containing (C) microparticles | fine-particles obtained from manufacture example 9 (B'-5) Film (E ') having a photosensitive resin composition layer (thickness 60 μm) containing the phosphor (A) and a resin layer (thickness 50 μm) containing no (C ′) fine particles, as in Preparation Example 10, except that -1) was produced.
Comparative Production Example 7
[Production of Film (E'-2) Having Photosensitive Resin Composition Layer Containing (A) Phosphor and Resin Layer without Containing (C ') Particles]
A photosensitive resin composition layer containing a phosphor (thickness of 50 μm) and an intermediate layer (thickness of 25 μm) were prepared in the same manner as in Production Example 11 except that the material shown in Table 10 was used and the material shown in Table 16 was used. And (C ') a film (E'-2) having a resin layer (50 µm thick) containing no fine particles.
materialCompounding amount (part by weight) Ethylene and Ethylene Acrylate Copolymer [Evaplex EEA 709, Mitsui DuPont Co., Ltd.]100 toluene334
[Production of Phosphor Feton]
Example 1
[Step of forming photosensitive resin composition layer containing (A) phosphor on uneven surface of (Ia) uneven surface of substrate]
Photosensitive photosensitive composition containing (A) phosphor obtained from manufacture example 2 on the side in which the barrier rib of the board | substrate for PDP (an opening width of 150 micrometers of a barrier rib and a barrier rib, 70 micrometers of a barrier rib, and 150 micrometers of a barrier rib) was formed. After the photosensitive element (A-1) having the resin composition layer was peeled off and stacked, the polyethylene terephthalate film was removed, and the polyethylene terephthalate film was removed and placed in a vacuum dryer to reduce the pressure to 1 × 10 ² Pa at room temperature.
Subsequently, under reduced pressure, the temperature was raised to 90 ° C. at a temperature increase rate of 5 ° C./min, held at 90 ° C. for 1 minute, and the pressure was returned to atmospheric pressure. (A) The photosensitive resin composition layer containing the phosphor was uneven. It was formed on the inner surface.
[Ib] Process of forming resin layer containing (C) fine particles on photosensitive resin composition layer containing (A) phosphor
The resin composition (B-1) containing (C) microparticles | fine-particles was dripped on the photosensitive resin composition layer containing (A) fluorescent substance, and spin-coated at 300 rpm. The substrate was dried for 10 minutes with a 110 ° C hot air convection dryer to remove distilled water, and a resin layer containing (C) microparticles was formed so that recesses were sufficiently embedded on the photosensitive resin composition layer containing (A) phosphors.
[II] Irradiating actinic light to the resin layer containing (C) microparticles | fine-particles and the photosensitive resin composition layer containing (A) fluorescent substance normally.
Subsequently, on the resin composition layer containing (C) microparticles | fine-particles, the center of the actinic-light transmission width 15 micrometers narrower than 150 micrometers of opening width between barrier ribs is made to adhere, and the HMW-201 GX type | mold exposure machine made by Oak Corporation Was irradiated with active light at 400 ml / cm ² .
[III] A step of forming a pattern for removing the resin layer containing the fine particles (C) and selectively removing the photosensitive resin composition layer containing the phosphor (A) by development.
Subsequently, after standing at room temperature for 1 hour, spray development was carried out at 30 ° C. for 120 seconds using 1% by weight aqueous sodium carbonate solution, and by the development, the layers (C) and (A) were selectively removed to form a pattern. After image development, it dried for 10 minutes at 80 degreeC, and irradiated with 3 J / cm <^2> ultraviolet-rays using the Toshiba ultraviolet irradiation apparatus of Toshiba electric material company, and heated at 150 degreeC for 1 hour in a dryer.
[(IV) Process of Removing Organic Components by Firing]
Subsequently, heat treatment (firing) at 550 ° C. for 30 minutes was performed to remove unnecessary resin components to form a phosphor pattern in the space of the PDP substrate.
[Evaluation of Phosphor Feton]
The cross section of the obtained phosphor pattern was observed with a stereoscopic microscope and SEM, and the formation state of the phosphor pattern was evaluated and the results are shown in Table 17. Evaluation criteria are as follows.
O: The phosphor layer is uniformly formed on the inner surface (barrier rib wall surface and substrate surface) of the PDP substrate.
X: The phosphor layer is not uniformly formed on the inner surface (barrier rib wall surface and substrate surface) of the PDP substrate.
