JP2005227607A - Inorganic powder-containing resin composition, transfer film and method for producing member for display panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inorganic powder-containing resin composition excellent in storage stability; a transfer film with a layer comprising the resin composition; and a method for producing a display panel using the transfer film. <P>SOLUTION: The inorganic powder-containing resin composition contains: (A) the inorganic powder; (B) a binder resin containing an alkali-soluble resin having a constitutional unit represented by formula (1) (where R denotes a monovalent organic group); (C) a polyfunctional (meth)acrylate; and (D) a photopolymerization initiator. A method for producing a member for a display panel involved in the invention comprises steps of: transferring a resin layer comprising the inorganic powder-containing resin composition onto a substrate using a transfer film with the resin layer; forming a latent image of a pattern by exposing the resin layer; forming the pattern by developing the resin layer; and baking the pattern. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an inorganic powder-containing resin composition suitable for producing a display panel member, a transfer film obtained from the composition, and a method for producing the display panel member using the transfer film.

  In recent years, plasma display panels (hereinafter also referred to as “PDP”), field emission displays (hereinafter also referred to as “FED”), and the like have attracted attention as flat fluorescent displays. A PDP forms a transparent electrode, encloses an inert gas such as argon or neon between two adjacent glass plates, causes plasma discharge to light up the gas, thereby causing phosphors to emit light and display information. It is a display. On the other hand, the FED is a display that displays information by causing a phosphor to emit light by emitting electrons from a cathode into a vacuum by applying an electric field and irradiating the electrons on the anode.

  FIG. 1 is a schematic diagram showing a cross-sectional shape of a conventionally known AC type PDP. In FIG. 1, reference numerals 101 and 102 denote opposing glass substrates, and reference numerals 103 and 111 denote partition walls. Cells are partitioned by the glass substrate 101, the glass substrate 102, the rear partition wall 103, and the front partition wall 111. 104 is a transparent electrode fixed to the glass substrate 101, 105 is a bus electrode formed on the transparent electrode 104 for the purpose of reducing the resistance of the transparent electrode 104, and 106 is an address fixed to the glass substrate 102. 107 is a fluorescent substance held in the cell, 108 is a dielectric layer formed on the surface of the glass substrate 101 so as to cover the transparent electrode 104 and the bus electrode 105, and 109 is an address electrode 106. The dielectric layer is formed on the surface of the glass substrate 102 so as to cover the substrate 110, and 110 is a protective film made of, for example, magnesium oxide. In a color PDP, a color filter (red / green / blue) or a black matrix may be provided between the glass substrate and the dielectric layer in order to obtain a high contrast image.

  FIG. 2 is a schematic view showing a cross-sectional shape of a conventionally known Spindt type FED disclosed in Japanese Patent Application Laid-Open No. 61-221784 (Patent Document 1) and Japanese Patent Application Laid-Open No. 6-124669 (Patent Document 2). . In FIG. 2, reference numerals 201 and 202 denote opposing glass substrates. A transparent electrode 204 and a phosphor 207 serving as an anode electrode are formed on the lower surface of the glass substrate 201, and a cathode electrode 206 is formed on the glass substrate 202. Are stacked. On the cathode electrode 206, an insulating layer 203 and a truncated cone-shaped emitter 205 are formed. A gate 208 having a large number of holes is formed on the insulating layer 203, and cells are partitioned by spacers 209 formed on the gate 208. The emitter 205 is a cathode of a cold cathode using high field emission, and has a feature that electrons can be emitted from the tip of the emitter even when the applied voltage is low. The emitted electrons collide with the phosphor 207 through the gate 208 that concentrates the electric field, and thereby the outermost electrons of the phosphor 207 are excited, whereby an image can be displayed.

  The PDP dielectric layer, partition walls, electrodes, phosphor, color filter, and black matrix are produced by forming a photosensitive resin layer containing an inorganic powder on a substrate and passing the resin layer through a photomask. For example, a photolithography method including a step of developing by irradiating ultraviolet rays and baking a pattern formed on a substrate is suitably used (see Patent Documents 3 to 5).

  As a method for forming a photosensitive resin layer containing an inorganic powder on a substrate, a transfer film in which the resin layer is formed on a flexible support film is used to transfer and form the resin layer. The method is preferably used. Thus, by using a transfer film, a resin layer with excellent thickness uniformity can be obtained, and work efficiency can be improved.

  However, in the photosensitive resin composition containing the inorganic powder, there is a problem that when the inorganic powder containing the polyvalent metal and / or the polyvalent metal oxide is used, the resin composition is gelled. . This is because an alkali-soluble polymer having an unsaturated double bond is usually used as a binder resin in order to impart photosensitivity and alkali-solubility to the composition. ) And the polyvalent metal hydroxide on the surface of the inorganic powder are caused to react with each other.

