JPH11231524A - Production of plasma display panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent undercut in development and to surely produce a pattern of each constituent element with high efficiency and high definition by exposing and developing a resist film contg. a specified compd. to form a resist pattern, forming a pattern of an inorg. powder dispersed paste layer corresponding to the resist pattern and baking the paste pattern. SOLUTION: A resist film contg. a compd. represented by the formula is formed on an inorg. powder dispersed paste layer, exposed to form a latent image of a resist pattern and developed to form an apparent resist pattern. The paste layer is then etched to form a pattern of the paste layer corresponding to the resist pattern and the paste pattern is baked. A panel material with an inorg. pattern is thus obtd. Curing reaction is sufficiently attained by irradiation with a small quantity of energy and development is easily carried out.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is capable of forming a high-definition pattern in forming partition walls, electrodes, dielectrics, resistors, phosphors, color filters and black matrices constituting each display cell of a plasma display panel. Further, the present invention relates to a method of manufacturing a plasma display panel which can substantially improve workability by using a transfer film as compared with a conventional method.

[0002]

2. Description of the Related Art Plasma display panels (PDPs)
Has been attracting attention in flat panel display technology because of its ease of manufacturing process despite its large size, wide viewing angle, and high display quality with its self-luminous type. Display panels are expected to become mainstream in the future as display devices for wall-mounted TVs of 20 inches or more. Color PDP
The color display can be performed by irradiating the phosphor with ultraviolet rays generated by gas discharge. In general, in a color PDP, a phosphor portion for red light emission, a phosphor portion for green light emission, and a phosphor portion for blue light emission are formed on a substrate, so that the light emitting display cells of each color are entirely formed. It is configured in a uniformly mixed state. Specifically, a partition wall made of an insulating material called a barrier rib is provided on the surface of a substrate made of glass or the like, and a large number of display cells are partitioned by the partition walls. Become space. By providing a phosphor region in the plasma working space and providing an electrode for causing plasma to act on the phosphor region, a plasma display panel having each display cell as a display unit is constructed.

FIG. 1 shows an example of the structure of an AC type PDP.
On the front substrate glass, a plurality of pairs of sustain electrodes are formed in a stripe shape, the upper portion is covered with a dielectric layer, and an MgO film serving as a protective film is deposited thereon. Further, in order to improve the contrast of the plasma display panel, a red, green, blue color filter or a black matrix may be provided below the dielectric layer. On the other hand, on the rear substrate glass, a plurality of signal electrodes are formed in a stripe shape,
A partition is provided between the signal electrodes, and a phosphor layer is formed on the side and bottom surfaces of the partition. The sustain electrodes on the front substrate and the signal electrodes on the rear substrate are attached and sealed so as to be vertical, and a mixed gas of neon and xenon is introduced into the interior.

FIG. 2 shows an example of the structure of a DC PDP.
A plurality of cathode electrodes are formed in a stripe shape on the front substrate glass. On the other hand, electrode terminals and leads of the display anode and the auxiliary anode are formed on the rear substrate glass, and a resistor is provided between the anode terminal and the anode lead and between the auxiliary anode terminal and the auxiliary anode lead. Except for the display anode terminal and the auxiliary anode terminal on the rear substrate, they are insulated by a dielectric. Next, partition walls are provided in a grid pattern to divide the discharge space, and a phosphor layer is formed on the side surfaces of the partition walls and on the bottom surface excluding the anode terminals. The cathode of the front substrate and the display anode and the auxiliary anode of the rear substrate are vertically adhered and sealed, and a mixed gas of neon and xenon is introduced therein.

[0005] As a method of manufacturing each component of such a plasma display panel, (1) a non-photosensitive inorganic powder-dispersed paste composition is screen-printed on a substrate to obtain a pattern, and the screen is fired. Printing method,
(2) A film of a photosensitive inorganic powder-dispersed paste composition is formed on a substrate, and the film is irradiated with ultraviolet rays through a photomask and developed to leave a pattern on the substrate. A baking photolithography method and the like are known.

However, the screen printing method has a problem that the positional accuracy of the pattern becomes very strict with the increase in size and definition of the panel, and cannot be dealt with by ordinary printing. In the photolithography method, one exposure and development process requires 10 to 10 times.
When a pattern having a thickness of 100 μm was formed, the sensitivity in the depth direction of the inorganic powder-dispersed paste layer was insufficient, and a high-definition pattern with sharp edges was not necessarily obtained.

As means for solving the above problems,
The present inventors formed a laminate of a photosensitive resist composition layer and an inorganic pigment paste layer on a substrate, and exposed the photosensitive resist composition layer constituting the laminate film to an exposure process to form a latent image of the resist pattern. Formed, developing the photosensitive resist composition layer to reveal a resist pattern, etching the inorganic pigment paste layer to form a pattern of the inorganic pigment paste layer corresponding to the resist pattern, and baking the pattern There has been proposed a method for manufacturing a plasma display panel, wherein a pattern of a color filter is formed by a method including a step of forming an inorganic pigment pattern by processing. Conventionally, as a photosensitive resist composition, radical polymerization comprising a binder polymer containing a carboxyl group and a polyfunctional acrylate such as pentaerythritol acrylate has been used. A substance containing an active substance and a photo-radical generator is used. As the photo-radical generator, for example, 1-hydroxycyclohexyl phenyl ketone is used.

[0008]

However, in the above-described photosensitive resist composition, the intensity of photocuring radiation in the coating film is attenuated in the depth direction, so that the photosensitivity of the coating film is low. A phenomenon in which the resist composition becomes smaller as approaching the bottom of the resist composition occurs, and the curing reaction tends to be insufficiently achieved. In this case, the bottom portion is hollowed out by the developing process in the manufacturing process of each component in the PDP, and the obtained resist pattern has a so-called undercut. There is a problem that the photosensitive resist layer flows away. As a result, the patterning becomes non-uniform, and the yield of the panel becomes extremely poor. The above problem can be solved by performing the irradiation treatment with a sufficient amount of energy, but in this case, the efficiency in manufacturing is low.