Example 2
[Ia] Process of forming photosensitive resin composition layer containing (A) phosphor on uneven surface of uneven substrate
Photosensitive photosensitive material containing (A) phosphor obtained from the manufacture example 2 on the side in which the barrier rib of the board | substrate for PDP (strip phase barrier rib, the opening width between barrier ribs, the barrier rib width 70 micrometers, and the barrier rib height 150 micrometers) was formed. Peel off the polyethylene film attached to the photosensitive element (A-1) having the resin composition layer, and heat-sensing the temperature of the photosensitive element by using a vacuum laminate [Hitachi Chemical Co., Ltd. product, brand name VLM-1 type] At a temperature of 30 ° C, lamination speed of 0.5 m / min, air pressure of 4000 Pa or less, and pressing pressure (cylinder pressure) of 5 × 10 ⁴ Pa (3 mm in thickness, 10 cm in length and 10 cm in width). The linear pressure of was laminated at 2. 4 x 10 ³ N / m).
[Ib] Process of forming resin layer containing (C) fine particles on photosensitive resin composition layer containing (A) phosphor
Subsequently, the resin layer containing (C) microparticles | fine-particles obtained from the manufacture example 6 on (A) layer is peeled off the polyethylene terephthalate of the photosensitive element (A-1) containing the photosensitive resin composition layer containing (A) fluorescent substance. Peel off the polyethylene terephthalate film attached to the film (B-2) including the laminator [Hitachi Chemical Co., Ltd., product name VLM-1 type] using a laminator speed of 0.5 m / min, air pressure of 4000 Pa or less, Since the contact pressure is the gauge pressure (cylinder pressure, a normal pressure of 1 atm is zero) to 4 × 10 ⁵ Pa (having a thickness of 3 mm, using a substrate of a vertical 10 cm × a width of 10 cm linear pressure at this time is 9. 8 × 10 ³ N / m) to form a layer (A) and a layer (C) on the inner surface of the recess.
[II] Irradiating actinic light to the resin layer containing (C) microparticles | fine-particles and the photosensitive resin composition layer containing (A) fluorescent substance normally.
Subsequently, on the polyethylene terephthalate film of the film (B-2) having the resin composition layer containing the fine particles (C), a feed mask having an active light transmission width of 15 μm narrower than the opening width of 150 μm between the barrier ribs was placed between the barrier ribs. The center of the opening width of the feed mask was in close contact with the center of the opening width of the feed mask, and the active light was irradiated at 400 ml / cm ² using an HMW-201 GX type exposure machine manufactured by Oak Corporation. .
[III] A step of removing the resin layer containing the fine particles (C) and forming a pattern to selectively remove the photosensitive resin composition layer containing the phosphor (A) by development. After that, the polyethylene terephthalate film of the film (B-1) having the resin layer containing the fine particles (C) was peeled off and spray development was carried out at 30 ° C. for 120 seconds using an aqueous solution of 1% by weight of sodium carbonate, followed by development (C The) layer and (A) layer were selectively removed to form a pattern. After the development, the film was dried at 80 ° C for 10 minutes, and was irradiated with ultraviolet light of 3 J / cm ² using a Toshiba ultraviolet irradiation device manufactured by Toshiba Electric Material Co., Ltd., and further heated in a dryer at 150 ° C for 1 hour.
[(IV) Process of Removing Organic Components by Firing]
Subsequently, heat treatment (firing) at 550 ° C. for 30 minutes was performed to remove unnecessary resin components to form a phosphor pattern in the space of the PDP substrate.
[Evaluation of Phosphor Feton]
The cross section of the obtained phosphor pattern was evaluated in the same manner as in Example 1 to form the phosphor pattern, and the results are shown in Table 17.
Example 3
In Example 2, the photosensitive resin composition layer containing the fluorescent substance (A) obtained in the manufacture example 3 which obtained the photosensitive element (A-1) which has the photosensitive resin composition layer containing the (A) phosphor of the process of (I) The branch was replaced with the photosensitive element (A-2), except that the process of (II) was shown below, except that the phosphor pattern was formed in the same manner as in Example 2, and the obtained phosphor pattern was evaluated and the results are shown in Table 17. .
[II] Irradiating actinic rays to the resin layer containing (C) microparticles | fine-particles and the photosensitive resin composition layer containing (A) fluorescent substance normally.
(C) On the polyethylene terephthalate film of the film (B-2) having the resin layer containing the fine particles, a feed mask having an active light transmission width of 30 μm narrower than the opening width of the barrier ribs is 150 μm, and the opening width between the barrier ribs. The center of the substrate was in close contact with the center of the active light transmission width of the feed mask, and the active light was irradiated at 400 ml / cm ² using an HMW-201 GX type exposure machine manufactured by Oak Corporation.
