JPH11352678A - Pattern forming method of light opaque material and power used for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a pattern of >=2 kinds of light opaque materials on the same substrate, which enables to precisely adjust the thickness of the pattern to a desired level and to sufficiently uniformalize the thickness. SOLUTION: The pattern of the light opaque material is formed by irradiating a photosensitive composition layer on the substrate, which changes the adhesivity by the irradiation of active ray, with the active ray, applying a polymer particle granulated by suspension polymerization, emulsion polymerization or kneading to pulverize and containing the light opaque material on the adhesive region of the surface to selectively stick the particle, successively fixing the sticking polymer particle with the photosensitive composition layer to the substrate by heating the photosensitive composition layer and successively repeating the processes to form the pattern composed of >=2 kinds of the light opaque materials and heating at 350-600 deg.C to melt and fire.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming two or more kinds of patterns of a light-impermeable material by the action of actinic rays, and more particularly to a pattern of two or more colors of phosphor pigments and a black matrix in a plasma display. Patterns, metal wiring circuits connecting the light emitting elements forming each pixel,
The present invention relates to a method for forming an insulating portion pattern and the like.

[0002]

2. Description of the Related Art A plasma display (hereinafter abbreviated as "PDP") is a display that excites and emits a phosphor with ultraviolet rays generated by gas discharge. A typical panel for a PDP has a structure as shown in FIG. 1, and a phosphor is formed inside a partition wall called a rib, and a phosphor layer has a thickness of 10 μm.
Since a film thickness of several tens of microns is required, a method of printing and forming a predetermined position by a silk screen printing method has been conventionally used. In FIG. 1, 1 is a surface glass substrate, 2 is a display electrode (transparent electrode), 3 is a bus electrode,
4 is a partition (rib), 5 is a back glass substrate, 6 is a dielectric layer, 7 is a protective layer (MgO), 8 is an address electrode, 9 is a phosphor (red), 10 is a phosphor (green), and 11 is a phosphor. Phosphor (blue)
And one pixel is formed by red, green, and blue phosphors.

The phosphor layer is formed by a silk screen printing method. The height of the rib is around 200 microns, and the rib must be printed with a uniform thickness on the side wall and the bottom of the rib. Therefore, the allowable range of physical properties required for the phosphor ink used in this printing is narrow, and the range of usable conditions is narrow. Also, silkscreens stretch and deform when squeezed with a skier. Repeated squeezing reduces the restoring force and exceeds the limits of elongation and deformation, so that the service life of the silk screen is not long. High-definition (miniaturized pixels) and large-sized screens require more precise screens and increase the amount of elongation and deformation, thus shortening the life of silk screens and at the same time satisfying the required accuracy. It is easy for situations where things cannot be done. One of the targets of the plasma display is a 40-inch class high-vision display. The enlargement and high definition of the display make it more difficult to print the phosphor on a silk screen.

A photolithography method (photolithography method) is well known as a highly accurate pattern forming method. However, since a phosphor is a pigment that does not transmit light and a required film thickness is as large as about 20 μm, It is extremely difficult to form a pattern with light from a photosensitive composition containing a phosphor. In addition, as can be seen from FIG. 1, the shape of the cell has a depth and width of 150 to 200 microns, and in a phosphor pattern which is desired to be formed with a uniform film thickness on the rib side wall and the cell bottom surface, It is difficult to meet this demand by the conventional photolithography method in which the intensity of light irradiated on the side wall and the bottom surface is different.

For example, Japanese Patent Application Laid-Open No. 63-309916 discloses a method of forming a black pattern by using a photosensitive material in which carbon black is mixed. Can be formed. However, it is hardened by light only in the vicinity of the surface of the film, and since the light hardly reaches the bottom of the film, the condition range in which the pattern can be formed is narrow, and it is difficult to apply it to a practical surface. . In particular, since the required film thickness of the PDP phosphor pattern is about 20 microns, it is difficult to form a pattern by this method.

JP-B-37-3193 and JP-B-49-7750 disclose a method in which a pigment or particle is sprinkled on an adhesive pattern and the pigment or particle is adhered to the adhesive region. A method for forming a pattern is disclosed. Japanese Patent Publication No. 37-3193 discloses a phosphor image forming method in which a layer of a photopolymerizable composition is applied to the surface of a support, exposed through a mask, and a zinc cadmium sulfide phosphor is dispersed. . However, these methods have an advantage that a light-opaque material can be used because pigments and particles are attached after exposure, but the thickness of a pattern layer formed of pigments and particles to be formed cannot be freely controlled. The point has not been solved, and no method for forming two or more types of patterns is disclosed.

[0007] Japanese Patent Publication No. 49-7750 discloses "stain".
In order to avoid the attachment of the pigment to the non-image area expressed as, the method of adjusting the pigment particle diameter to the optimum range is disclosed, and a `` resin matrix '' containing uniformly dispersed pigment particles is disclosed. ing. However, at present, a technique for controlling the thickness of a pattern of a light-impermeable material such as a phosphor has not yet been realized.

As a method for solving the drawbacks of the method for forming a pattern of a light-impermeable material, one of the present inventors has previously described, "After irradiating a photosensitive composition layer which loses tackiness by irradiation with active light, By adhering particles containing the light-impermeable material to the viscous region on the surface thereof, and repeating the operation of fixing the particles to the substrate together with the photosensitive composition by heating, it is composed of two or more kinds of light-impermeable materials. A method for forming a pattern was devised and filed as Japanese Patent Application No. 8-330918. This method can adjust the thickness of the light-impermeable particles and can also improve the uniformity of the thickness. However, the thickness of the pattern made of the light-impermeable material necessary for a plasma display or the like is appropriate. Since uniformity is an important factor influencing the performance of a display, further improvement is desired in this regard.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method disclosed in Japanese Patent Application No. Hei 8-330918, which claims that "a pattern made of two or more types of light-impermeable materials can be formed. A method for forming a pattern of a light-impermeable material that can also prevent movement or peeling of the formed pattern "is specifically aimed at forming a pattern composed of two or more kinds of light-impermeable materials. It is therefore an object of the present invention to provide a method for forming a pattern of a light-impermeable material that can accurately adjust the thickness of a pattern to a desired level and can make the thickness sufficiently uniform.

[0010]

SUMMARY OF THE INVENTION The present inventors have thought that the object of the present invention is to control the size of particles containing a light-impermeable material and to make them uniform are key to achieving the object. As a result of intensive research, the present invention has been achieved. That is, the present invention has been achieved by the following constitutions.

1. Forming a photosensitive composition layer that changes the adhesiveness by irradiation with actinic light on the substrate, irradiating the photosensitive composition layer with actinic light through a mask, a suspension polymerization method,
Emulsion polymerization or kneading and pulverization, and polymer particles containing a light-impermeable material are applied to the surface of the composition layer to selectively adhere the particles to the tacky region,
Next, the excess polymer particles that did not adhere and the polymer particles present in the non-tacky region were removed, and then the photosensitive composition layer was heated or irradiated with active light to remove the adhered polymer particles from the photosensitive composition. By sequentially repeating a series of steps of fixing the substrate together with the material layer, a pattern made of two or more types of light-impermeable materials is formed.
A method for forming a pattern of a light-impermeable material, wherein the pattern is formed by heating to 50 to 600 ° C., melting and baking to form a pattern of the light-impermeable material.

2. 2. The method for forming a pattern of a light impermeable material as described in 1 above, wherein the weight average particle size of the polymer particles containing the light impermeable material is 3 to 100 microns.

3. 3. The method for forming a pattern of a light impermeable material according to the above 1 or 2, wherein the light impermeable material is at least one material selected from a phosphor, a pigment, a metal powder, and a metal oxide powder. .

4. The method for forming a pattern of a light-opaque material according to any one of the above items 1 to 3, wherein the weight ratio of the light-opaque material to the polymer in the polymer particles is 0.04 to 9.0.

[0015] 5. 5. The method for forming a pattern of a light-impermeable material according to any one of the above items 1 to 4, wherein the change in the adhesiveness of the photosensitive composition layer due to irradiation with actinic rays is an increase in the adhesiveness.

6. 6. The method for forming a pattern of a light-impermeable material according to any one of the above items 1 to 5, wherein the change in the adhesiveness of the photosensitive composition layer due to irradiation with actinic rays is a decrease in the adhesiveness.

[7] In the pattern formation of polymer particles that are granulated by a suspension polymerization method, an emulsion polymerization method or a kneading and pulverizing method, and that contain a light-impermeable material, the particles selectively adhered to the tacky region are heated to form a photosensitive layer. Wherein the heating for fixing the composition layer to the substrate together with the composition layer is performed by a heat treatment at 80 to 300 ° C.
5. The pattern forming method for a light-impermeable material according to any one of the above items 5.

[8] Form a photosensitive composition layer that loses its tackiness by irradiating with actinic light on the substrate, irradiate this photosensitive composition layer with actinic light through a mask, and suspend, polymerize, or knead and pulverize the surface. Polymer particles that are granulated by the method and contain a light-opaque material to selectively adhere the particles to the sticky areas, and then to the excess non-adhered particles and to the non-sticky areas By removing the particles to be applied, by subsequently irradiating the photosensitive composition layer with actinic rays, a series of steps of fixing the attached particles to the substrate together with the photosensitive composition layer, by sequentially repeating,
Forming a pattern composed of two or more light-opaque materials,
A method for forming a pattern of a light impermeable material, comprising heating the composition to 350 to 600 ° C. to burn and burn off the photosensitive composition and the binder to form a pattern of the light impermeable material.