The present invention has been made in view of the above circumstances, and an object of the present invention is to prevent undercuts in a developing process, and to manufacture a pattern of each component with high efficiency and high precision. It is an object of the present invention to provide a method of manufacturing a plasma display panel.

[0010]

According to a method of manufacturing a plasma display panel of the present invention, an inorganic powder dispersion paste layer formed on a support film is transferred onto a substrate, and the inorganic powder dispersion paste layer is formed on the inorganic powder dispersion paste layer. A resist film containing a compound represented by the following formula (1) is formed, the resist film is exposed to light, a latent image of the resist pattern is formed, and the resist film is developed to reveal the resist pattern. Forming a pattern of the inorganic powder-dispersed paste layer corresponding to the resist pattern by etching the inorganic powder-dispersed paste layer, and forming a panel material having an inorganic pattern by a method including a step of baking the pattern. It is characterized by doing.

[0011]

Embedded image

In the method of manufacturing a plasma display panel according to the present invention, the effect is more preferably exhibited by forming a laminated film of a resist film and an inorganic powder paste layer on a support film in advance.

[0013]

In the production method of the present invention, the inorganic powder-dispersed paste layer is not formed by directly applying an inorganic powder-dispersed paste composition in which an inorganic powder is dispersed on a rigid substrate. Formed on a flexible support film. For this reason, as a method for applying the paste-like composition, an application method using a roll coater or the like can be adopted, and thereby, the inorganic powder-dispersed paste having a large film thickness and excellent uniformity of the film thickness can be used. A layer (eg, 10 μm ± 1 μm) can be formed on the support film. Then, the inorganic powder-dispersed paste layer can be reliably formed on the substrate by a simple operation of collectively transferring the inorganic powder-dispersed paste layer thus formed to the surface of the substrate. In addition, by applying a specific photosensitive resist composition on the inorganic powder paste layer and performing patterning, an undercut in a development process is prevented, and a pattern of each component in a PDP is reliably manufactured with high efficiency. And the quality of the formed pattern can be improved (higher definition).

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The production method of the present invention will be described below in detail. In the production method of the present invention, [1]
Transferring the inorganic powder dispersed paste layer, [2] forming the resist film, [3] exposing the resist film, [4] developing the resist film, [5] etching the inorganic powder dispersed paste layer, [6] A panel material having an inorganic pattern is formed by a firing step of the inorganic powder-dispersed paste layer pattern. Here, the panel material having an inorganic pattern is not particularly limited as long as it is a component of the plasma display panel. For example, a partition, an electrode, a dielectric, a resistor,
Examples include a phosphor, a color filter, a black matrix, and the like.

<Transfer Step of Inorganic Powder Dispersion Paste Layer> FIGS. 3 and 4 are schematic cross-sectional views showing an example of a step of forming an inorganic powder dispersion paste layer in the production method of the present invention. In FIG. 3A, reference numeral 11 denotes a glass substrate.

The manufacturing method of the present invention is characterized in that a transfer film is used and the inorganic powder-dispersed paste layer constituting the transfer film is transferred to the surface of the substrate. Here, the transfer film is a support film,
An inorganic powder-dispersed paste layer formed on the support film, and a protective film layer may be provided on the surface of the inorganic powder-dispersed paste layer. The specific configuration of the transfer film will be described later.

An example of the transfer step is as follows. After the protective film layer of the transfer film used as necessary is peeled off, the surface of the inorganic powder-dispersed paste layer 21 is brought into contact with the surface of the glass substrate 11 as shown in FIG. After the transfer film 20 is thermocompressed with a heating roller or the like, the transfer film 20 is transferred from the inorganic powder-dispersed paste layer 21 to the support film 22.
Is peeled off. Thereby, as shown in FIG. 3C, the inorganic powder-dispersed paste layer 2
1 is transferred and comes into close contact. Here, as the transfer condition, for example, the surface temperature of the heating roller is 80 to 14
0 ° C, roll pressure by heating roller is 1-5kg / c
m ² , and the moving speed of the heating roller can be 0.1 to 10.0 m / min. The glass substrate may be preheated, and the preheating temperature may be, for example, 40 to 100 ° C.

<Step of Forming Resist Film> In this step, as shown in FIG. 3D, a resist film 31 is formed on the surface of the transferred inorganic powder dispersed paste layer 21.
The resist constituting the resist film 31 may be either a positive resist or a negative resist, and the specific composition thereof will be described later. Resist film 3
1 is screen printing, roll coating, spin coating,
It can be formed by applying a resist by various methods such as a casting coating method and then drying the coating film.
Further, the resist film may be formed by transferring the resist film formed on the support film to the surface of the inorganic powder dispersed paste layer 21. According to such a forming method, it is possible to improve the process (higher efficiency) in the process of forming the resist film, and it is possible to achieve a uniform thickness of the formed inorganic powder pattern. The thickness of the resist film 31 is generally 0.1 to 40 μm, preferably 0.5 to 2 μm.
0 μm.

<Resist Film Exposure Step> In this step, as shown in FIG. 3E, the surface of the resist film 31 formed on the inorganic powder dispersed paste layer 21 is exposed through an exposure mask M via an exposure mask M. Then, radiation such as ultraviolet rays is selectively irradiated (exposed) to form a latent image of the resist pattern. In the figure, MA and MB are a light transmitting part and a light shielding part in the exposure mask M, respectively. Here, the radiation irradiating apparatus is not particularly limited, such as an ultraviolet irradiating apparatus used in the photolithography method, an exposure apparatus used in manufacturing a semiconductor and a liquid crystal display device.