Example 4
In Example 3, the photosensitive element (A-2) which has the photosensitive resin composition layer containing the fluorescent substance (A) of the process (I) has the photosensitive resin composition layer containing the (A) fluorescent substance obtained by manufacture example 4. Instead of the photosensitive element (A-3), the film (B-2) which has a resin layer containing (C) microparticles | fine-particles was obtained by the manufacture example 7.
(C) A phosphor pattern obtained by forming a phosphor pattern in the same manner as in Example 3 except for replacing the film (B-3) having the resin layer containing fine particles with the following It evaluated, and the result is shown in Table 17.
[III] A step of removing the resin layer containing the fine particles (C) and selectively removing the photosensitive resin composition layer containing the phosphor (A) by development to form a pattern;
After irradiating actinic light, it was left to stand at room temperature for 1 hour, and then the polyethylene terephthalate film of the film (B-3) having a resin layer containing (C) microparticles was peeled off, and 3-methyl-3-methoxybutyl acetate and Spray development at 30 ° C. for 70 seconds using an emulsion solution of water (3-methyl-3-methoxybutylacetate / water (weight ratio) = 25/75) and layer (C) and (A) were developed by development. It was selectively removed to form a pattern. After development, it dried for 10 minutes at 80 degreeC, the Toshiba ultraviolet-ray irradiation apparatus of Toshiba Electric Material Co., Ltd. was irradiated with the ultraviolet-ray of 3 J / cm <^2> , and further heated in 150 degreeC for 1 hour at dryer.
Example 5
In Example 1, except that the processes of (Ia), (Ib) and (II) were replaced with those shown below, phosphor phosphors were formed in the same manner as in Example 1, and the obtained phosphor patterns were evaluated. The results are shown in Table 17.
[Ia] Process of forming photosensitive resin composition layer containing (A) phosphor on uneven surface of uneven substrate
In the area where the barrier ribs of the substrate for PDP (strip phase barrier ribs, the opening width between barrier ribs, the barrier rib width 70 µm and the barrier rib height 150 µm) were formed, the materials shown in Table 3 of the Preparation Example 3 were mixed and Screen printing machine containing photosensitive resin paste (AP-2) containing (A) phosphor obtained by mixing for 15 minutes using this machine [SSA-PC1310 AN of Donghae Junggi Co., Ltd., screen mesh = 100 μm, skiddy speed = 10 cm / sec, Adduct angle = 75 degrees].
Subsequently, it heated at 80 degreeC for 15 minutes, and formed the photosensitive resin composition layer containing (A) fluorescent substance in the uneven | corrugated inner surface.
[Ib] Process of forming resin layer containing (C) fine particles on photosensitive resin composition layer containing (A) phosphor
(A) A film containing a resin layer containing (C) fine particles on a photosensitive resin composition layer containing a phosphor (B-1) is a screen printing machine [SSA-PC1310 AN of Donghae Junggi Co., Ltd., screen = 100 μm, skiddy velocity = 10 cm / sec, adduct angle = 75 degrees].
The substrate was dried in a 110 ° C. hot air convection dryer for 10 minutes, and distilled water was removed to sufficiently embed a resin layer containing (C) fine particles in the recessed surface on which the photosensitive resin composition layer containing (A) phosphor was formed. (C) layer was formed.
[II] Irradiating actinic light to the resin layer containing (C) microparticles | fine-particles and the photosensitive resin composition layer containing (A) fluorescent substance normally;
Subsequently, a feed mask having an active light transmission width 30 μm narrower than 150 μm of the opening width between barrier ribs is placed on the resin composition layer containing (C) fine particles so as to be spaced 100 μm upward from the layer (C), and the barrier The center of the opening width of the feed mask was positioned at the center of the opening width between the ribs, and the active light was irradiated at 400 ml / cm ² by using an HMW-590 exposure machine manufactured by Oak Co., Ltd. .
Example 6
In Example 5, except that the steps of (Ib) and (II) were substituted for those shown below, phosphor phosphors were formed in the same manner as in Example 5, the obtained phosphor patterns were evaluated, and the results are shown in Table 17. Indicated.