9. At least a light-opaque material, for forming a pattern of a light-opaque material for use in the above 1 to 8 obtained by suspension polymerization of a dispersion containing a light or heat polymerizable monomer and a polymerization initiator. Granules.

[10] A granulated product for pattern formation of a light-impermeable material for use in the above 1 to 8, which is obtained by melt-kneading and pulverizing a mixture containing at least a light-impermeable material and a thermoplastic polymer.

As described at the beginning of the prior art, in manufacturing a display device such as a PDP,
It is necessary to form two or more types of light-opaque material patterns on the same substrate. In this type of a plurality of light-opaque material pattern forming methods, each light-opaque material pattern is formed. When the photosensitive composition is burned and burned by heating each time, the pattern of the light-impermeable material already formed burns and burns the photosensitive composition when forming the second and subsequent patterns. For this reason, the conventional method often fails to obtain satisfactory pattern accuracy due to deformation, movement, or peeling due to heating. In particular, the pattern formed in the first stage has a problem that the number of times of exposure to heating increases as the pattern formation process of the second and third stages is performed, and the pattern is deformed and peeled off. Also, as described above,
In a method of forming a pattern of at least one kind of light impermeable material,
Heating at a high temperature for each pattern involves complicated operations and increases running costs.

[0022] One of the present inventors has previously filed a Japanese Patent Application No. Hei 8-
No. 330918 discloses that "a photosensitive composition layer that loses tackiness by irradiation with actinic light is formed on a substrate, and the photosensitive composition layer is irradiated with actinic light through a mask, and the surface thereof is coated with a light-impermeable material. After applying particles containing a binder to selectively adhere the particles to the tacky areas (non-exposed areas), excess particles that did not adhere and particles present in the non-sticky areas were removed. Then, by heating, a step of fixing the adhered particles to the substrate together with the photosensitive composition layer is sequentially repeated to form a pattern made of two or more types of light-impermeable materials. A method of forming a pattern of a light-opaque material by heating to 350 to 600 ° C. to burn and burn off the photosensitive composition and the binder. By this method, In the above method of forming a pattern of a light impermeable material, movement, deformation or peeling of the pattern can be prevented, and a pattern of two or more light impermeable materials can be formed with a simple operation at a low running cost. It became.

The present invention is a further improvement of this method. However, the novel invention of the present invention and the effects thereof with respect to Japanese Patent Application No. 8-330918 are the following two points. First, the “particles containing a light-impermeable material and a binder” in the method of the above application are referred to as “polymer particles containing a light-impermeable material granulated by suspension polymerization” (hereinafter “polymer particles”). ), The thickness of the pattern could be increased, and the thickness and dimensions could be adjusted with higher accuracy. Secondly, in addition to the "process of forming a photosensitive composition layer that" loses "the adhesiveness by irradiation with actinic rays on the substrate" in the method of the above-mentioned application, "the tackiness is increased by the irradiation with actinic rays." The present inventors have found that a “process of forming a photosensitive composition layer” can also be used, and have made it possible to broaden the application range of the pattern forming method.

[0024]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. In the present invention, in forming each pattern of two or more kinds of polymer particles, as a means for applying the polymer particles selectively adhered to the adhesive region to the substrate together with the photosensitive composition layer, heating or active Light irradiation is performed. Further, the polymer particles attached by heating may be softened or melted, and the surface of the attached particles may be flattened. Heating for this purpose is preferable in that it can also serve as heating for fixing.

The heating temperature for fixing the polymer particles selectively adhered to the adhesive region together with the photosensitive composition layer to the substrate is preferably from 80 to 350 ° C., more preferably from 150 to 350 ° C. The temperature is 300 ° C, more preferably 200 to 250 ° C. 80-350 ° C
Is preferably 5 to 60 minutes, more preferably 10 to 30 minutes. Thereby, the particles can be more firmly fixed to the substrate together with the photosensitive composition layer, and the flattening of the pattern surface becomes better.

As a means for fixing the substrate to the substrate in each of the above steps, irradiation with actinic rays may be performed instead of heating. In this case, the irradiation amount of the actinic ray (ultraviolet light, an ultra-high pressure mercury lamp is mainly used as a light source) is required to be 100 mJ / cm ² or more, and a higher irradiation amount is preferable. Although there is no upper limit of the irradiation amount, the optimum range is narrowed down naturally from the economic aspect (power) and throughput (irradiation time). Since the irradiation is not a pattern exposure, the requirements such as the distribution of the irradiation light amount are not strict. Therefore, a large amount of irradiation can be given in a short time by irradiating the light source close to the light source, so that the condition of about 500 to 1500 mJ / cm ² can be easily selected.

In the present invention, the fixation to the substrate together with the photosensitive composition layer refers to a process such as a photocrosslinking reaction in which the tackiness of the tacky region is lost by heat or light, and a process such as thermal melting. It may be a step, in the former, the particles adhering to the adhesive composition are fixed together with the loss of tackiness, even in the latter, while the particles are fixed by heat attraction between the particles and the photosensitive composition layer Loses stickiness. The flattening of the pattern surface is based on the fact that the polymer particles are softened (or melted) by heating, and the particles collapse, flow and spread.
Burnout is the burning of organic matter, leaving only inorganic matter.

When polymer particles containing a light-impermeable material are adhered to the adhesive surface of the photosensitive composition layer, the particles are arranged only on the surface. Is usually difficult. In the present invention,
By adjusting the particle size of the polymer particles containing the light-impermeable material to the size necessary to obtain a desired film thickness pattern by adjusting the conditions of the manufacturing method described below, such as prepolymerization treatment and stress application conditions, A pattern having an appropriate film thickness can be obtained.

The larger the weight ratio of the light-impermeable material to the polymer in the polymer particles, the smaller the amount of the organic matter disappeared, which is advantageous because the thickness of the light-impermeable material can be effectively increased. The ratio varies depending on the type of the target light-impermeable material, that is, the phosphor as the light emitting source of the PDP, the pigment for the black matrix, and other materials such as silver and glass, and is usually 0.5 to 5.0. is there.

Next, the present invention will be described in more detail. First, the photosensitive composition layer whose adhesiveness changes will be further described. When the photosensitive composition layer in the present invention is a composition layer which loses tackiness by irradiation with actinic rays, the composition itself has tackiness and is a material which loses tackiness by irradiation with actinic rays. For example, US Pat.
The photopolymerizable composition disclosed in the specification of Japanese Patent No. 9,367 can be used.

The photopolymerizable composition used in such a photosensitive composition layer comprises an addition polymerizable unsaturated monomer, a photopolymerization initiator and a binder. The adherent polymerizable unsaturated monomer is a compound having at least one ethylenically unsaturated group capable of addition polymerization and having a boiling point of 100 ° C. or more at normal pressure. Specifically, monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri ( (Meth) acrylate, neopentyl glycol (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyl) Polyfunctional such as oxyprooil) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane After adding ethylene oxide or propylene oxide to alcohol (meth) those acrylated, JP-B-48-4
No. 1708, Japanese Patent Publication No. 50-6034, Japanese Patent Application Laid-Open No. 51-3
Urethane acrylates described in JP-A-7193, JP-A-48-64183, JP-B-49-64183;
Polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-A-43191 and JP-B-52-30490, and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid.

The polymerizable monomer contained in the composition that loses the tackiness due to the exposure is represented by the following general formula (1):
At least one monomer selected from the monomer group represented by the formula (1) can also be used effectively.

Formula (1) H ₂ C ＝ C (R) —COO— (C ₂ H ₄ O) _m —CO—Y—COOZ In the general formula (1), R represents a hydrogen atom or a group having 1 to 1 carbon atoms.
4 represents an alkyl group, Y represents a phenylene group or a cycloalkylene group, Z represents a hydrogen atom, and has 1 to 3 carbon atoms.
Alkyl or _{- (C 2 H 4 O)} n -H ( wherein, n
Is an integer of 1 to 9), and m is
It is an integer of 1 to 9. Specific examples when R in the general formula (1) is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and a sec-butyl group. be able to. Specific examples of preferred R are a hydrogen atom or a methyl group.

Specific examples of Y include a phenylene group and a cycloalkylene group. The cycloalkylene group preferably has 5 to 6 carbon atoms, and specific examples thereof include cyclopentene and cyclohexylene. Can be. Preferred specific examples of Y are phenylene and cyclohexylene. Further, specific examples when Z in the general formula (1) is an alkyl group include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group.
Is the number of repeating ethylene oxide groups, and 1 to 9
, Preferably an integer of 1-4.