<Developing Step of Resist Film> In this step, a resist pattern (latent image) is exposed by developing the exposed resist film. Here, the development processing conditions include the type, composition, and concentration of the developer, the development time, the development temperature, and the development method (for example, the immersion method, the oscillating method, the shower method,
(Spray method, paddle method), a developing device, and the like can be appropriately selected. As a result of this development step, as shown in FIG.
A resist pattern 35 (a pattern corresponding to the exposure mask M) composed of B and B is formed. The resist pattern 35 functions as an etching mask in the next step (etching step), and the constituent material (photocured resist) of the resist remaining portion 35A is smaller than the constituent material of the inorganic powder dispersion paste layer 21. It is necessary that the dissolution rate with respect to the etching solution is low.

<Etching Step of Inorganic Powder Dispersion Paste Layer> In this step, the inorganic powder dispersion paste layer is etched to form a pattern of the inorganic powder dispersion paste layer corresponding to the resist pattern. That is, FIG.
As shown in (g), a portion of the inorganic powder-dispersed paste layer 21 corresponding to the resist removal portion 35B of the resist pattern 35 is dissolved in an etching solution and selectively removed. Here, FIG. 4 (g) shows a state during the etching process. Then, when the etching process is further continued, as shown in FIG. 4H, the surface of the glass substrate is exposed at a portion corresponding to the resist removal portion in the inorganic powder dispersed paste layer 21. Thus, an inorganic powder dispersed paste layer pattern 25 composed of the material layer remaining portion 25A and the material layer removing portion 25B is formed. Here, as the etching treatment conditions, the type, composition, concentration, treatment time, treatment temperature, treatment method (for example, immersion method, rocking method,
A shower method, a spray method, a paddle method), a processing device, and the like can be appropriately selected. The type of the resist film 31 and the type of the inorganic powder-dispersed paste layer 21 are selected so that the same solution as the developing solution used in the developing step can be used as the etching solution. Can be continuously performed, and the manufacturing efficiency can be improved by simplifying the process. Here, the resist remaining portion 35A constituting the resist pattern 35 is gradually dissolved during the etching process, and is completely removed at the stage when the inorganic powder dispersed paste layer pattern 25 is formed (at the end of the etching process). Preferably, it is Even if a part or the whole of the remaining resist portion 35A remains after the etching process, the remaining resist portion 35A is removed in the next baking step.

<Baking Step of Inorganic Powder-Dispersed Paste Layer Pattern> In this step, the inorganic powder-dispersed paste layer pattern 25 is baked to form an electrode, a resistor, a phosphor, a color filter or a black matrix.
As a result, the organic substance in the remaining portion of the material layer is burned off, and an inorganic layer such as a metal layer and a phosphor layer is formed.
A panel material 50 in which an electrode, a resistor, a phosphor, a color filter or a black matrix pattern 40 is formed on the surface of a glass substrate as shown in FIG. Here, the temperature of the baking treatment needs to be a temperature at which the organic substance in the material layer residual portion 25A is burned off, and is usually 400 to 600 ° C. Also,
The firing time is generally set to 10 to 90 minutes.

<Preferred Embodiment> In the manufacturing method of the present invention, it is preferable that a laminate comprising a plurality of inorganic powder-dispersed paste layers having different solubilities in an etching solution is transferred and formed on a substrate. By performing an etching process on such a stacked body, anisotropy in the depth direction with respect to the etching is generated, so that a material layer remaining portion having a rectangular shape or a preferable cross-sectional shape close to a rectangle can be formed. The number of layers of the inorganic powder dispersion paste layer is usually 1
0 or less, preferably 2 to 5. Where n
As a method for forming a laminate comprising the inorganic powder-dispersed paste layers on a substrate, (1) a method of transferring an inorganic powder-dispersed paste layer (one layer) formed on a support film n times, 2) Any method of batch-transferring a laminate composed of n layers of inorganic powder-dispersed paste layers may be used, but from the viewpoint of simplification of the transfer step, the method of (2)
Is preferred.

<Another Method for Forming Inorganic Powder Pattern> The method for forming an inorganic powder pattern in the present invention is as follows.
The method is not limited to the method shown in FIGS. Here, as another method for forming the inorganic powder pattern, a forming method by the following steps (1) to (3) can be mentioned. (1) After forming a resist film on a support film, an inorganic powder-dispersed paste layer is laminated on the resist film. Here, when forming the resist film and the inorganic powder-dispersed paste layer, a roll coater or the like can be used, whereby a laminated film having excellent uniformity in film thickness can be formed on the support film. Can be. (2) Transfer a laminated film of a resist film and an inorganic powder-dispersed paste layer formed on a support film onto a substrate. Here, the transfer conditions may be the same as the conditions in the above-mentioned “transfer step of the inorganic powder-dispersed paste layer”. (3) Perform the same operations as those of the above-mentioned “resist film exposure step”, “resist film development step”, “inorganic powder dispersion paste layer etching step” and “inorganic powder dispersion paste layer pattern baking step”. . According to the method as described above, since the inorganic powder-dispersed paste layer and the resist film are collectively transferred onto the substrate, the production efficiency can be further improved by simplifying the steps.

The materials used in each of the above steps are as follows:
Various conditions will be described. <Substrate> As a substrate material, for example, glass, silicon,
It is a plate-like member made of an insulating material such as polycarbonate, polyester, aromatic amide, polyamide imide, and polyimide. The surface of the plate-like member may be subjected to a chemical treatment with a silane coupling agent or the like as necessary; a plasma treatment; a thin film forming treatment by an ion plating method, a sputtering method, a gas phase reaction method, a vacuum deposition method, or the like. Such an appropriate pretreatment may be performed.

<Transfer Film> The transfer film used in the production method of the present invention comprises a support film and an inorganic powder-dispersed paste layer formed on the support film. May be provided with a protective film layer.