As described above, when the resin composition containing the inorganic powder is gelled, not only the film formation becomes difficult, but even if the film can be formed into a film, the development process becomes unstable. The composition could not be stored for a long time. Therefore, an inorganic powder-containing resin composition that hardly gels even after long-term storage has been desired.
Japanese Patent Application Laid-Open No. Sho 61-221783 JP-A-6-124669 JP-A-9-102273 Japanese Patent Laid-Open No. 11-144628 Japanese Patent Laid-Open No. 11-162339

  An object of the present invention is to provide an inorganic powder-containing resin composition excellent in storage stability, a transfer film having a layer made of the resin composition, and a method for producing a display panel member using the transfer film. is there.

Inorganic powder-containing resin composition according to the present invention,
(A) inorganic powder,
(B) a binder resin containing an alkali-soluble resin having a structural unit represented by the following general formula (1);

(In the formula, R represents a monovalent organic group.)
It contains (C) a polyfunctional (meth) acrylate and (D) a photopolymerization initiator.

The transfer film according to the present invention has an inorganic powder-containing resin layer formed using the inorganic powder-containing resin composition.

A method for producing a member for a display panel according to the present invention is as follows.
Transferring the inorganic powder-containing resin layer constituting the transfer film onto a substrate;
A step of exposing the inorganic powder-containing resin layer to form a latent image of a pattern,
It includes a step of developing the inorganic powder-containing resin layer to form a pattern, and a step of baking the pattern.

  According to the present invention, an inorganic powder-containing resin composition that can suppress an increase in viscosity due to gelation even when stored for a long period of time is obtained.

  The transfer film of the present invention having a photosensitive resin layer formed from the resin composition is excellent in transferability, and by using the transfer film, a display panel member having an excellent pattern shape can be formed. .

  Hereinafter, the inorganic powder-containing resin composition according to the present invention, a transfer film having a layer made of the resin composition, and a method for producing a display panel member using the transfer film will be described in detail.

<Inorganic powder-containing resin composition>
The inorganic powder-containing resin composition of the present invention is a paste comprising (A) inorganic powder, (B) a binder resin, (C) a polyfunctional (meth) acrylate, and (D) a photopolymerization initiator. Composition.

(A) Inorganic powder The inorganic powder used in the inorganic powder-containing resin composition of the present invention is an inorganic powder containing a metal and / or a metal oxide, although it varies depending on the type of components to be formed. is there.

  For example, glass powder is mentioned as an inorganic powder used for the composition for forming the "dielectric layer" and "partition" which comprise PDP. The glass powder preferably has a softening point in the range of 400 to 600 ° C. When the softening point of the glass powder is in the above range, the firing step in producing the PDP or FED member can be performed satisfactorily. As a result, an organic substance such as a binder resin does not remain in the constituent member, so that the lifetime of the phosphor is not reduced due to diffusion of outgas into the panel, and the glass substrate is not distorted. .

As the glass powder suitably used for the resin composition of the present invention,
(1) Lead oxide, boron oxide, silicon oxide, calcium oxide (PbO—B ₂ O ₃ —SiO ₂₎
-CaO system),
(2) Zinc oxide, boron oxide, silicon oxide type (ZnO—B ₂ O ₃ —SiO ₂ type),
(3) Lead oxide, boron oxide, silicon oxide, aluminum oxide system (PbO—B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ system),
(4) Lead oxide, zinc oxide, boron oxide, silicon oxide system (PbO—ZnO—B ₂ O ₃ —SiO ₂ system),
(5) Lead oxide, zinc oxide, boron oxide, silicon oxide, titanium oxide system (PbO—ZnO—B ₂ O ₃ —SiO ₂ —TiO ₂ system),
(6) Bismuth oxide, boron oxide, silicon oxide system (Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ system),
(7) Zinc oxide, phosphorus oxide, silicon oxide type (ZnO—P ₂ O ₅ —SiO ₂ type),
(8) Zinc oxide, boron oxide, potassium oxide (ZnO—B ₂ O ₃ —K ₂ O),
(9) Phosphorus oxide, boron oxide, aluminum oxide system (P ₂ O ₅ —B ₂ O ₃ —Al ₂ O ₃ system),
(10) Zinc oxide, phosphorus oxide, titanium oxide (ZnO—P ₂ O ₅ —TiO ₂ ) mixture and the like can be mentioned. Moreover, you may mix and use inorganic oxide powders, such as aluminum oxide, chromium oxide, manganese oxide, for example to the said glass powder.