Specific examples of the monomer represented by the general formula (1) are shown below, but embodiments of the present invention are not limited thereto. 2-acryloyloxyethyl phthalic acid, 2-
Acryloyloxyethyl-1-methylphthalate, 2
-Acryloyloxyethyl-1-ethylphthalate,
2-acryloyloxyethyl-1-propylphthalate, 2-acryloyldioxyethylphthalic acid, 2-acryloyltrioxyethylphthalic acid, 2-acryloyltetraoxyethylphthalic acid, 2-acryloylpentaoxyethylphthalic acid, 2-acryloyl Hexaoxyethylphthalic acid, 2-acryloylheptaoxyethylphthalic acid, 2-acryloyloctaoxyethylphthalic acid, 2-acryloyl nanooxyethylphthalic acid,

2-acryloyloxyethyl-1-hydroxyethyl phthalate, 2-acryloyloxyethyl-1-dihydroxyethyl phthalate, 2-acryloyloxyethyl-1-trihydroxyethyl phthalate, 2-acryloyloxyethyl-1-tetrahydroxy Ethyl phthalate, 2-acryloyloxyethyl-1-pentahydroxyethyl phthalate, 2-acryloyloxyethyl-1-hexahydroxyethyl phthalate, 2-acryloyloxyethyl-1-heptahydroxyethyl phthalate, 2-acryloyloxyethyl-1 -Octahydroxyethyl phthalate, 2-acryloyloxyethyl-1-nanohydroxyethyl phthalate, 2-acryloyldioxyethyl-1-dihydroxyethyl phthalate Rate, 2-acryloyl trioxyethyl-1-tri-hydroxyethyl phthalate, 2-
Acryloyltetraoxyethyl-1-tetrahydroxyethylphthalate, 2-acryloylpentaoxyethyl-1-pentahydroxyethylphthalate, 2-acryloylhexaoxyethyl-1-hexahydroxyethylphthalate, 2-acryloylheptaoxyethyl- 1-heptahydroxyethyl phthalate, 2-acryloyl octaoxyethyl-1-octahydroxyethyl phthalate, 2-acryloyl nanooxyethyl-
1-nanohydroxyethyl phthalate, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxyethyl-1-methyl hydrogen phthalate, 2-acryloyloxyethyl-1-ethyl hydrogen phthalate, 2-acryloyloxyethyl-
1-propyl hydrogen phthalate,

2-acryloyldioxyethyl hydrogen phthalate, 2-acryloyl trioxyethyl hydrogen phthalate, 2-acryloyl tetraoxyethyl hydrogen phthalate, 2-acryloyl pentaoxyethyl hydrogen phthalate, 2-acryloyl Hexaoxyethyl hydrogen phthalate, 2-
Acryloyl heptaoxyethyl hydrogen phthalate, 2-acryloyl octaoxyethyl hydrogen phthalate, 2-acryloyl nanooxyethyl hydrocogen phthalate, 2-acryloyloxyethyl-1
-Hydroxyethyl hydrogen phthalate, 2-acryloyloxyethyl-1-dihydroxyethyl hydrogen phthalate, 2-acryloyloxyethyl-1-trihydroxyethyl hydrogen phthalate, 2-acryloyloxyethyl-1-tetrahydroxyethyl hydrogen phthalate 2-acryloyloxyethyl-1-pentahydroxyethyl hydrogen phthalate, 2-acryloyloxyethyl-1
-Hexahydroxyethyl hydrogen phthalate,
2-acryloyloxyethyl-1-heptahydroxyethyl hydrogen phthalate, 2-acryloyloxyethyl-1-octahydroxyethyl hydrogen phthalate, 2-acryloyloxyethyl-1-nanohydroxyethyl hydrogen phthalate, 2-acryloyldioxy Ethyl-1-dihydroxyethyl hydrogen phthalate, 2-acryloyltrioxyethyl-1-trihydroxyethyl hydrogen phthalate, 2-acryloyltetraoxyethyl-1-tetrahydroxyethyl hydrogen phthalate, 2-
Acryloyl pentaoxyethyl-1-pentahydroxyethyl hydrogen phthalate, 2-acryloylhexaoxyethyl-1-hexahydroxyethyl hydrogen phthalate, 2-acryloylheptaoxyethyl-1-heptahydroxyethyl hydrogen phthalate, 2-acryloyl octa Oxyethyl-1-
Octahydroxyethyl hydrogen phthalate, 2
-Acryloyl nanooxyethyl-1-nanohydroxyethyl hydrogen phthalate and the like.

Among the above specific examples, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hydrogen phthalic acid, 2-acryloyloxyethyl-1-hydroxyethyl phthalate, 2-acryloyloxyethyl-1-dihydroxyethyl Phthalate,
2-acryloyloxyethyl-1-trihydroxyethyl phthalate, 2-acryloyloxyethyl-1-
Hydroxyethyl hydrogen phthalate, 2-acryloyloxyethyl-1-dihydroxyethyl hydrogen phthalate, 2-acryloyloxyethyl-
1-trihydroxyethyl hydrogen phthalate can be mentioned as a preferred monomer.

The above monomers can be used alone or in combination of two or more. Further, those described as photocurable monomers and oligomers in the Adhesion Society of Japan, Vol. 20, No. 300-308, can also be used.

Since the monomer is liquid or waxy at room temperature, a coating film exhibiting tackiness is formed by an appropriate blending ratio with the binder. Preferably it is 40 to 100% by weight. When a film can be formed only with a monomer or oligomer, it is not necessary to use a binder. The above monomers or oligomers may be used alone or in combination of two or more.

As the photopolymerization initiator, US Pat.
Bicinal polyketo aldonyl compounds disclosed in US Pat. No. 67,660, US Pat. No. 2,367,661.
-Carbonyl compounds disclosed in U.S. Pat. No. 2,448,82 and U.S. Pat. No. 2,448,82.
No. 8, disclosed in U.S. Pat. No. 2,722,512.
-Aromatic acyloin compounds substituted with hydrocarbons, U.S. Pat. Nos. 3,046,127 and 2,951,75
No. 8 disclosed, polynuclear quinone compounds disclosed in US Pat. No. 3,549, and aromatic acyloin compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758. Quinone compounds, combinations of triallylimidazole dimer / p-aminophenyl ketone disclosed in U.S. Pat. No. 3,549,367, benzothiazole compounds / trihalo disclosed in Japanese Patent Publication No. 51-48516 Methyl-s-
A triazine compound, a photosensitive-s-triazine compound described in Japanese Patent Application No. 61-186238, a trihalomethyl-s-triazine compound disclosed in U.S. Pat. No. 4,239,850, Oxadiazole compounds described in U.S. Pat. No. 4,212,976, acetophenone-type compounds disclosed in U.S. Pat. No. 4,318,791, U.S. Pat. No. 3,926,643 The thioxanthone compound disclosed in the specification and the coumarin compound disclosed in U.S. Pat. No. 4,147,552 can be exemplified, but not limited thereto. The amount used is about 0.2 to 30% by weight relative to the monomer, more preferably 0.1 to 30%.
5-20% is suitable.

The binder is preferably a linear organic high molecular polymer compatible with the monomer and soluble in an organic solvent. As such a linear organic high molecular polymer, a polymer having a carboxylic acid in a side chain, for example,
JP-A-59-44615, JP-B-54-34327.
No., JP-B-58-12577, JP-B-54-2595
7, JP-A-59-53836, JP-A-59-710
No. 48, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. There is also an acidic cellulose derivative having a carboxylic acid in the side chain.

Further, a polymer obtained by adding an acid anhydride to a polymer having a hydroxyl group as a binder is also useful.
Among them, benzyl (meth) acrylate / (meth) acrylic acid copolymers and benzyl (meth) acrylate / (meth) acrylic acid / multi-component copolymers with other monomers are particularly preferable. In addition, polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful as the water-soluble polymer. Alcohol-soluble nylon to increase the strength of the cured film,
Acrylic acid ester polymer or copolymer or 2,2
Also useful are polyethers of -bis- (4-hydroxyphenyl) -propane and epichlorohydrin.

A thermal polymerization inhibitor may be added to the photosensitive composition for improving storage stability. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-
6-t-butylphenol), 2,2'-methylene (4
-Methyl-6-t-butylphenol), 2-mercaptobenzimidazole and the like are useful, and are usually added in an amount of about 500 to 2000 PPM to the monomer. Usually, an appropriate amount of a thermal polymerization inhibitor is added to commercially available monomers.

The photosensitive composition layer is formed on the substrate surface by using a solvent having low toxicity and good coating properties as required. Examples of the solvent used here include methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, and 3-methoxypropionate.
Alkoxypropionic acid esters such as ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester and 3-ethoxypropionic acid propyl ester, and alkoxy alcohols such as 2-methoxypropyl acetate, 2-ethoxypropyl acetate and 3-methoxybutyl acetate Esters, methyl lactate, lactate esters such as ethyl lactate, methyl ethyl ketone, cyclohexanone, ketones such as methylcyclohexanone,
In addition, gamma-butyrolactone, N-methylpyrrolidone, dimethyl sulfoxide and the like are useful.

Many of the monomers or oligomers in the photopolymerizable composition are liquid at room temperature. Therefore, when an appropriate mixing ratio with the binder is selected, the solvent shows adhesiveness even after the solvent is evaporated by drying. The coating film made of the photopolymerizable composition undergoes a polymerization and curing reaction upon irradiation with actinic light, and loses the stickiness due to the disappearance of the monomer or oligomer, so that the particles do not physically adhere. here,
The actinic ray is ultraviolet light, and an ultra-high pressure mercury lamp is mainly used as a light source. The irradiation amount of this actinic ray is 50 to 1000 mJ / cm ² , more preferably 100 to 60 mJ / cm ² .
The range is 0 mJ / cm ² . Is less than 50 mJ / cm ^2, stickiness occurs, reduces the working efficiency exceeds 1000 mJ / cm ^2, it is both unsuitable.