(1) Support Film: The support film constituting the transfer film is preferably a resin film having heat resistance and solvent resistance and having flexibility. When the support film has flexibility, the paste-like composition can be applied by a roll coater, and the inorganic powder-dispersed paste layer can be stored and supplied in a rolled state. As the resin forming the support film, for example, polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, fluorine-containing resin such as polyfluoroethylene,
Examples include nylon and cellulose. The thickness of the support film is, for example, 20 to 100 μm.

(2) Inorganic powder-dispersed paste layer: The inorganic powder-dispersed paste layer constituting the transfer film is composed of inorganic powder,
A paste-like inorganic powder-dispersed paste composition containing a binder resin and a solvent as essential components (for example, a composition for forming a partition, a composition for forming an electrode, a composition for forming a dielectric, a composition for forming a resistor, A composition for forming a phosphor, a composition for forming a color filter, a composition for forming a black matrix, etc.) on the support film, and drying the coating film to remove a part or all of the solvent. be able to.

(3) Inorganic powder-dispersed paste composition The inorganic powder-dispersed paste composition used for producing a transfer film contains (a) an inorganic powder, (b) a binder and (c) a solvent. It is a paste-like composition obtained by the following.

(A) Inorganic Powder The inorganic powder used in the inorganic powder-dispersed paste composition of the present invention varies depending on the type of the forming material. For example, as the inorganic powder used for the partition wall forming material and the dielectric forming material, glass powder, preferably having a softening point of 400 to 6 is used.
Glass powder at 00 ° C. is exemplified. Examples of the inorganic powder used for the electrode forming material include Ag, Au, Al, Ni, Ag-Pd alloy, Cu, and Cr. Examples of the inorganic powder used for the resistor forming material include RuO ₂ . The inorganic powder used for the phosphor forming material is Y ₂
O ₃ : Eu ³⁺ , Y ₂ SiO ₅ : Eu ³⁺ , Y ₃ Al ₅ O ₁₂ : Eu ³⁺ , YVO ₄ : Eu ³⁺ ,
Red phosphor such as (Y, Gd) BO ₃ : Eu ³⁺ , Zn ₃ (PO ₄ ) ₂ : Mn; Zn
₂ SiO ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, BaMgAl ₁₄ O ₂₃ : Mn, LaPO ₄ : (Ce,
Green phosphors such as Tb) and Y ₃ (Al, Ga) ₅ O ₁₂ : Tb; Y ₂ SiO ₅ : C
e, BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , BaMgAl ₁₄ O ₂₃ : Eu ²⁺ , (Ca, Sr, Ba)
Blue phosphors such as ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ²⁺ and (Zn, Cd) S: Ag can be given. The inorganic powder used for the color filter forming material is Fe ₂ O ₃ , Pb ₃ O ₄ , CdS, CdSe, PbCr
Red pigments such as O ₄ , PbSO ₄ , Fe (NO ₃ ) ₃ ; Cr ₂ O ₃ , TiO ₂ -C
oO-NiO-ZnO, CoO-CrO-TiO ₂ -Al ₂ O ₃ , Co ₃ (PO4) ₂ , CoO-ZnO
Green pigments such as 2 (Al ₂ Na ₂ Si ₃ O ₁₀ ) ・ Na ₂ S ₄ ), CoO-Al
_In addition to blue pigments such as ₂ O ₃ , PbCrO ₄ -PbSO ₄ , PbCrO ₄ , PbCrO ₄ -PbO, CdS, TiO ₂ -Ni as inorganic pigments for color correction
Yellow pigments such as _{O-Sb 2 O 3; Pb} (Cr-Mo-S) O 4 orange pigments such as; Co ₃ (PO ₄₎ can be cited purple pigments such as _2.
Examples of the inorganic powder used for the black matrix forming material include Mn, Fe, and Cr.

(B) Binder As the binder used in the inorganic powder-dispersed paste composition of the present invention, various resins can be used.
It is particularly preferable to use a binder containing 30 to 100% by weight of an alkali-soluble resin. here,
The term “alkali-soluble” refers to a property of being dissolved by an alkaline etchant described below and having such solubility that the desired etching treatment is performed. Specific examples of such alkali-soluble resins include, for example, (meth) acrylic resins, hydroxystyrene resins, novolak resins, polyester resins, and the like. Among such alkali-soluble resins, particularly preferred are a copolymer of the following monomer (a) and monomer (b), or a copolymer of monomer (a), monomer (b) and monomer (c): Copolymers can be mentioned.

Monomers (A): acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid,
Carboxyl group-containing monomers such as citraconic acid, mesaconic acid, and cinnamic acid; hydroxyl group-containing such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate Monomers; o-hydroxystyrene, m-
Alkali-soluble functional group-containing monomers represented by phenolic hydroxyl group-containing monomers such as hydroxystyrene and p-hydroxystyrene. Monomer (b): methyl (meth) acrylate, (meth)
(Meth) acrylates other than the monomer (a) such as ethyl acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, and dicyclopentanyl (meth) acrylate;
Aromatic vinyl monomers such as styrene and α-methylstyrene; and monomers copolymerizable with monomers (a) represented by conjugated dienes such as butadiene and isoprene. Monomer (c): A polymerizable polymer such as a (meth) acryloyl group is attached to one end of a polymer chain such as polystyrene, poly (methyl) methacrylate, ethyl poly (meth) acrylate, and benzyl poly (meth) acrylate. Macromonomers represented by macromonomers having a saturated group:

The content ratio of the binder in the inorganic powder-dispersed paste composition is usually 1 to 50 parts by weight, preferably 1 to 40 parts by weight, per 100 parts by weight of the inorganic powder.
Parts by weight.