  The glass powder may be contained (combined) in a composition for forming another component, for example, an electrode, a resistor, a phosphor, a color filter, and a black matrix. When using together the said glass powder and inorganic powders other than this glass powder with the resin composition of this invention, this glass powder is normally used in the quantity of 90 mass% or less with respect to the inorganic powder whole quantity.

  Examples of the inorganic powder used in the composition for forming the “electrode” constituting the PDP, for example, the transparent electrode 104, the bus electrode 105, and the address electrode 106 in FIG. 1 include Ag, Au, Al, Ni, and Ag. -Metal powder made of -Pd alloy, Cu, Cr or the like.

Examples of the inorganic powder used in the composition for forming the “resistor” constituting the PDP include inorganic powders such as RuO ₂ .

As inorganic powders used in the composition for forming the “phosphor” constituting the PDP, Y ₂ O ₃ : Eu ³⁺ , Y ₂ SiO ₅ : Eu ³⁺ , Y ₃ Al ₅ O ₁₂ : YVO ₄ : Eu ³⁺ , (Y, Gd
) Red fluorescent material having a composition such as 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 :
A green phosphor having a composition such as (Ce, Tb), Y ₃ (Al, Ga) ₅ O ₁₂ : Tb;
Y ₂ SiO ₅ : Ce, BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , BaMgAl ₁₄ O ₂₃ : Eu ²⁺ , (Ca, Sr, Ba) ₁₀ (PO ₄ ) _{6 Cl 2} : Eu ²⁺ , (Zn, Cd) S: Inorganic powder made of a fluorescent material for blue having a composition such as Ag.

Inorganic powders used in the composition for forming the “color filter” constituting the PDP include red materials such as Fe ₂ O ₃ and Pb ₃ O ₄ , green materials such as Cr ₂ O ₃ , 2 Examples thereof include inorganic powders made of blue materials such as (Al ₂ Na ₂ Si ₃ O ₁₀ ) · Na ₂ S ₄ .

  Examples of the inorganic powder used in the composition for forming the “black matrix” constituting the PDP include metal powder made of Mn, Fe, Cr and the like.

(B) Binder Resin As the binder resin in the composition of the present invention, an alkali-soluble resin is used. The binder resin used in the composition of the present invention contains an alkali-soluble resin in a proportion of 30 to 100% by weight. The term “alkali-soluble” in the present invention refers to a property of being dissolved in an alkaline etching solution described later and having solubility to such an extent that a desired etching process is performed.

  The alkali-soluble resin used in the present invention is a resin having a structural unit represented by the following general formula (1) (hereinafter also referred to as the structural unit (1)), specifically, an acrylate having an α-hydroxymethyl group. Is a resin having as a constituent monomer.

  In the formula (1), R represents a monovalent organic group, for example, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, or an n-butyl group.

  By using the alkali-soluble resin having the structural unit (1), a reaction with a metal and / or metal oxide hardly occurs, and an inorganic powder-containing resin composition excellent in storage stability can be obtained.

  Examples of the (meth) acrylate having an α-hydroxymethyl group preferably used in the present invention include methyl-α- (hydroxymethyl) acrylate, ethyl-α- (hydroxymethyl) acrylate, and n-propyl-α- (hydroxymethyl). Examples include acrylate and alkyl-α- (hydroxymethyl) acrylate such as n-butyl-α- (hydroxymethyl) acrylate. Among these, methyl-α- (hydroxymethyl) acrylate, ethyl-α- (hydroxymethyl) acrylate and n-butyl-α- (hydroxymethyl) acrylate are particularly preferable.

  In the alkali-soluble resin used in the present invention, the content of the structural unit (1) is 30 to 100 mol%, preferably 40 to 90 mol%. When the content is in the above range, the storage stability which is the effect of the present invention is sufficiently expressed.

  Examples of other constituent monomers in the alkali-soluble resin used in the present invention include monomers selected from the group consisting of the following monomers (A) to (C).

Monomer (I):
Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene Alkali-soluble functional group-containing monomers copolymerizable with (meth) acrylates having an α-hydroxymethyl group, such as phenolic hydroxyl group-containing monomers such as

Monomer (b):
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, ethoxyethyl (meth) acrylate, dicyclopentanyl ( (Meth) acrylates other than the monomer (a) such as (meth) acrylate; aromatic vinyl monomers such as styrene and α-methylstyrene; α-hydroxymethyl groups such as conjugated dienes such as butadiene and isoprene Monomers copolymerizable with (meth) acrylates.