The present invention can also be applied to a case where the photosensitive composition layer is a composition layer which becomes sticky by irradiation with actinic rays. As a method of attaching a phosphor using a so-called photo-adhesive which generates tack when exposed to light,
A photo-adhesive composition containing a diazo compound as a main component is exemplified. The composition mainly composed of the photo-adhesive diazo compound is a double salt of the diazo compound and a metal halide such as zinc chloride, tin chloride or cadmium chloride or a non-metal fluoride such as borofluoric acid. Is a main component, and contains a polymer compound, a surfactant, and the like as additives. These are considered to exhibit tackiness because they release a deliquescent substance upon exposure.

As an example of the aromatic diazonium salt,
There are the following compounds. (I) Aromatic diazonium chloride / zinc chloride double salt
For example, 4-dimethylaminobenzenediazonium chloride
-(1) Zinc chloride double salt [(CH _Three)_TwoNC₆H_FourN_TwoCl / ZnC
l_Two], 4-diethylaminobenzenediazonium chloride
-(1) ・ Zinc chloride double salt, chloride 4- (N-ethyl-N
-Hydroxyethylamino) benzenediazonium-
(1) ・ Zinc chloride double salt, chloride anthraquinonediazoni
Um- (1) / Zinc chloride double salt, 2-methoxy-4 chloride
-Nitrobenzenediazonium- (1), zinc chloride double
Salt, 4-nitronaphthalenediazonium chloride- (1)
・ Zinc chloride double salt, 4-methoxybenzenediazoni chloride
Um- (1) / double zinc chloride, 2-methoxyben chloride
Zendiazonium- (1), double salt of zinc chloride, etc. (ii)
Aromatic diazonium tetrafluoroborate, for example
4-dimethylaminobenzenediazonium- (1) bor
Hydrofluoric acid, 4-diethylaminobenzenediazoni
Um- (1) borohydrofluoride, 4- (N-ethyl-
N-hydroxyamino) benzene- (1) fluorinated water
Citrate, 4-methoxybenzenediazonium- (1) e
Hydrofluoric acid, 2-methoxybenzenediazonium
-(1) borofluoride or the like, or (iii) aromatic di
Azonium acid sulfates such as 4-dimethylaminobenz
Nzendiazonium- (1) sulfate, 4-diethylamido
Nobenzenediazonium- (1) sulfate, 4- (phenyl
Ruamino) benzenediazonium- (1) sulfate etc.
Used.

Of course, two or more of these diazonium salts may be used as a mixture. The photo-adhesive photosensitive agent used in the present invention may be the aromatic diazonium salt alone, but for the purpose of improving applicability to a substrate, an organic polymer compound is added to the aromatic diazonium salt. 0.5 to 500% by weight, more preferably 1%
Desirably, it is contained in an amount of about 50% by weight. It is recognized that the coating property is improved by adding 0.5% by weight or more of the organic polymer compound, but a remarkable effect is observed when 1% by weight or more is added.

When the amount of the organic polymer compound is large, the photosensitivity is lowered. Therefore, the amount is preferably 500% by weight or less, more preferably 50% by weight or less. Examples of such organic polymer compounds include gum arabic, polyvinyl alcohol, polyacrylamide, poly (N-vinylpyrrolidone), acrylamide / diacetone acrylamide copolymer, methyl vinyl ether / maleic anhydride copolymer, alginic acid, and alginic acid. Water-soluble ones such as propylene glycol ester and hydroxyl methyl cellulose are preferred. Of course, two or more kinds can be used in combination.

The photo-adhesive photosensitive agent used in the present invention separates zinc chloride and the like by light irradiation, and absorbs moisture from the atmosphere because the photolysis products such as zinc chloride absorb moisture.
It becomes sticky to powder. A preferred embodiment of the present invention using the photo-adhesive composition is not limited to forming a pattern for a phosphor. When the pattern is formed using ceramic or colored low melting point glass frit powder, a projection image through a mask is projected on the photo-viscous layer photosensitive agent application surface in combination with the above-mentioned photo-adhesive photosensitive agent, and the projection is performed. Only the part is made adhesive and a colored frit corresponding to the mask pattern is sprayed. In addition, a metal pattern is formed using metal powder particles, and a colored pattern is formed using pigment. By repeating this operation for the polymer particles containing each light-opaque material, a pattern of two or more kinds of light-opaque materials can be formed.

After being divided into an adhesive area and a non-adhesive area by patterning and irradiating an actinic ray through a mask, particles containing a light-impermeable material such as a phosphor pigment are sprinkled. Attaches to the area. Alternatively, instead of sprinkling the particles, they may be sprayed or rubbed. After the particles containing the light-impermeable material are sprinkled, the light-impermeable material pattern is formed by sucking, blowing, or brushing off the particles.

The actinic ray is ultraviolet light, and an ultra-high pressure mercury lamp is mainly used as a light source. The conditions are the same as in the case where the photosensitive composition layer is composed of the above-mentioned photopolymerizable composition whose adhesiveness is reduced by irradiation with actinic rays.

In the present invention, a glass is usually used as a substrate (in some cases, a support), and a glass substrate having a partition wall (rib) formed on its surface when a phosphor pattern such as a plasma display is formed. It is. As a coating method for forming the photosensitive composition layer on the surface of the substrate (and / or the support), a spinner, a roll coater, a bar coater, a curtain coater, a spray or a shower, or the like is used. In order to leave a required amount of the coating film uniformly on the substrate surface and the rib side wall, it is desirable to remove an excess photosensitive solution after coating. How to remove
A method of sucking, blowing, rotating and shaking off the substrate, or a method of turning the substrate upside down or leaning on the substrate and flowing the substrate may be used.

Next, in the present invention, in order to improve the accuracy such as the thickness and uniformity of the pattern of the light impermeable material,
Particularly effective polymer particles will be described. The polymer particles are produced by a suspension polymerization method, an emulsion polymerization method or a kneading-pulverization method described below. In the suspension polymerization method, a monomer composition (oil phase) comprising at least a polymerizable monomer and a light-impermeable material is granulated to a desired particle size in an aqueous medium using a suitable stirrer ( (Granulation step), and a polymerizable monomer is polymerized by a radical generated when a previously added polymerization initiator or a newly added polymerization initiator is decomposed by heat to form a polymer (polymerization step). ) To produce polymer particles containing a light-impermeable material. Since the shape of the polymer particles obtained by the suspension polymerization method is spherical, the polymer particles have characteristics such as excellent fluidity.

It is desirable to use a suspension stabilizer in the aqueous phase used in the suspension polymerization method of the present invention in order to prevent coalescence of the granulated particles. As the suspension stabilizer used in the present invention, a water-soluble polymer having a hydrophilic group and a hydrophobic group in its molecule, for example, polyvinyl alcohol, casein, gelatin, methylcellulose, methylhydroxypropylcellulose, cellulose derivatives such as ethylcellulose , Starch and derivatives thereof, poly (meth) acrylic acid and salts thereof, and solid fine powder. Examples of the solid fine powder include tertiary calcium phosphate, calcium carbonate, metal fine powder such as copper and iron, silica, and alumina. Among such suspension stabilizers, the solid fine powder is preferred because it is insoluble in water and relatively stable when heated. It is preferable because polymer particles including light-impermeable particles having a uniform particle size can be obtained irrespective of the type, amount, and properties of the monomer, colorant, magnetic powder, and the like. These suspension stabilizers may be used alone or in combination of two or more. The addition amount of the suspension stabilizer in the aqueous phase is preferably 0.05 to 20 parts by weight based on 100 parts by weight of water in the aqueous phase. If the amount is less than 0.05 parts by weight, the suspension becomes unstable. On the other hand, if it is more than 20 parts by weight, the viscosity of the aqueous phase increases, and it is difficult to obtain polymer particles having a uniform particle size. The suspension stabilizer composed of tricalcium phosphate and calcium carbonate can be removed from the surface of the polymer particles by washing with an acid after obtaining the polymer particles in the aqueous phase.

In order to stabilize the monomer composition suspended in the aqueous phase and obtain uniform polymer particles, a surfactant such as sodium dodecylsulfonate or sodium dodecylbenzenesulfonate is used as a suspending aid. Is preferably added to the aqueous phase. The addition amount of the suspension aid is preferably 0.005 to 0.05 parts by weight based on 100 parts by weight of the aqueous phase.

Next, the oil phase will be described. The oil phase constituting the present invention is obtained by dispersing at least a polymerizable monomer, light-impermeable particles and a polymerization initiator. As the monomer used in the present invention, for example, polymerizable monomers as described below can be used. That is, examples of the polymerizable monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methylstyrene.
Methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n -Styrene such as hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene and the like: ethylene unsaturated monoolefins such as ethylene, propylene, butylene, isobutylene and the like: chloride Vinyl, vinylidene chloride, vinyl chloride, vinyl fluoride,
Vinyl halides such as vinyl acetate, vinyl propionate, vinyl benzoate, and the like; organic acid vinyl esters such as methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, and n-methacrylate -Octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate,
Methacrylic acid and its derivatives: acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, acrylic Acrylic acid and its derivatives such as stearyl acid, 2-chloroethyl acrylate and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone , Etc .; vinyl ketones; N-vinyl pyrrole, N-vinyl carbazole, N
N-vinyl compounds such as vinylindole and N-vinylpyrrolidone: vinylnaphthalenes: acrylonitrile,
Polymerizable monomers such as methacrylonitrile and acrylamide can be mentioned, and they may be used alone or as a mixture depending on the purpose.