(C) Solvent The solvent constituting the inorganic powder-dispersed paste composition is contained in order to impart appropriate fluidity or plasticity and good film-forming properties to the inorganic powder-dispersed paste composition. . Solvents constituting the inorganic powder dispersion paste composition are not particularly limited, for example, ethers, esters, ether esters, ketones, ketone esters, amides, amide esters, lactams, Lactones, sulfoxides, sulfones, hydrocarbons, halogenated hydrocarbons and the like can be mentioned. Specific examples of such a solvent include tetrahydrofuran, anisole, dioxane, ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers,
Propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, acetates, hydroxyacetates, alkoxyacetates, propionates, hydroxypropionates, alkoxypropionates, lactates, ethylene glycol Monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, alkoxyacetates, cyclic ketones, acyclic ketones, acetoacetates, pyruvates, N, N-dialkylformamides, N, N-dialkylacetamides, N-alkylpyrrolidones, γ-lactones, dialkylsulfoxides, dialkylsulfones, terpineol, N-methyl-2-pyrrolide And the like can be illustrated, it may be used alone or in combination of two or more. As the content ratio of the solvent in the inorganic powder dispersion paste composition, a good film-forming property (flowability or plasticity)
Can be appropriately selected within a range in which is obtained.

The inorganic powder-dispersed paste composition may contain, as optional components, a plasticizer, a development accelerator, an adhesion aid, an antihalation agent, a storage stabilizer, an antifoaming agent, an antioxidant, an ultraviolet absorber, a filler, Various additives such as low melting point glass may be contained.

As a method of applying the inorganic powder-dispersed paste composition on a support film, a method capable of efficiently forming a large (for example, 10 μm or more) coating film having excellent uniformity of the film thickness is used. It is necessary that the coating method be used, and specific examples thereof include a coating method using a roll coater, a coating method using a doctor blade, a coating method using a curtain coater, and a coating method using a wire coater. In addition, it is preferable that the surface of the support film to which the inorganic powder-dispersed paste composition is applied is subjected to a release treatment. Thereby, in the transfer step described later, the operation of peeling the support film can be easily performed.

The drying conditions of the coating film are, for example, 50 to
The drying is performed at 150 ° C. for about 0.5 to 30 minutes, and the residual ratio of the solvent after drying (content in the inorganic powder dispersed paste layer) is usually within 2% by weight.

The thickness of the inorganic powder-dispersed paste layer formed on the support film as described above varies depending on the content of the inorganic powder, the type and size of the member, and is, for example, 10 to 100 μm. You. In addition, as a protective film layer which may be provided on the surface of the inorganic powder dispersion paste layer, a polyethylene film, a polyvinyl alcohol-based film, or the like can be used.

<Resist Film (Resist Composition)> In the production method of the present invention, a resist film is formed on the inorganic powder-dispersed paste layer transferred onto the substrate, and the resist film is subjected to an exposure treatment and a development treatment. The application forms a resist pattern on the inorganic powder-dispersed paste layer. The resist film used in the production method of the present invention is characterized in that it contains a compound represented by the above formula (1) as a photoradical generator. The resist composition used to form the resist film includes (A) a binder polymer, (B) a polyfunctional monomer, and (C) a compound represented by the above formula (1) as a photoradical generator. Contains as an essential component.

(A) Binder polymer Binder polymer (A) used in resist composition
Is an ethylenically unsaturated carboxyl group-containing monomer having at least one carboxyl group in the molecule (A
-1) and a carboxyl group obtained by polymerizing a monomer composition comprising a copolymerizable monomer (A-2) copolymerizable with the carboxyl group-containing monomer (A-1). It is preferable to be a containing copolymer.

Specific examples of the carboxyl group-containing monomer (A-1) include (a) unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, (b) itaconic acid, maleic acid and fumaric acid. Unsaturated dicarboxylic acids, such as
And (c) other unsaturated carboxylic acids.
These can be used alone or in combination of two or more.

The carboxyl group-containing monomer (A-
The copolymer containing the structural unit derived from 1) has alkali solubility, and particularly, the copolymer obtained by using the monomer (A-1) in the above ratio is used in an alkali developer. Therefore, the photosensitive resist composition using this as the component (A) has excellent solubility.
The generation of undissolved substances in the alkali developing solution is essentially reduced, and background contamination, film residue, and the like are less likely to occur in portions other than the resist pattern forming portion of the substrate in the developing process. Further, the resist pattern obtained when this copolymer is used as the component (A) does not dissolve excessively in an alkali developing solution and has excellent adhesion to the inorganic powder paste layer. It is hard to fall off from the powder paste layer.

Specific examples of the copolymerizable monomer (A-2) include (a) aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene, (b) methyl acrylate, methyl methacrylate, ethyl Acrylate,
Ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2
-Unsaturated carboxylic acid alkyl esters such as hydroxyethyl methacrylate, benzyl acrylate and benzyl methacrylate; (c) unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate;
(D) unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate;
(E) vinyl carboxylate esters such as vinyl acetate and vinyl propionate; (f) vinyl cyanide compounds such as acrylonitrile, methacrylonitrile and α-chloroacrylonitrile; (g) 1,3-butadiene, isoprene and the like. Aliphatic conjugated dienes, and (h) macromonomers such as polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and polysilicone each having an acryloyl group or a methacryloyl group at each terminal. These can be used alone or in combination of two or more.

The carboxyl group-containing monomer (A-1)
Specific examples of the binder polymer (A) obtained by copolymerizing the copolymer with the copolymerizable monomer (A-2) include methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / methyl methacrylate / styrene. Copolymers, methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymers, methacrylic acid / methyl methacrylate / polystyrene macromonomer copolymers and the like can be mentioned.

The copolymerization ratio of the carboxyl group-containing monomer (A-1) in the binder polymer (A) is from 5 to 50% by weight, especially from 10 to 40% by weight, based on the total amount of the monomers.
It is preferred that Carboxyl group-containing monomer (A
When the copolymerization ratio of -1) is less than 5% by weight, the obtained resist composition tends to have low solubility in an alkali developing solution. On the other hand, when the copolymerization ratio of the carboxyl group-containing monomer (A-1) exceeds 50% by weight, the resist pattern tends to fall off from the inorganic powder paste layer during development.