[Ib] Process of forming resin layer containing (C) fine particles on photosensitive resin composition layer containing (A) phosphor
(A) The polyethylene film of the film (B-4) which has the resin layer containing the (C) microparticles | fine-particles obtained by the manufacture example 8 on the photosensitive resin composition layer containing fluorescent substance was peeled off, and a laminator [Hitachi Chemical Co., Ltd. Product, Product Name: HLM-3000 type] Laminator speed is 0.5 m / min, pressing pressure is gauge pressure (cylinder pressure, normal pressure 1 atmospheric pressure is 0) and 4 × 10 ⁵ Pa (3 mm thick, vertical) Since the board | substrate of 10 cm x 10 cm was used, the linear pressure at this time was laminated | stacked by 9.8 * 10 <^3> N / m), and (C) layer was formed on (A) layer.
[III] A step of removing the resin layer containing the fine particles (C) and selectively removing the photosensitive resin composition layer containing the phosphor (A) by development to form a pattern. The adhesive film was adhered on the polyethylene terephthalate film on the film (B-4) having the resin layer, and the film (B-4) having the resin layer physically containing (C) fine particles was peeled off and removed.
Subsequently, after standing at room temperature for 1 hour, spray development was carried out at 30 ° C. for 50 seconds using 1% by weight aqueous sodium carbonate solution, and (A) the layer was selectively removed to form a pattern. After image development, it dried for 10 minutes at 80 degreeC, and irradiated with 3 J / cm <^2> ultraviolet-rays using the Toshiba ultraviolet irradiation apparatus of the Toshiba electric material company.
Example 7
In Example 5, the phosphor pattern was formed in the same manner as in Example 5 except that the process of (Ia) was replaced with the one shown below, and the obtained phosphor pattern was evaluated and the results are shown in Table 17.
[Step of forming photosensitive resin composition layer containing (A) phosphor on uneven surface of (Ia) uneven surface of substrate]
Photosensitive photoresist containing (A) phosphor obtained in Preparation Example 2 in a region in which a barrier rib having a substrate for a PDP (an opening width between stripe barrier ribs and a barrier rib 150 μm, a barrier rib 70 μm and a barrier rib 150 μm) was formed. After peeling and stacking the polyethylene terephthalate film of the photosensitive element (A-1) which has a resin composition layer, the polyethylene terephthalate film was peeled off, put into a vacuum dryer, and it pressure-reduced to 1 * 10 <^2> Pa at normal temperature.
Subsequently, in a pressure-reduced state, the temperature was raised to 90 ° C. at a temperature increase rate of 5 ° C./min, held at 90 ° C. for 1 minute, and the pressure was returned to atmospheric pressure, thereby providing a photosensitive resin composition layer containing (A) phosphor. It was formed on the inner surface of the recess.
Example 8
In Example 2, a phosphor pattern was formed and obtained in the same manner as in Example 2 except for replacing the steps of (Ia), (Ib), (II), and (III) with those shown below. The phosphor pattern was evaluated and the results are shown in Table 17.
[Step of forming photosensitive resin composition layer containing (A) phosphor on uneven surface of (Ia) uneven surface of substrate]
Photosensitive photosensitive material containing (A) phosphor obtained in the manufacture example 2 on the side in which the barrier rib of the board | substrate for PDP (an opening width between strip-shaped barrier ribs, a barrier rib 150 micrometers, the width of a barrier rib 70 micrometers, and a barrier rib 150 micrometers) is formed. After peeling off the polyethylene film of the photosensitive element (A-1) which has a resin composition layer, the laminator roll temperature was 70 degreeC and a laminator speed was set using a laminator [Hitachi Chemical Co., Ltd. product, brand name: HLM-3000 type]. At 0.5 m / min, the crimping pressure is 2 × 10 ⁵ Pa (3 mm thick, 10 cm x 10 cm wide) at gauge pressure (cylinder pressure, normal atmospheric pressure is 0 atm). The linear pressure was laminated at 4.9 × 10 ³ N / m), and the photosensitive resin composition layer containing the phosphor (A) was laminated. Then, the polyethylene terephthalate film which is a support film was peeled off, and the board | substrate was heated at 80 degreeC for 10 minutes.
[Ib] Process of forming resin layer containing (C) fine particles on photosensitive resin composition layer containing (A) phosphor
Subsequently, the polyethylene film of the film (B-4) containing the resin layer containing the (C) microparticles | fine-particles obtained by the manufacture example 8 on the (A) layer was peeled off, and a laminator [Hitachi Chemical Co., Ltd. product, brand name : Laminator speed is 0.5 m / min, crimping pressure is 4 × 10 ⁵ Pa (thickness is 3 mm, length 10 cm ×) at gauge pressure (cylinder pressure, normal pressure 1 atmospheric pressure is 0). Since the board | substrate of width 10cm was used, the linear pressure at this time was laminated | stacked at 9.8x10 <^3> N / m), and (A) layer and (C) layer were formed in the recessed part inner surface.