The polymerization initiator used in the present invention is preferably soluble in a polymerizable monomer. Examples of such a polymerization initiator include 2,2′-azobisvaleronitrile, 2,2′-azobisibbutyronitrile,
2'-azobis- (2,4-dimethoxypareronitrile), 2,2'-azobis-4-methoxy-2,4-dimethylpareronitrile, other azo or diazo polymerization initiators: benzoyl peroxide , Methyl ethyl ketone peroxide, isopropyl peroxycarbonate, and other peroxide-based polymerization initiators. In addition, benzoyl peroxide-based polymerization initiators decompose to produce carboxylic acid such as benzoic acid as a by-product, which may have an adverse effect on the preservability of polymer particles, and also has the disadvantage of generating an aromatic odor. Therefore, it is preferable to use an azo-based polymerization initiator. In the present invention, two or more of the above-mentioned polymerization initiators may be used in combination with various compositions for the purpose of controlling the molecular weight and the molecular weight distribution or controlling the reaction time. Further, a water-soluble initiator such as ammonium persulfate and potassium persulfate may be used in combination, if necessary. The amount of the polymerization initiator to be used is generally 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the polymerizable monomer. If the amount of the polymerization initiator is less than 0.1 part by weight, the polymerization time may be prolonged and the molecular weight of the polymer particles may be too high. On the other hand, if the polymerization initiator exceeds 20 parts by weight, the molecular weight of the polymer particles may be too low, which is not preferable. Furthermore, in the oil phase in the present invention, in order to improve blocking resistance in the polymer particles,
There is no problem even if a crosslinking agent for the polymer of the polymerizable monomer is added. As such a crosslinking agent, a crosslinking agent such as divinylbenzene can be added to the monomer composition.

The light-impermeable material in the present invention is a light-impermeable or light-impermeable material such as a phosphor. For example, an ultraviolet-excited phosphor, a metal or a transition metal, a powder or fine particles of an alkaline earth metal or an oxide thereof, or the like is a light-impermeable material that is the object of the present invention. Phosphors described below, metal powders such as gold, silver, platinum, aluminum, copper, nickel and zinc, or ITO (indium tin oxide), alumina, barium oxide, titanium oxide, magnesium oxide, lead oxide,
Metal oxides such as zirconium oxide and mixtures thereof, for example, low-melting glass, sulfide pigments exemplified by zinc sulfide, and the like are light-impermeable or light-impermeable materials used in the construction of this type of display element. . In addition, the light-opaque pattern forming method of the present invention can be made by a photolithography method, such as forming a metal wiring circuit pattern and forming an insulating portion pattern as in the above-described examples in addition to the phosphor pattern. Suitable for pattern formation of difficult materials.

As the ultraviolet-excited phosphor, for example, red = Y ₂ O ₃ : Eu, Y ₂ SiO ₅ : Eu, Y ₂ Al
_{5 O 12: Eu, YVO 4} : Eu, (Y, Gd) BO 3: E
u, YBO ₃ : Eu, Zn ₃ (PO ₄ ) ₂ : Eu, GdB
O ₃ : Eu, ScBO ₃ : Eu, LuBO ₃ : Eu Green = Zn ₂ SiO ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, B
aMgAl ₁₄ O ₂₃ : Mn, SrAl ₁₂ O ₁₉ : Mn, Z
nAl ₁₂ O ₁₉ : Mn, CaAl ₁₂ O ₁₉ : Mn Blue = B
aMgAl ₁₄ O ₂₃ : Eu, BaMgAl ₁₆ O ₂₇ : Eu,
Y ₂ SiO ₅ : Ce and the like can be mentioned.

The present invention can also be used for patterning pigments and glass. Preferred pigments include metal oxide pigments such as lead oxide, zirconium oxide, titanium oxide, iron oxide, zinc oxide, chromium oxide, and alumina; sulfide pigments exemplified by zinc sulfide; and other carbonates and silicates. be able to. The size of these pigments differs depending on the type, but in any case, it can be used in an appropriate size that is usually used, and is generally 10 μm or less, preferably 8 μm or less, more preferably 4.
5 microns or less. If it is 10 microns or more, there is a problem in dispersibility of the pigment in the resin particles. These pigments are used singly or in combination of two or more, depending on the type. These pigments are used in a weight ratio of 0.04 to 9.
0, particularly preferably 0.1 to 7.0. 0.1
If it is less than 1, it becomes difficult to form a uniform pattern in the image area. On the other hand, if it exceeds 9.0, it may be difficult to completely enclose the pigment in the resin particles, which may cause inconvenience.

Regardless of the type of pigment used, it is desirable that the particle size is fine, in order to avoid light scattering and ensure flatness, and is 0.4 μm or less, especially 0.2 μm.
It is preferably not more than μm. In particular, when the particles are coarse, the pigment can be pulverized in advance and finely divided. Such fine pulverization is preferably performed by a method using a wet pulverizer using a medium, but is not necessarily limited to such a device. The means for dispersing the inorganic material in the polymerizable monomer, various methods can be applied,
In addition to the above wet pulverizer, for example, a rotor / stator type disperser such as a TK homomixer (manufactured by Tokushu Kika Co., Ltd.), an ultrasonic disperser, or the like can be used. Furthermore, by using a dispersant according to the properties of the inorganic material and the polymerizable monomer, it becomes possible to uniformly disperse the inorganic material in the resin particles, which contributes to flattening after sintering. Becomes possible. As such a dispersant, a titanate-based coupling agent, a silane-based coupling agent, an aluminum-based coupling agent, or the like can be used, but a dispersant that can be used for dispersing an inorganic substance in an organic material is used. The coupling agent is not necessarily limited to the above-described coupling agent.

The method for producing the polymer particles of the present invention using the suspension polymerization method will be described in more detail with reference to the drawings. FIG. 2 is an example of an apparatus used to carry out the present invention. In the figure, reference numeral 21 denotes a continuous phase tank, and 22 denotes a dispersion phase tank, which are connected to a disperser 25 having a stirrer as a device for applying a shearing force through channels 28 and 29, respectively. Reference numeral 23 denotes a reaction tank provided with a condenser 26 and a heating jacket 27, and is connected to the disperser 25 by a flow path 30. 24 is a metering pump. In order to carry out the present invention, an aqueous phase component composed of an aqueous medium is held in an aqueous phase tank 1,
The oil phase component composed of the monomer composition is held in the dispersion phase tank 22. The oil phase component is supplied simultaneously and continuously to the vicinity of the shearing region of the disperser 25 having the stirrer by driving the metering pumps 24, 24 provided in the independent flow paths 28 and 29. Each component supplied in the vicinity of the shearing region of the dispersing machine is dispersed by the shearing force of the stirrer to form a dispersion composed of a dispersed phase and a continuous phase. The formed dispersion is
It is sent to the reaction tank 23 via the flow path 30, and suspension polymerization is performed by a usual method.

After completion of the polymerization, the polymer particles of the present invention can be obtained by dehydrating by a method such as centrifugation and drying the obtained polymer particles. Incidentally, the granulation method is suitable for controlling the particle size distribution using the above method, but is not limited thereto, for example,
A commercially available dispersing device such as a TK homomixer and a TK homogenizer (both manufactured by Tokushu Kika Co., Ltd.) may be used. Further, in the present invention, other various polymerization methods such as an emulsion polymerization method, a dispersion polymerization method, and a seed polymerization method can be applied in addition to the suspension polymerization method.

In the present invention, the dispersion component and the continuous phase component, which are preliminarily polymerized by the bulk polymerization method and adjusted to have the desired viscoelastic properties, are supplied at a predetermined flow rate to a dispersing machine equipped with a stirrer. Since they are continuously supplied at the same time, the dispersion conditions such as the amount, size, or phase ratio of the droplets passing through the shearing region are completely controlled, and the dispersed phase and the continuous phase are always kept under constant conditions. Shear forces will result, and a dispersion with a narrow particle size distribution will be obtained.

In the present invention, in addition to the above-mentioned method for producing polymer particles by the suspension polymerization method, a method for producing polymer particles by the kneading and pulverizing method can be applied. The details will be described below. A mixture in which at least a polymer and an inorganic material having thermoplasticity are dispersed by a dry stirrer represented by a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) is hot-melt-kneaded with an extruder. The kneading temperature is usually 120 to 180 ° C. at the material temperature of the hot melt kneaded product,
It is appropriately set according to the softening point of the polymer. The hot melt kneaded product obtained by the above operation is cooled and solidified, coarsely pulverized to an average particle size of 2 to 3 mm, and finely pulverized using a pulverizer such as a jet mill. Next, when adjusting to a desired particle size distribution, the particles can be classified using an airflow classifier or the like. Here, as the polymer having thermoplasticity, for example, an acrylic polymer, a polyolefin such as a styrene-based polymer, a polyester-based polymer, a homopolymer or a copolymer mainly containing an epoxy-based polymer, and the like, have thermoplasticity. Any of these can be used alone or in combination of two or more. Also, for the purpose of controlling the melt diffusibility during pattern formation,
A polymer having a relatively low viscosity such as wax may be used in combination.