Such a binder polymer (A) is
The weight average molecular weight in terms of polystyrene (hereinafter, simply referred to as “weight average molecular weight”) measured by gel permeation chromatography (GPC, carrier: tetrahydrofuran) is 3000 to 300000, particularly 50.
It is preferably from 00 to 200,000. By using a binder polymer having such a molecular weight, a resist composition having high developability can be obtained, whereby a resist pattern having a sharp pattern edge can be formed, and a color filter having a uniform pattern can be obtained. Can be formed.

(B) Polyfunctional Monomer Preferred specific examples of the polyfunctional monomer (B) include trimethylolpropane triacrylate, pentaerythritol triacrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetraacrylate, and dipentaerythritol. Examples include trifunctional or higher polyfunctional acrylates such as pentaacrylate and dipentaerythritol hexaacrylate, and oligomers thereof. Among them, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate or pentaerythritol triacrylate is particularly preferable since the strength of the resist pattern is high and background stain or film residue is hardly generated in portions other than the pattern forming portion.

The proportion of the polyfunctional monomer (B) used is usually 100 parts by weight of the binder polymer (A).
It is 5 to 500 parts by weight, preferably 20 to 300 parts by weight. If this proportion is less than 5 parts by weight, the resist pattern strength tends to be insufficient.
On the other hand, when this proportion exceeds 500 parts by weight, the alkali resolution tends to decrease, and background stains other than the resist pattern forming portion, film residue, and the like tend to occur.

(C) Photo-Radical Generator In the present invention, the photo-radical generator of the component (C) is a compound represented by the formula (1), that is, bis (2,6-dimethoxybenzoyl) -2. , 4,4-trimethylpentylphosphine oxide (hereinafter also referred to as "specific compound") is used. By containing the photo-radical generator composed of this specific compound, the curing reaction is sufficiently achieved by the radiation irradiation treatment with a small irradiation energy amount, and the curing reaction does not occur at the place where the radiation is not irradiated, As a result, the coating film after the irradiation treatment is in a state in which a cured portion insoluble in an alkali developing solution and an uncured portion having high solubility in an alkali developing solution are formed.

The specific compound is preferably used in an amount of 0.01 to 200 parts by weight, more preferably 1 to 120 parts by weight, based on 100 parts by weight of the polyfunctional monomer (B). If the proportion is less than 0.01 parts by weight, the curing reaction may not be sufficiently performed in the irradiation treatment, and the resist pattern may be undercut. If this proportion exceeds 200 parts by weight, the resist pattern tends to fall off the substrate during development, and background contamination and film residue may occur at portions other than the resist pattern forming portion.

In the present invention, another photo-radical generator can be used in combination with the specific compound (C). Specific examples of other photoradical generators include:
2,2′-bis (2-chlorophenyl) -4,4 ′,
5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'
-Tetraphenylbiimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-
Tetraphenylbiimidazole, 2,2′-bis (2,
4,6-trichlorophenyl) -4,4 ', 5,5'-
Tetraphenylbiimidazole, 2,2′-bis (2,
4,6-tribromophenyl) -4,4 ', 5,5'-
Tetraphenylbiimidazole, 2-hydroxy-2-
Methyl-1-phenylpropan-1-one, 1- (4-
Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy)
Phenyl- (2-hydroxy-2-propyl) ketone,
1-hydroxycyclohexylphenyl ketone, 2,2
-Dimethoxy-2-phenylacetophenone, 2-methyl (4-methylthiophenyl) -2-morpholino-1
-Propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1
-One, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 2,4-diethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone,
4-azidobenzaldehyde, 4-azidoacetophenone, 4-azidobenzalacetophenone, azidopyrene, 4-diazodiphenylamine, 4-diazo-4'-
Methoxy-diphenylamine, 4-diazo-3-methoxy-diphenylamine, dibenzoyl, benzoinnoisobutylether, N-phenyl-thioacridone,
Triphenylpyrylium perchlorate and the like.

Among these, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl (4
-Methylthiophenyl) -2-morpholino-1-propan-1-one or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-
ON is preferable in that the resist pattern does not drop off from the substrate during development and high resist pattern strength or sensitivity can be obtained. The usage ratio of the other photo radical generator is preferably 80% by weight or less based on the entire photo radical generator.

(D) Solvent The resist composition used in the present invention usually contains a solvent in order to impart appropriate fluidity or plasticity to the photosensitive resist composition and good film-forming properties. . The solvent contained in the resist composition is not particularly limited, and examples thereof include ethers, esters, ether esters, ketones, ketone esters, amides, amide esters, lactams, and lactones. , Sulfoxides, sulfones, hydrocarbons, halogenated hydrocarbons and the like. Specific examples of such a solvent include tetrahydrofuran, anisole, dioxane, ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, acetates, hydroxyacetates, and alkoxyacetic acid. Esters, propionates, hydroxypropionates,
Alkoxypropionates, lactates,
Ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, alkoxyacetates, cyclic ketones, acyclic ketones, acetoacetates, pyruvates, N, N-dialkylformamides, N, N-
Dialkylacetamides, N-alkylpyrrolidones, γ-lactones, dialkylsulfoxides, dialkylsulfones, terpineol, N-methyl-2-
Pyrrolidone and the like can be mentioned, and these can be used alone or in combination of two or more. The content ratio of the solvent in the resist composition can be appropriately selected within a range where good film-forming properties (fluidity or plasticity) can be obtained.

The resist composition used in the present invention includes:
As an optional component, various additives such as a development accelerator, an adhesion aid, an antihalation agent, a storage stabilizer, an antifoaming agent, an antioxidant, an ultraviolet absorber, a filler, a phosphor, a pigment, and a dye are contained. Is also good.