[II] Irradiating actinic light to the resin layer containing (C) microparticles | fine-particles and the photosensitive resin composition layer containing (A) fluorescent substance normally.
Subsequently, a feed mask having an active light transmission width 30 μm narrower than 150 μm of the opening width between the barrier ribs on the resin composition layer containing (C) fine particles was spaced 300 μm upward from the polyethylene terephthalate on the layer (C). Position so that the center of the opening width of the feed mask is positioned at the center of the opening width between the barrier ribs, and is activated at 400 ml / cm ² using the HMW-590 type exposure machine manufactured by Oak Co., Ltd. The beams were irradiated with light.
[III] A step of removing the resin layer containing the fine particles (C) and selectively removing the photosensitive resin composition layer containing the phosphor (A) by development to form a pattern;
Next, the adhesive film is adhered onto the polyethylene terephthalate film on the film (B-4) having the resin layer containing the (C) microparticles, and the film having the resin layer physically containing the (C) microparticles (B-4) Was stripped and removed.
Subsequently, after standing at room temperature for 1 hour, spray development was carried out at 30 ° C. for 50 seconds using 1% by weight aqueous sodium carbonate solution, and (A) the layer was selectively removed to form a pattern. After image development, it dried for 10 minutes at 80 degreeC, and irradiated with 3 J / cm <^2> ultraviolet-rays using the Toshiba ultraviolet irradiation device of Toshiba electric material company.
Example 9
In Example 8, the photosensitive element (A-1) which has the photosensitive resin composition layer containing phosphor (A) obtained from manufacture example 2 has the photosensitive resin composition layer containing (A) phosphor obtained in manufacture example 3 Instead of the photosensitive element (A-2), the film (B-4) which has the resin layer containing the (C) microparticles | fine-particles obtained in manufacture example 8 has a resin layer containing the (C) microparticles obtained in manufacture example 9 Except replacing with film (B-5), the phosphor pattern was formed in the same manner as in Example 8, and the obtained phosphor pattern was evaluated, and the results are shown in Table 17.
Example 10
In Example 8, it was the same as Example 8 except having replaced the process of (Ia) and the process of (Ib) with the process of (I) shown below, and replacing the process of (III) as shown below. In order to form the phosphor pattern, the obtained phosphor pattern was evaluated, and the results are shown in Table 17.
[Steps of sequentially forming a photosensitive resin composition layer containing (A) phosphor and a resin layer containing (C) fine particles on (Ia) uneven substrate
The substrate for PDP preheated to 80 ° C. (barrier ribs in strip form, 150 μm in opening width between barrier ribs, 70 μm in width of barrier ribs, and 150 μm in height of barrier ribs) was formed on the side where barrier ribs were formed (A) obtained in Production Example 10. After peeling the polyethylene film of the film (E-1) which has the photosensitive resin composition layer containing fluorescent substance and the resin composition layer containing (C) microparticles | fine-particles, (A) layer contact | connects, a laminator [Hitachi Chemical Industries ( Note) Product, product name: HLM-3000 type], laminator roll temperature is 120 ℃, laminator speed is 0.5 m / min, crimping pressure is 4 × 10 at gauge pressure (cylinder pressure, atmospheric pressure is 1 atm). ^{Since 5} Pa (3 mm thick, 10 cm long by 10 cm wide substrates are used, the linear pressure at this time is laminated at 9.8 x 10 ³ N / m), and (A) a photosensitive resin composition layer containing a phosphor and ( C) A resin composition layer containing fine particles was formed.
[III] A step of removing the resin layer containing the fine particles (C) and selectively removing the photosensitive resin composition layer containing the phosphor (A) by development to form a pattern. A pressure-sensitive adhesive film is adhered onto a polyethylene terephthalate film on a film (E-1) having a photosensitive resin composition layer and a resin layer containing (C) fine particles, and physically peeling and removing the resin layer portion containing (C) fine particles. It was.
Subsequently, after standing at room temperature for 1 hour, spray development was carried out at 30 ° C. for 50 seconds using 1% by weight aqueous sodium carbonate solution, and (A) the layer was selectively removed to form a pattern. After image development, it dried for 10 minutes at 80 degreeC, and irradiated with 3 J / cm <^2> ultraviolet-rays using the Toshiba ultraviolet irradiation apparatus of the Toshiba electric material company.