The particle size of the polymer particles of the present invention obtained by the above polymerization method or kneading method is usually from 1 to 1000 μm.
m is preferred, and more preferably 10 to 200 μm. The thickness of the pattern forming layer can be adjusted to a preferable range, usually 10 to 200 μm, by changing the size of the particles containing the light-impermeable material (that is, polymer particles). If the method of adjusting the particle size of the polymer particles is a suspension polymerization method, the flow ratio and flow rate of the oil phase and the aqueous phase to the disperser,
Alternatively, it is determined by the strength of mechanical stress on the object to be dispersed by the dispersing machine. On the other hand, in the kneading and pulverizing method, it is determined by an impact force in a pulverizer. Furthermore, since the classification means described in the kneading and pulverizing method can be applied in common to any of the production methods, the above-mentioned desirable particle size of 1
It can be easily adjusted to 0 to 200 μm.

When mixing and dispersing the light-impermeable material and the binder, for example, if glass is mixed, the glass is melted at the same time as the organic component is burned off, and the light-impermeable due to the melted glass. The material is fixed to the substrate. The light-opaque material is retained even without the fixing agent, but the light-opaque material is more firmly fixed to the substrate when the fixing agent is present.
When the light-impermeable material emits light by irradiation with ultraviolet rays such as a phosphor, the fixing agent is preferably a material that does not hinder the luminous efficiency.

In the case where the light-impermeable material according to one embodiment of the present invention is a phosphor, in the case of color display, the formation of a phosphor pattern of red (R), green (G), and blue (B) is performed. Will be needed. In this case, the above-mentioned step, that is, (1) a step of applying a photosensitive composition coating liquid on the substrate surface,
(2) drying, (3) exposing, (4) attaching particles containing a phosphor and an adhesive, (5) removing excess particles, (6) heating or exposure and heating The first color pattern is formed by the step of fixing the particles containing the phosphor to the substrate together with the photosensitive composition layer (at the same time, melting the binder and flattening the phosphor pattern).

By repeating the above steps (1) to (6),
Form a pattern of red, green and blue phosphors. After forming each color pattern as described above,
To 600 ° C., preferably 380 to 550 ° C., and more preferably 400 to 520 ° C., and all the organic substances of the binder fixing the phosphor and the photosensitive composition which loses the tackiness by light. Is burned and burned to fix a phosphor or a phosphor pattern containing a small amount of inorganic binder to the substrate. Here, the time for the heat treatment at 350 to 600 ° C. is preferably 5 to 60 minutes, more preferably 10 to 60 minutes.
30 minutes.

[0072]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. [Production Example of Polymer Particles] In Production Examples 1 to 12,
A production example of a suspension polymer particle dispersion containing phosphor particles as light-impermeable particles, which is a typical example of the polymer particles of the present invention, will be described. In addition, all parts of the mixing ratio are parts by weight.

<Production Example 1 of Polymer Particles> Styrene 80
After adding 5 parts of 2,2'-azobis-2,4-dimethylpareronitrile to a polymerizable monomer composed of 20 parts of n-butyl acrylate and 20 parts of n-butyl acrylate, the polymerizable monomer was added using an ultrasonic cleaner. 100 parts of the following red phosphor pigment 1 was dispersed in the monomer to prepare an oil phase. Next, an aqueous phase was prepared by adding 3 parts of tribasic calcium phosphate and 0.05 parts of sodium dodecylbenzenesulfonate dispersed in a small amount of water to 100 parts of water. The oil phase and the aqueous phase adjusted by the above-described operations were respectively charged into the dispersed phase tank 22 and the continuous phase tank 21 shown in FIG. Next, the water phase was supplied at a flow rate of 300 ml / min, and the oil phase was supplied at a flow rate of 10 ml / min.
The mixture was supplied to the disperser 25 at a flow rate of 0 ml / min for 10 minutes. The disperser 25 having a rotating part having a diameter of 50 mm was used, and the mixture of the oil phase and the aqueous phase was stirred under the condition of 5000 rpm. The dispersion passed through the disperser 25 was guided into the reaction tank 23 shown in FIG. 1 while stirring at 30 rpm with a turbine-type stirring blade, and reacted at 80 ° C. for 8 hours to obtain polymer particles. After cooling the polymer particles obtained above, the tribasic calcium phosphate on the polymer particles surface is removed with dilute nitric acid, washed with water until the washing solution is neutral, filtered, and dried to obtain polymer particles according to the present invention. I got As a result of measuring the particle diameter of the obtained polymer particles using a Coulter counter (aperture diameter: 100 μm), the volume average particle size of the polymer particles was 25 μm.

<Production Examples 2 to 6 of Polymer Particles> Production Example 2
6 to 6, except that the red phosphor particles 1 in Production Example 1 were sequentially changed to green phosphor particles 1, blue phosphor particles 1, red phosphor particles 2, green phosphor particles 2, and blue phosphor particles 2. Polymer particles containing red, green and blue phosphor particles were obtained in the same manner as in Production Example 1. Red phosphor pigment 1 Y ₂ O ₃ : Eu is partially pulverized so that the particle size becomes 2.5 μm (dispersion coefficient, that is, standard deviation 0.4 μm). Green phosphor pigment 1 Zn ₂ SiO ₄ : Mn is partially pulverized so that the particle size becomes 4 μm (dispersion coefficient, that is, standard deviation 0.5 μm). Blue phosphor pigment 1 BaMgAl ₄ O ₂₃ : Eu is partially pulverized so that the particle size becomes 4 μm (dispersion coefficient, that is, standard deviation 0.5 μm).

Red phosphor pigment 2 Y ₂ O ₃ : Eu is partially pulverized so that the particle size becomes 5 μm (dispersion coefficient, that is, standard deviation 0.7 μm). Green phosphor pigment 2 Zn ₂ SiO ₄ : Mn is partially pulverized so that the particle size becomes 10 μm (dispersion coefficient, that is, standard deviation 2 μm). Blue phosphor pigment 2 BaMgAl ₄ O ₂₃ : Eu is partially pulverized so that the particle size becomes 10 μm (dispersion coefficient, that is, standard deviation 2 μm).

<Production Example 7 of Polymer Particles> (Production Example 7a) 2,2'-azobis-2,4-dimethylvaleronitrile was added to a polymerizable monomer comprising 80 parts of styrene and 20 parts of n-butyl acrylate. 5 parts were added, and the following red phosphor pigment 1 was added to the polymerizable monomer using an ultrasonic cleaner.
Was dispersed to prepare an oil phase. Next, 3 parts of tribasic calcium phosphate and 0.05 parts of sodium dodecylbenzenesulfonate were dispersed in a small amount of water, and added to 240 parts of water to prepare an aqueous phase. 60 g of the oil phase and 240 g of the aqueous phase thus prepared were added to a separable flask having a capacity of 1 liter, and dispersed at room temperature using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 10,000 rpm for 1 minute. 80 ° C., 5
Under the conditions of time, the monomer composition having the phosphor particles as the core was granulated and polymerized. After cooling the polymer particles having the phosphor particles as the core obtained above, the tertiary calcium phosphate on the surface of the polymer particles is removed with dilute nitric acid, washed with water until the washing solution is neutral, filtered, and dried, and the present invention The polymer particles used for the above were obtained. The particle size of the obtained polymer particles was measured using a Coulter counter (aperture 100 μm). As a result, the polymer particles had a volume average particle size of 25 μm. (Production Example 7b) Polymer particles having green phosphor particles as the core by the same operation as in Production Example 7a, except that 100 parts of the red phosphor pigment 1 in the above Production Example 7a was replaced with 100 parts of the green phosphor pigment 1. I got These polymer particles also had a volume average particle size of 25 microns. (Production Example 7c) Polymer particles having blue phosphor particles as the core by the same operation as in Production Example 7a, except that 100 parts of the red phosphor pigment 1 in the above Production Example 7a was replaced with 100 parts of the blue phosphor pigment 1. I got These polymer particles also had a volume average particle size of 25 microns.

<Production Example 8 of Polymer Particles> In this production example, a production example of polymer particles containing silver powder as light-impermeable particles will be described. Polymer particles were produced in the same manner as in Production Example 1 except that 120 parts of silver powder having an average particle diameter of 3 μm was used as the light-impermeable particles instead of 100 parts of the red phosphor particles 1. The particle size of the obtained polymer particles was measured using a Coulter counter (average diameter 1).
As a result, the volume average particle size of the polymer particles was 20 microns.

<Production Example 9 of Polymer Particles> In this production example, a production example of polymer particles containing fine powder of low-melting glass containing lead oxide will be described. In place of silver powder, fine powder of low-melting glass having an average particle size of 0.1 to 1.0 micron is used.
Polymer particles were produced in the same manner as in Production Example 8 except that 0 part was used. The particle size of the obtained polymer particles was measured using a Coulter counter (aperture 100 μm).
m), the volume average particle size of the polymer particles was 18 microns.

<Production Example 10 of Polymer Particles> The following raw materials were mixed with a Henschel mixer. Styrene-2-ethylhexyl acrylate resin: 100 parts Red phosphor 1: 100 parts The obtained mixture was heated and melted and kneaded with an extruder, and the obtained kneaded material was cooled, coarsely ground, and then ground with a jet mill. Classification was performed using an airflow classifier to obtain polymer particles of the present invention. As a result of measuring the particle diameter of the obtained polymer particles using a Coulter counter (aperture diameter: 100 μm), the volume average particle size of the polymer particles was 25 μm.