<Exposure Mask> The exposure pattern of the exposure mask M used in the exposure process of the resist film varies depending on the material, but is generally 10 to 500 μm.
It is a stripe of width.

<Developer> In the present invention, an alkaline developer is used in the step of developing the resist film. Examples of the effective component of the alkali developer include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, and ammonium dihydrogen phosphate. , Potassium dihydrogen phosphate, sodium dihydrogen phosphate,
Lithium silicate, sodium silicate, potassium silicate,
Inorganic alkaline compounds such as lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, and ammonia; tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monomethylamine Ethylamine, diethylamine, triethylamine, monoisopropylamine,
Organic alkaline compounds such as diisopropylamine and ethanolamine can be exemplified. The alkali developer used in the step of developing the resist film can be adjusted by dissolving one or more of the above alkaline compounds in water or the like. Here, the concentration of the alkaline compound in the alkaline developer is usually 0.0
The content is 0.01 to 10% by weight, preferably 0.01 to 5% by weight. After the development processing with an alkali developing solution, a washing treatment is usually performed.

<Etching liquid> The etching liquid used in the etching step of the inorganic powder dispersed paste layer includes:
Preferably, it is an alkaline solution. Thereby, the alkali-soluble resin contained in the inorganic powder dispersion paste layer can be easily dissolved and removed. Since the inorganic powder contained in the inorganic powder-dispersed paste layer is uniformly dispersed in the alkali-soluble resin, the inorganic powder is dissolved by dissolving the alkali-soluble resin as a binder in an alkaline solution, and then washing. Is also removed at the same time. Here, examples of the alkaline solution used as the etching solution include a solution having the same composition as the developing solution.
When the etching solution is the same solution as the alkali developing solution used in the developing step, the developing step and the etching step can be performed continuously, and the manufacturing efficiency is reduced by simplifying the steps. Improvement can be achieved.
After the etching treatment with the alkaline solution is performed, a water washing treatment is usually performed.

An organic solvent capable of dissolving the binder of the inorganic powder-dispersed paste layer can also be used as the etching solution. As such an organic solvent,
The solvents exemplified as constituents of the inorganic powder dispersion paste composition can be exemplified. After the etching with the organic solvent is performed, a rinsing with a poor solvent is performed as necessary.

[0059]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited by these. In the following, “parts” and “%” indicate “parts by weight” and “% by weight”, respectively. The weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC) (trade name: HLC-8, manufactured by Tosoh Corporation).
02A) is the average molecular weight in terms of polystyrene measured by the method described in Example 02A).

Example 1 (1) Preparation of Inorganic Powder Dispersion Paste Composition (Composition for Forming Color Filter): Fe powder was used as a red inorganic pigment powder.
20 parts of ₂ O ₃ , butyl methacrylate (50% by weight) and methyl methacrylate (30% by weight) as binder resins
(Weight average molecular weight in terms of polystyrene measured by GPC: 100,000) acrylic resin obtained by copolymerizing methacrylic acid (20 wt%) 20 _{parts, PbO-SiO 2 -B 2 O} 3 -ZnO as low melting glass System glass 80
Parts, and by kneading 15 parts of propylene glycol monomethyl ether as a solvent using a disperser,
An inorganic powder dispersion paste composition for red color having a viscosity of 5,000 cp and used for forming a color filter was prepared.
(Hereinafter referred to as paste (R)). Next, a green inorganic powder dispersed paste composition was prepared in the same manner as the red inorganic powder paste composition, except that Cr ₂ O ₃ was used as the green inorganic pigment. The viscosity was 6,000 cp. (Less than,
Paste (G)) Next, Co as an inorganic pigment for blue color
Except using O-Al ₂ O _3, as well as the red inorganic powder paste composition was prepared blue inorganic powder dispersed paste composition. The viscosity was 5,500 cp. (Less than,
Paste (B))

(2) Preparation of resist composition: 50 parts by weight of methacrylic acid / benzyl methacrylate / styrene copolymer (weight composition ratio: 25/65/10, weight average molecular weight: 40000) as component (A); ) 40 parts by weight of trimethylolpropane triacrylate as a component,
A photosensitive resist composition comprising 24 parts by weight of bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide as the component (C) and 790 parts by weight of ethyl cellosolve acetate as the component (D) Was manufactured.

(3) Production of transfer film:
By the operation of (b), a transfer film having a laminated film of the inorganic powder-dispersed paste layer and the photosensitive resist layer formed on the support film was produced. (A) A supporting film (200 mm wide, 30 mm long) made of a PET film which has been previously subjected to a release treatment of the resist composition.
m, a thickness of 38 μm) using a roll coater,
The coating film is dried at 100 ° C. for 5 minutes to completely remove the solvent,
A resist film having a thickness of 5 μm was formed on the support film. (B) The paste (A) is applied on the resist film using a roll coater, and the coating film is dried at 100 ° C. for 5 minutes to completely remove the solvent, and a 20 μm-thick inorganic powder-dispersed paste layer is formed on the resist film. A transfer film (hereinafter, also referred to as “transfer film (R)”) was formed on the film. For the paste (G) and the paste (B), the same operation as in the above (a) to (b) was performed to produce a transfer film (G) and a transfer film (B).

(4) Laminating film transfer step: A transfer film (R) is superimposed on the surface of a glass substrate for a 6-inch panel so that the surface of the inorganic powder-dispersed paste layer is in contact with the glass substrate.
Thermocompression bonding was performed with a heating roller. Here, as the crimping conditions,
The surface temperature of the heating roller is 120 ° C and the roll pressure is 4kg /
cm ² , and the moving speed of the heating roller was 0.5 m / min.
After the completion of the thermocompression bonding, the support film was peeled off from the laminated film [the surface of the resist film]. Thereby, the laminated film was transferred to the surface of the glass substrate and brought into close contact therewith. When the film thickness of this laminated film [laminated film of the inorganic powder-dispersed paste layer and the resist film] was measured, 25 μm ± 1 μm was obtained.
m.