Example 11
In Example 10, the film (E-1) having the photosensitive resin composition layer containing the (A) phosphor obtained from Production Example 10 and the resin layer containing the (C) fine particles (A) phosphor obtained in Production Example 11 Phosphor pattern in the same manner as in Example 10 except for replacing the film (E-2) having the photosensitive resin composition layer containing the resin layer and the resin layer containing the fine particles (C) and the step (III) shown below. Was formed and the resulting phosphor pattern was evaluated, and the results are shown in Table 17.
[III] A step of removing the resin layer containing the fine particles (C) and selectively removing the photosensitive resin composition layer containing the phosphor (A) by development to form a pattern.
Next, the adhesive film is adhered onto the polyethylene terephthalate film on the film (E-1) having the photosensitive resin composition layer (A) containing the phosphor and the resin layer (C) containing the fine particles, and physically (C) the fine particles. The resin layer and the intermediate layer part containing were peeled off.
Subsequently, after standing at room temperature for 1 hour, spray development was carried out at 30 ° C. for 50 seconds using 1% by weight aqueous sodium carbonate solution, and (A) the layer was selectively removed to form a pattern. After image development, it dried for 10 minutes at 80 degreeC, and irradiated with 3 J / cm <^2> ultraviolet-rays using the Toshiba ultraviolet irradiation device of Toshiba electric material company.
Comparative Example 1
In Example 1, the resin composition (B-1) containing the fine particles obtained in Production Example 5 was replaced with the resin composition (B'-1) not containing the (C ') fine particles obtained in Comparative Production Example 1. The phosphor pattern was formed in the same manner as in Example 1, and the phosphor pattern obtained was evaluated. The results are shown in Table 18.
Comparative Example 2
Example 2 WHEREIN: The film (B-2) which has the resin composition layer containing the (C) microparticles | fine-particles obtained in manufacture example 6 has a resin composition layer which does not contain the (C ') microparticles | fine-particles obtained by comparative manufacture example 2. Except for replacing with the film (B'-2), the phosphor pattern was formed in the same manner as in Example 2, and the obtained phosphor pattern was evaluated, and the results are shown in Table 18.
Comparative Example 3
Example 3 WHEREIN: The film (B-2) which has the resin composition layer containing the (C) microparticles | fine-particles obtained in manufacture example 6 has a resin composition layer which does not contain the (C ') microparticles | fine-particles obtained by comparative manufacture example 2. Except replacing with the film (B'-2), the phosphor pattern was formed in the same manner as in Example 3, and the obtained phosphor pattern was evaluated, and the results are shown in Table 18.
Comparative Example 4
Example 4 WHEREIN: The film (B-3) which has the resin composition layer containing the (C) microparticles | fine-particles obtained by manufacture example 7 has a resin composition layer which does not contain the (C ') microparticles | fine-particles obtained by comparative manufacture example 3. Except for replacing with the film (B'-2), the phosphor pattern was formed in the same manner as in Example 4, and the obtained phosphor pattern was evaluated, and the results are shown in Table 18.
Comparative Example 5
In Example 5, the resin composition (B-1) containing the (C) fine particles obtained in Production Example 5 was added to the resin composition (B'-1) not containing the (C ') fine particles obtained in Comparative Production Example 1. Except for the substitution, the phosphor pattern was formed in the same manner as in Example 5, and the obtained phosphor pattern was evaluated, and the results are shown in Table 18.
Comparative Example 6
Example 6 WHEREIN: The film (B-4) which has the resin composition layer containing the (C) microparticles | fine-particles obtained in manufacture example 8 has a resin composition layer which does not contain the (C ') microparticles | fine-particles obtained in comparative manufacture example 4. Except replacing with the film (B'-4), the phosphor pattern was formed in the same manner as in Example 6, and the obtained phosphor pattern was evaluated, and the results are shown in Table 18.
Comparative Example 7
In Example 7, the resin composition (B-1) containing the fine particles (C) obtained in Production Example 5 was used as the resin composition (B'-1) not containing the (C ') fine particles obtained in Comparative Production Example 1. Except for the substitution, the phosphor pattern was formed in the same manner as in Example 7, and the obtained phosphor pattern was evaluated. The results are shown in Table 18.