<Production Example 11 of Polymer Particles> Production Example 10
Was replaced with green phosphor particles 1 to obtain polymer particles of the present invention having a volume average particle size of 25 μm.

<Production Example 12 of Polymer Particles> Production Example 10
Was replaced with blue phosphor particles 1 to obtain polymer particles of the present invention having a volume average particle size of 25 μm.

Example 1 This example shows an example in which the photosensitive composition layer is a layer that loses tackiness when irradiated with light. [Photosensitive composition (material composition for forming adhesiveness)] Benzyl methacrylate / methacrylic acid copolymer 32 g [Molar ratio 70/30, average molecular weight Mw 20,000] Pentaerythritol tetraacrylate 68 g 4- [O-bromo -P-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6 di (trichloromethyl) -s-triazine 4 g 2-benzoylmethylene-3-methyl-β-naphthothiazoline 2 g Hydroquinone monomethyl ether 0.01 g Propylene glycol monomethyl ether acetate 500g

The photosensitive composition solution having the above formulation was applied to the surface of a glass substrate having electrodes and ribs formed thereon as shown in FIG. 1 and subsequently dried at 85 ° C. for 5 minutes. Average film thickness is about 2.0μ
m. A mask was set at a distance of 70 microns from the top of the rib to give a 150 mJ / cm ² exposure. Thereafter, the polymer particles of Production Example 1 containing the red phosphor pigment 1 are sprayed on the entire surface, and excess particles are removed by suction. The particles adhered to the substrate surface including the electrodes and to the rib side walls perpendicular to the substrate surface. Next, it was heated to 200 ° C. for fixing the polymer particles and averaging the thickness. Such a series of steps was repeated three times to form red, green, and blue patterns. The polymer particles of Production Example 2 containing the green phosphor pigment 1 were used as the second particles, and the polymer particles of Production Example 3 containing the blue phosphor pigment 1 were used as the third particles.

Subsequently, the above three-color pattern was applied to about 30
The temperature was raised from room temperature to 450 ° C. over a period of minutes. At this stage,
The layer made of the photopolymerizable composition (the part cured by exposure and the part to which the polymer particles in the unexposed area were adhered) and the organic component of the polymer particles were completely burned out. If it is difficult to burn, oxygen can be blown to help combustion. Cool slowly,
The substrate taken out after returning to room temperature is the substrate surface including the electrodes,
The phosphor uniformly formed a layer of about 25 μm on the side wall of the rib perpendicular to the substrate surface. Further, each of the red, green, and blue patterns on the obtained substrate was firmly fixed to the substrate, and was an excellent pattern without being peeled, deformed, or moved. On the surface of the red, green and blue patterns, a layer in which spherical fine particles were arranged formed a substantially flat layer.

In the conventional method in which an ink-like dispersion obtained by dispersing a phosphor in a resin solution, which has been usually performed before, is inserted between the ribs by silk-screen printing, the height of the ribs is about 200 μm. As a result, the ink-like dispersion was dropped into the 200-micron valley and was not firmly fixed to the substrate surface.Burning off the resin used as the vehicle of the phosphor easily resulted in an uneven layer containing voids. . Also, compared to the method of the above-mentioned JP-A-8-330918 filed by one of the present inventors, the thickness can be easily adjusted by employing the polymer particles by the suspension polymerization method of the present invention, Further, the uniformity of the thickness was excellent.

Example 2 (Photosensitive composition (material composition for forming adhesiveness)) Methyl methacrylate polymer 42 g Trimethylolpropane trimethacrylate 58 g 2- (naphth-1-yl) -4,6-bis- Trichloromethyl-s-triazine 4 g Hydroquinone monomethyl ether 0.01 g Ethyl ethoxypropionate 650 g

The photosensitive composition solution having the above formulation was applied to the surface of a glass substrate on which electrodes and ribs were formed as shown in FIG. 1, and then placed in a convection oven at 110 ° C. for 5 minutes to remove the solvent. . Next, pattern exposure was performed using a projection type exposure machine. Thereafter, the polymer particles of Production Example 4 including the red phosphor pigment 2 are sprayed on the entire surface, and excess polymer particles are removed by suction. Particles adhering to the non-pattern area of the exposed area and not removed by suction were removed by sweeping with a soft brush at the tip of the tip. The particles adhere to the substrate surface including the electrodes and to the rib side walls perpendicular to the substrate surface. Next, the glass substrate was heated in a convection oven at 250 ° C. for 30 minutes. When the photosensitive composition layer and the particles are melted and the particles are integrated with each other to form a film, the photosensitive layer undergoes thermal polymerization at the same time. A phosphor pattern layer having an average of 30 microns was formed.

The series of steps is repeated three times,
Green and blue patterns were formed. The polymer particles of Production Example 5 containing the green phosphor pigment 2 were used for the second time, and the polymer particles of Production Example 6 containing the blue phosphor pigment 2 were used for the third time. Subsequently, the temperature was raised to 550 ° C. over about 30 minutes. At this stage, the photosensitive layer made of the photopolymerizable composition (the part cured by exposure and the part where the phosphor pigment was adhered in the unexposed area) and the organic component of the polymer particles were completely burned out. If it is difficult to burn, oxygen can be blown to help combustion. After the substrate was gradually cooled and returned to room temperature, the substrate taken out had a phosphor layer uniformly formed on the substrate surface including the electrodes and on the rib side walls perpendicular to the substrate surface to a thickness of about 20 μm.

The obtained red, green, and blue patterns on the substrate were firmly fixed to the substrate, and were excellent patterns without peeling, deformation, or movement. Was. On the red, green, and blue pattern surfaces, a layer in which spherical fine particles were arranged formed a substantially flat layer, which was better than that in Example 1.

Example 3 (Photopolymerizable composition (material composition forming tackiness)) Butyl methacrylate / methacrylic acid copolymer 35 g [Molar ratio 70/30, average molecular weight Mw 20,000] Pentaerythritol tetraacrylate 65 g 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine 6.5 g Hydroquinone monomethyl ether 0.01 g 3-methoxybutyl acetate 650 g

The photosensitive composition solution having the above formulation was applied to the surface of a glass substrate on which electrodes and ribs were formed as shown in FIG. 1, and then placed in a convection oven at 110 ° C. for 5 minutes to remove the solvent. . In order to avoid contact with the mask, pattern exposure was performed using a projection type exposure machine. Thereafter, the polymer particles of Production Example 1 including the red phosphor particles 1 are sprayed on the entire surface, and excess polymer particles are removed by suction. The polymer particles adhere to the substrate surface containing the electrodes and the rib sidewalls perpendicular to the substrate surface. Next, the entire surface of the glass substrate was exposed to 1200 mj / cm ² from the back surface to fix the polymer particles. Repeat the series of steps over three times, red,
Green, blue and silver patterns were formed. The second polymer particle is the polymer particle of Production Example 2 including the green phosphor particles 1, the third polymer particle is the polymer particle of Production Example 3 including the blue phosphor particles 1, and the fourth polymer particle is the one of Production Example 8 Polymer particles containing fine silver particles were used. afterwards,
Heated in a convection oven at 250 ° C. for 30 minutes. When the binder was melted and the pigment particles were integrated with each other, and the temperature was returned from the oven to room temperature, the layers containing the phosphor or silver were fixed.

Subsequently, the temperature was raised to 550 ° C. over about 30 minutes. At this stage, the photosensitive layer made of the photopolymerizable composition (the part cured by exposure and the part where the phosphor pigment was adhered in the unexposed area) and the organic component of the polymer particles were completely burned out. If it is difficult to burn, oxygen can be blown to help combustion. After slowly cooling and returning to room temperature, the substrate taken out has a phosphor layer formed uniformly on the substrate surface including the electrodes and on the rib side walls perpendicular to the substrate surface with a layer of about 20 microns and a silver pattern. I was In addition, each pattern of red, green, blue phosphor and silver on the obtained substrate is firmly fixed to the substrate, and is peeled or deformed,
It was an excellent pattern without any movement. Also,
On the red, green, and blue pattern surfaces, a layer in which spherical fine particles were arranged formed a substantially flat layer.

Example 4 In this example, an example is shown in which a convenient phthalic acid group-containing monomer is used as a component of the photosensitive composition layer. A photosensitive solution of a photosensitive composition sample 1 having the following formulation was flowed in a curtain shape over the surface of a glass substrate on which electrodes and ribs were formed as shown in FIG. 1 and allowed to spread over the entire surface. Then, the excess liquid was removed and dried to form a photosensitive layer. On the photosensitive layer, exposure was performed through a mask to only the region where the phosphor layer was not formed. Since the surface of the photosensitive layer was still sticky even after drying, the mask was set with a gap of 50 microns from the top of the rib (under air atmosphere). Thereafter, the polymer particles of Production Example 1 containing the red phosphor particle pigment 1 were sprayed on the entire surface, and excess powder was removed by suction. The powder adhered to the substrate surface including the electrodes and to the rib sidewalls perpendicular to the substrate surface. This process was repeated for the polymer particles of Production Example 2 containing the green phosphor composition pigment 1 and the polymer particles 3 of Production Example 3 containing the blue phosphor composition pigment 1, and then placed in an electric heating furnace at 250 ° C. After a lapse of minutes, the temperature was raised to 400 ° C. over about 30 minutes. 5 liters /
Minutes of dry air.