(5) Exposure process and development process of resist film:
The resist film formed on the inorganic powder-dispersed paste layer was exposed to an i-line (wavelength 365) by an ultra-high pressure mercury lamp through an exposure mask (300 μm width stripe pattern).
nm ultraviolet light). Here, the irradiation amount is 100 m
J / cm ² . Then, a 0.2% by weight aqueous solution of potassium hydroxide (25 wt.
(° C.) as a developing solution by a shower method over 20 seconds. Next, a water washing treatment with ultrapure water was performed, whereby the uncured resist not irradiated with the ultraviolet rays was removed, and a resist pattern was formed.

(6) Etching step of the inorganic powder-dispersed paste layer: Continuing with the above steps, an etching treatment by a shower method using a 0.2% by weight aqueous solution of potassium hydroxide (25 ° C.) as an etching solution is performed. Went over a minute. Next, a washing treatment and a drying treatment with ultrapure water were performed. As a result, a pattern of the inorganic powder-dispersed paste layer composed of the material layer remaining portion and the material layer removing portion was formed. Thereafter, post-baking was performed in an oven at 200 ° C. for 30 minutes.

(7) Green and Blue Laminating Step On the pattern of the inorganic powder dispersion paste layer for red formed in (6), using the transfer film (G) and the transfer film (B), ) To (6) were performed in the same manner to form a stripe pattern composed of the inorganic powder dispersion paste layers for red, green, and blue color filters.

(8) Firing Step of Inorganic Powder Dispersion Paste Layer: A glass substrate on which a pattern of an inorganic powder dispersion paste layer for red, green and blue color filters is formed is placed in a firing furnace at a temperature of 520 ° C. For 30 minutes. As a result, a panel material having the color filter pattern formed on the surface of the glass substrate was obtained. After the above-described processing operation, the substrate and the pattern surface were observed with an optical microscope, and no undissolved matter remained on the substrate. The pattern edge of the formed color filter was sharp, and the pattern width was as good as 300 μm ± 3 μm.

Comparative Example 1 (1) Preparation of resist composition: methacrylic acid / benzyl methacrylate / styrene copolymer as component (A) (weight composition ratio: 25/65/10, weight average molecular weight: 4)
0000) 50 parts by weight, trimethylolpropane triacrylate as component (B) 40 parts by weight, 1-hydroxy-cyclohexyl-phenyl as photoinitiator 24 parts by weight, ethylcellosolve acetate 79 as component (D)
A photosensitive resist composition was produced using 0 parts by weight.

Next, a color filter was formed in the same manner as in Example 1 except that the photosensitive resist composition was used instead of the photosensitive resist composition. After the above-mentioned processing operation, when observed with an optical microscope, peeling was observed at the edge of the pattern.

[0070]

According to the method of manufacturing a plasma display panel of the present invention, since the photo-radical generator (C) comprising a specific compound is contained in the resist composition to be used, radiation with a small irradiation energy amount is obtained. Since the curing reaction is sufficiently achieved by the irradiation treatment, development processing can be easily performed without applying a pattern, and a high-definition pattern can be reliably produced with high efficiency.

[Brief description of the drawings]

FIG. 1 is an explanatory sectional view showing a general AC type PDP.

FIG. 2 is an explanatory sectional view showing a general DC-type PDP.

FIG. 3 is a sectional view for illustrating a method of manufacturing a plasma display panel according to one embodiment of the present invention in the order of steps.

FIG. 4 is an explanatory cross-sectional view showing a step subsequent to the step of FIG. 3 in the manufacturing method according to the embodiment of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Front board 2 Back board 3 Dielectric 3A MgO
Layer 3B Color filter / black matrix layer 4 Phosphor 5 Barrier 6A Sustain electrode 6B Signal electrode 6a Cathode 6b Display anode 6b 'Display anode lead 6c Auxiliary anode 6c' Auxiliary anode lead 7 Resistance 8 Display cell 9 Auxiliary cell 10 Bus line 11 Substrate Reference Signs List 20 transfer film 21 inorganic powder-dispersed paste layer 22 support film 25 inorganic powder-dispersed paste layer pattern 25A material layer remaining portion 25B material layer removing portion 31 resist film M exposure mask MA light transmitting portion (exposure mask) MB light shielding portion (Exposure mask) 35 resist pattern 35A resist remaining portion 35B resist removing portion 40 inorganic pattern 50 panel material

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Nobuo Bessho 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Corporation

Claims (2)

[Claims] An inorganic powder-dispersed paste layer formed on a support film is transferred onto a substrate, and a resist film containing a compound represented by the formula (1) is formed on the inorganic powder-dispersed paste layer. Forming, exposing the resist film to form a latent image of the resist pattern, developing the resist film to reveal the resist pattern, etching the inorganic powder dispersion paste layer to form a resist pattern A method for manufacturing a plasma display panel, comprising forming a panel material having an inorganic pattern by a method including a step of forming a pattern of a corresponding inorganic powder-dispersed paste layer and baking the pattern. 2. A laminated film of a resist film containing a compound represented by the formula (1) and an inorganic powder-dispersed paste layer is formed on a support film, and the laminated film is transferred onto a substrate. The resist film constituting the laminated film is exposed to light to form a latent image of the resist pattern, the resist film is developed to reveal the resist pattern, and the inorganic powder-dispersed paste layer is etched to form a resist pattern. A method for manufacturing a plasma display panel, comprising forming a panel material having an inorganic pattern by a method including a step of forming a pattern of a corresponding inorganic powder-dispersed paste layer and baking the pattern.