Comparative Example 8
Example 8 WHEREIN: The film (B-4) which has the resin composition layer containing the (C) microparticles | fine-particles obtained in manufacture example 8 has a resin composition layer which does not contain the (C ') microparticles | fine-particles obtained by comparative manufacture example 4. Except for replacing with the film (B'-4), the phosphor pattern was formed in the same manner as in Example 8, and the obtained phosphor pattern was evaluated. The results are shown in Table 18.
Comparative Example 9
Example 9 WHEREIN: The film (B-5) which has the resin composition layer containing the (C) microparticles | fine-particles obtained in manufacture example 9 has a resin composition layer which does not contain the (C ') microparticles | fine-particles obtained by comparative manufacture example 5. Except replacing with the film (B'-5), the phosphor pattern was formed in the same manner as in Example 9, and the obtained phosphor pattern was evaluated, and the results are shown in Table 18.
Comparative Example 10
In Example 10, a film (E-1) having a photosensitive resin composition layer containing (A) phosphor obtained in Production Example 10 and a resin composition layer containing (C) fine particles was obtained in Comparative Production Example 6 (A ) The phosphor pattern obtained by forming a phosphor pattern in the same manner as in Example 10 except for replacing with a film (E′-1) having a photosensitive resin composition layer containing a phosphor and a resin composition layer containing no (C ′) fine particles The results are shown in Table 18.
Comparative Example 11
In Example 11, the film (E-2) which has the photosensitive resin composition layer containing the fluorescent substance (A) obtained in manufacture example 11, and the resin composition layer containing (C) microparticles | fine-particles was obtained by comparative manufacturing example 7 (A ) Except for replacing with a film (E'-2) having a photosensitive resin composition layer containing a phosphor and a resin layer containing (C ') fine particles, a phosphor pattern was formed in the same manner as in Example 11, and the obtained phosphor pattern was evaluated. The results are shown in Table 18.
(C) fine particles in the resin layerFormability of Phosphor Feton Example 1has existO Example 2has existO Example 3has existO Example 4has existO Example 5has existO Example 6has existO Example 7has existO Example 8has existO Example 9has existO Example 10has existO Example 11has existO
(C) fine particles in the resin layerFormability of Phosphor Feton Comparative Example 1none× Comparative Example 2none× Comparative Example 3none× Comparative Example 4none× Comparative Example 5none× Comparative Example 6none× Comparative Example 7none× Comparative Example 8none× Comparative Example 9none× Comparative Example 10none× Comparative Example 11none×
Examples 1 to 11 using the resin composition containing the (C) microparticles and the film containing the resin layer containing the (C) microparticles from Table 17 and Table 18 show the formability of the phosphor pattern on the inner surface of the main part of the substrate for PDP. It is understood that (the property of forming a phosphor pattern with a uniform thickness only on the barrier rib wall surface of the PDP substrate or on the inner surface of the recess portion surrounded by the substrate bottom surface) is good.
Compared with this, Comparative Examples 1-11 using the film containing the resin composition which does not contain the (C ') microparticles | fine-particles or the resin layer which does not contain the (C') microparticles | fine-particles are FIGS. 10A and 10B. As indicated by, the photosensitive resin layer containing the phosphor of the barrier rib wall portion is eroded, so that the phosphor pattern is not formed with a uniform film thickness over the barrier rib wall surface and the recessed inner surface surrounded by the substrate bottom, and the main portion of the substrate for the PDP is The internal formability of the phosphor pattern is poor. In particular, 15 is a phosphor pattern in which the barrier rib wall is eroded.
The method for producing a phosphor pattern according to claim 1 is a method for embedding a substrate having irregularities such as a substrate for PDP (if the substrate is a substrate for PDP, formation of a photosensitive resin composition layer containing phosphor on a barrier rib wall surface or a space bottom surface) It can be formed by having excellent tolerance, good yield, and having a tolerance of phosphor pattern of uniform shape with high precision.
The method for producing the phosphor pattern according to claim 2 has an effect on the method for producing the phosphor pattern according to claim 1 or 2, and is more excellent in workability and environmental safety.
The method for producing the phosphor pattern according to claim 3 has an effect on the method for producing the phosphor pattern according to claim 1 or 2, and is more excellent in workability.
The method for producing the phosphor pattern according to claim 4 has an effect on the method for producing the phosphor pattern according to claim 1 or 2, and furthermore, the film erosion phenomenon (erosion of the photosensitive resin layer containing phosphor on the barrier rib wall portion). It is excellent in suppressing).