At this stage, the baked organic components in the photosensitive layer comprising the photosensitive composition and the polymer particles were completely burned out. If it is difficult to burn, oxygen can be blown to help combustion. After the substrate was gradually cooled and returned to room temperature, the substrate taken out of the substrate formed a uniform layer of the phosphor on the substrate surface including the electrodes and on the rib side walls perpendicular to the substrate surface.
A micron layer was formed and no phosphor adhered to the exposed areas.

(Photosensitive composition (material composition forming tackiness) -1) Benzyl methacrylate / methacrylic acid copolymer 32 g [Molar ratio 70/30, weight average molecular weight Mw 20,000] Pentaerythritol tetraacrylate 32 g 2-acryloyloxyethyl-1-phthalic acid 64 g 4- [O-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6 di (trichloromethyl) -s-triazine 4 g 2- Benzoylmethylene-3-methyl-β-naphthothiazoline 2 g Hydroquinone monomethyl ether 0.01 g Propylene glycol monomethyl ether acetate 650 g

Example 5 In this example, an example of the present invention using a photosensitive composition layer whose tackiness is increased by light irradiation will be described. A photosensitive liquid of a photo-adhesive having the following composition 1 is applied and dried, and is dried for about 0.7.
After forming a photosensitive resin film having a thickness of μm, the exposure illuminance is about 9 W / m ² and about 9 W
Exposure was performed for 0 second, and thereafter, the polymer particles of Production Example 5 containing the green phosphor pigment 2 were applied to form green phosphor stripes. Then, this was heated to 200 ° C. to perform fusion and fixation. Composition 1 P-diazodimethylaniline chloride zinc chloride 3% by weight propylene glycol alginate 0.6% by weight polyvinyl alcohol 0.07% by weight ethylene glycol 0.02% by weight Pluronic L-92 (surfactant) ... 0.005% by weight ammonium bichloroate ... ... 0.007% by weight water balance The same process is repeated using each of the polymer particles of Production Examples 4 and 6 containing the red phosphor pigment 2 and the blue phosphor pigment 2, respectively. A layer of a pattern of material was formed.

Example 6 The same photosensitive composition as in Example 1 was used, except that the polymer particles of Production Examples 1, 2 and 3 used in the example were changed to Production Examples 7a, b and c, respectively. A layer of a three-color phosphor particle material pattern was formed by the method.

Subsequently, the phosphor particle pattern of the above three colors was applied from room temperature to 450 ° C. in about 30 minutes in the same manner as in Example 1.
Temperature. At this stage, the organic components of the photopolymerizable composition and the polymer particles have completely burned out. After slowly cooling and returning the temperature to room temperature, the substrate taken out was uniformly coated with phosphor on the substrate surface including the electrodes and the rib side walls perpendicular to the substrate surface for about 25 minutes.
A layer of μm was formed. Further, each of the red, green, and blue patterns on the obtained substrate was firmly fixed to the substrate, and was an excellent pattern without being peeled, deformed, or moved. Also, red, green,
On the blue pattern surface, a layer in which spherical fine particles were arranged formed a substantially flat layer.

Example 7 The same photosensitive composition as in Example 1 was used, except that the polymer particles of Production Examples 1, 2 and 3 used in the Example were changed to Production Examples 10, 11 and 12, respectively. A layer of a three-color phosphor particle material pattern was formed by the method.

The resulting three-color phosphor particle pattern was heated from room temperature to 450 ° C. in about 30 minutes in the same manner as in Example 1 to completely burn out the organic components. After the substrate was cooled down slowly and returned to room temperature, the substrate taken out was uniformly coated with phosphor on the substrate surface including the electrodes and the rib side walls perpendicular to the substrate surface by about 2 μm.
A layer of 5 μm was formed. Further, each of the red, green, and blue patterns on the obtained substrate was firmly fixed to the substrate, and was an excellent pattern without being peeled, deformed, or moved. Also, red, green,
On the blue pattern surface, a layer in which spherical fine particles were arranged formed a substantially flat layer.

[0101]

As described above, in a pattern forming method for forming a plurality of patterns of a light-impermeable material in a single firing step, a polymer produced by a suspension polymerization method, an emulsion polymerization method or a kneading-pulverization method. By the method of the present invention in which the particles are applied to the photo-adhesive photosensitive composition layer, the thickness of the pattern of the light-impermeable material can be adjusted to a desired level with high accuracy, and the uniformity of the thickness can be improved. it can.
In particular, in the case of a plasma display substrate, a pattern having a uniform thickness can be formed on the substrate surface including the electrodes and the rib partition walls perpendicular to the substrate surface, and the range of applicable inorganic fine particle materials can be expanded. it can.

[Brief description of the drawings]

FIG. 1 is a perspective view showing a typical configuration example of a panel for exciting and emitting phosphors of three primary colors with ultraviolet rays by gas discharge for a plasma display.

FIG. 2 is a schematic structural view of an example of an apparatus for use in a suspension polymerization method for polymer particles according to the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 front glass substrate 2 display electrode (transparent electrode) 3 bus electrode 4 partition (rib) 5 back glass substrate 9 phosphor (red) 10 phosphor (green) 11 phosphor (blue) 21 continuous phase tank 22 dispersed phase tank 23 Reaction tank 24 Metering pump 25 Disperser 26 Concentrator 27 Heating jacket 28, 29 and 30

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI H01L 21/027 H01L 21/30 568 (72) Inventor Hiromi Tozuka 3-1, Yomibacho, Shizuoka-shi, Shizuoka Pref. In-house (72) Inventor Masahiro Maeda 3-1 Yomoe-cho, Shizuoka-shi, Shizuoka Prefecture Inside the Technical Research Laboratory of Hamakawa Paper Mill Co., Ltd. (72) Inventor Masayuki Kurosaki 3-1 Yomune-cho, Shizuoka-shi, Shizuoka (72) Katsuhiro Okukawa, Inventor Katsuhiro Okugawa, 3-1 Bamboo-cho, Shimooka-shi, Shizuoka Pref.

Claims (10)

[Claims] 1. A photosensitive composition layer whose adhesiveness is changed by irradiation with actinic light is formed on a substrate, and the photosensitive composition layer is irradiated with actinic light through a mask to obtain a suspension composition, emulsion polymerization method or Polymer particles granulated by a kneading and pulverizing method and containing a light-impermeable material are applied to the surface of the composition layer to selectively adhere the particles to the tacky region, and then the excess not adhered The polymer particles and the polymer particles present in the non-adhesive region are removed, and then the photosensitive composition layer is heated or irradiated with active light to fix the attached polymer particles together with the photosensitive composition layer to the substrate. By sequentially repeating a series of steps, a pattern made of two or more kinds of light-impermeable materials is formed.
A method for forming a pattern of a light-impermeable material, wherein the pattern is formed by heating to about 600 ° C., melting and firing to form a pattern of the light-impermeable material. 2. The method according to claim 1, wherein the weight average particle size of the polymer particles containing the light impermeable material is 3 to 100 microns. 3. The light opaque material according to claim 1, wherein the light opaque material is at least one material selected from a phosphor, a pigment, a metal powder, and a metal oxide powder. Forming method of conductive material. 4. The light-opaque material according to claim 1, wherein the weight ratio of the light-opaque material to the polymer in the polymer particles is 0.04 to 9.0. Pattern formation method. 5. The method for forming a pattern of a light impermeable material according to claim 1, wherein the change in the adhesiveness of the photosensitive composition layer due to the irradiation of the actinic ray is an increase in the adhesiveness. 6. The method for forming a pattern of a light impermeable material according to claim 1, wherein the change in the tackiness of the photosensitive composition layer due to the irradiation with actinic rays is a decrease in tackiness. 7. In the pattern formation of polymer particles which are granulated by a suspension polymerization, an emulsion polymerization method or a kneading and pulverizing method and which contain a light-impermeable material, the particles selectively adhered to the tacky region are heated. Wherein the heating for fixing to the substrate together with the photosensitive composition layer is performed by a heat treatment at 80 to 300 ° C. 8. A photosensitive composition layer, which loses tackiness upon irradiation with actinic light, is formed on a substrate, and the photosensitive composition layer is irradiated with actinic light through a mask, and the surface thereof is subjected to suspension polymerization,
Applying polymer particles granulated by an emulsion polymerization method or a kneading and pulverizing method and containing a light-impermeable material to selectively adhere the particles to the tacky region, and then excess particles that did not adhere and Remove particles present in the non-stick area,
Subsequently, a series of steps of irradiating the photosensitive composition layer with actinic rays and fixing the adhered polymer particles to the substrate together with the photosensitive composition layer are sequentially repeated, whereby two or more kinds of light-impermeable materials are used. Is formed, and this is 35
A method for forming a pattern of a light-impermeable material, comprising heating the photosensitive composition and the binder by heating to 0 to 600 [deg.] C. to burn and burn off to form a pattern of the light-impermeable material. 9. A granulated product for pattern formation of a light-impermeable material obtained by suspension-polymerizing a dispersion containing at least a light-impermeable material, a light- or heat-polymerizable monomer and a polymerization initiator. . 10. A granulated product for pattern formation of a light-impermeable material obtained by melt-kneading and pulverizing a mixture containing at least a light-impermeable material and a thermoplastic polymer.