The manufacturing method of the fluorescent pattern of Claim 5 has an effect on the manufacturing method of the fluorescent pattern of Claim 1, 2, 3, or 4, and is further excellent in workability and light sensitivity.
The photosensitive element for forming the phosphor pattern according to claim 6 is designed for suppressing edge push and embedding into a space of a substrate having irregularities such as a PDP substrate (if the substrate is a PDP substrate, the phosphor is formed on the barrier rib wall surface and the space bottom surface). Formability of the photosensitive resin composition layer containing a) may be formed to have an excellent tolerance, a good yield and a tolerance of the phosphor pattern of uniform shape with high precision.
The photosensitive element for phosphor pattern formation according to claim 7 has an effect on the photosensitive element for phosphor pattern formation according to claim 6, and is further excellent in workability and light sensitivity.
The phosphor pattern according to claim 8 is excellent in luminance in a uniform shape with high precision.
The back plate for the plasma display panel according to claim 9 can be made of a phosphor pattern having excellent luminance in a uniform shape with high precision.

权利要求:
Claims (9)
[1" claim-type="Currently amended] In the production of the phosphor pattern, (I) forming a photosensitive resin composition layer containing (A) phosphor and a resin layer containing (C) fine particles on a substrate having unevenness,
(II) process of irradiating actinic light to the resin layer containing (C) microparticles | fine-particles, and the photosensitive resin composition layer containing (A) fluorescent substance normally,
(III) removing the resin layer containing the fine particles (C) and selectively removing the photosensitive resin composition layer containing the phosphor (A) by development to form a pattern; and
(IV) Process of Removing Organic Components by Firing
Method for producing a phosphor pattern, characterized in that it comprises each step of.
[2" claim-type="Currently amended] The phosphor pattern forming according to claim 1, wherein the process of (I) has a resin layer containing (C) fine particles on a (I '') support film, and a photosensitive resin composition layer containing (A) phosphor thereon. Preparation of phosphor pattern characterized in that the photosensitive element is laminated on the substrate having unevenness by contacting the above-mentioned layer (A) and forming the above-mentioned layers (A) and (C) on the uneven substrate Way.
[3" claim-type="Currently amended] The method of claim 1 or 2, wherein the steps (I) to (III) are repeated to form a multicolored pattern consisting of a photosensitive resin composition layer containing phosphors colored in red, green and blue, and then (IV) A process for producing a phosphor pattern, characterized in that to form a multi-color phosphor pattern by performing the process of.
[4" claim-type="Currently amended] The method for producing a phosphor pattern according to claim 1 or 2, wherein the process of (I) to (IV) is repeated to form a multicolor phosphor pattern which is colored red, green, and blue.
[5" claim-type="Currently amended] The photosensitive resin composition layer according to claim 1, 2, 3 or 4, wherein the photosensitive resin composition layer containing (A) phosphor is
(a) a film imparting polymer,
(b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group,
(c) a photoinitiator that generates free radicals by irradiation of actinic light, and
(d) phosphor
As containing
(C) The manufacturing method of fluorescent substance pattern characterized by the resin layer containing microparticles | fine-particles containing a thermoplastic resin.
[6" claim-type="Currently amended] A photosensitive element for forming a phosphor pattern, characterized by having a resin layer containing (C) fine particles and a photosensitive resin composition layer containing (A) phosphor on a support film.
[7" claim-type="Currently amended] The photosensitive resin composition layer according to claim 6, wherein the photosensitive resin composition layer containing (A) phosphor is
(a) a film imparting polymer,
(b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group,
(c) a photoinitiator that generates free radicals by irradiation of actinic light, and
(d) phosphor
As containing
(C) The photosensitive element for phosphor pattern formation characterized by the resin layer containing microparticles | fine-particles containing a thermoplastic resin.
[8" claim-type="Currently amended] The phosphor pattern manufactured by the manufacturing method of the phosphor pattern of Claim 1, 2, 3, 4 or 5.
[9" claim-type="Currently amended] A back plate for plasma display petals comprising the phosphor pattern of claim 8 on a substrate for a plasma display panel.

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引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
1997-12-09|Priority to JP33919597

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1997-12-09|Priority to JP339195/1997

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1998-12-08|Application filed by 와까바야시 구니히꾀, 히따찌 케미칼 컴퍼니, 리미티드

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1999-07-26|Publication of KR19990062901A

优先权:

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申请号 | 申请日 | 专利标题

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JP33919597|1997-12-09|

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JP339195/1997|1997-12-09|