Monomer (C):
Polystyrene, poly (meth) acrylate, poly (meth) ethyl acrylate, poly (
Macromonomers such as a macromonomer having a polymerizable unsaturated group such as a (meth) acryloyl group at one end of a polymer chain such as benzyl methacrylate.
Of these, 2-ethylhexyl (meth) acrylate and ethoxyethyl (meth) acrylate are particularly preferred.

  The alkali-soluble resin preferably has a weight average molecular weight (Mw) of 5,000 to 5,000,000, particularly preferably 10,000 to 300,000. When Mw is in the above range, sufficient alkali solubility and film formability can be obtained. In addition, said Mw is the weight average molecular weight of polystyrene conversion by GPC measurement.

  The content of the binder resin containing the alkali-soluble resin in the composition of the present invention is usually 1 to 50 parts by weight, preferably 1 to 40 parts by weight with respect to 100 parts by weight of the inorganic powder. When the content of the binder resin is in the above range, the effects of the present invention are sufficiently exhibited.

(C) Polyfunctional (meth) acrylate The polyfunctional (meth) acrylate constituting the composition of the present invention has a property of being polymerized by exposure so that the exposed portion becomes alkali-insoluble or alkali-insoluble.

As the polyfunctional (meth) acrylate used in the present invention,
Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Di (meth) acrylates of both end hydroxylated polymers such as both end hydroxy polybutadiene, both end hydroxy polyisoprene, both end hydroxy polycaprolactone;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, 1,2,4-butanetriol, trimethylolalkane, tetramethylolalkane, pentaerythritol, dipentaerythritol;
Poly (meth) acrylates of polyalkylene glycol adducts of trihydric or higher polyhydric alcohols;
Poly (meth) acrylates of cyclic polyols such as 1,4-cyclohexanediol and 1,4-benzenediol;
Examples include oligo (meth) acrylates such as polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirane resin (meth) acrylate. . These may be used alone or in combination of two or more. Among these, poly (meth) acrylates of trihydric or higher polyhydric alcohols and di (meth) acrylates of polyalkylene glycol are particularly preferably used.

  The molecular weight of the polyfunctional (meth) acrylate is preferably 100 to 2,000.

  Content of the said polyfunctional (meth) acrylate in the composition of this invention is 30-70 weight part normally with respect to 100 weight part of said inorganic powder, Preferably it is 40-60 weight part.

(D) Photopolymerization initiator As the photopolymerization initiator constituting the composition of the present invention, benzyl, benzoin, benzophenone, camphorquinone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- [4 '-(methylthio) phenyl] -2-morpholino-
Carbonyl compounds such as 1-propanone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; azo compounds such as azoisobutyronitrile and 4-azidobenzaldehyde or azide compounds Organic sulfur compounds such as mercaptan disulfide; organic peroxides such as benzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, and paraffin hydroperoxide; 1,3-bis (trichloro Methyl) -5- (2′-chlorophenyl) -1,3,5-triazine, 2- [2- (2-furanyl) ethylenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine Trihalomethanes such as 2,2′-bis (2-chloro Phenyl) 4,5,4 ', such as imidazole dimer such as 5'-tetraphenyl 1,2'-biimidazole and the like. These may be used alone or in combination of two or more.

  Content of the said photoinitiator in the composition of this invention is 0.1-100 weight part normally with respect to 100 weight part of said polyfunctional (meth) acrylates, Preferably it is 1-50 weight part.

(E) Others The composition of the present invention usually contains a solvent for imparting appropriate fluidity or plasticity and good film-forming properties. As the solvent used in the present invention, the affinity with the inorganic powder and the solubility of the binder resin are good, the composition can be imparted with an appropriate viscosity, and can be easily removed by evaporation. A solvent is preferred.

  The solvent used in the present invention is not particularly limited as long as it has the above characteristics. For example, ethers, esters, ether esters, ketones, ketone esters, amides, amide esters, lactams, Examples include lactones, sulfoxides, sulfones, hydrocarbons, and halogenated hydrocarbons.

  More specifically, tetrahydrofuran, anisole, dioxane, ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, acetate esters, hydroxyacetate esters, alkoxyacetate esters , Propionic acid esters, hydroxypropionic acid esters, alkoxypropionic acid esters, lactic acid esters, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, alkoxyacetic acid esters, cyclic ketones, acyclic Ketones, acetoacetic esters, pyruvates, N, N-dialkylformamides, N, N-dialkylamides Toamido acids, N- alkylpyrrolidones, .gamma.-lactones, dialkyl sulfoxides, dialkyl sulfones, terpineol, etc. N- methyl-2-pyrrolidone. These may be used alone or in combination of two or more.

  What is necessary is just to select suitably content of the said solvent in the composition of this invention in the range in which favorable film-forming property (fluidity or plasticity) is obtained.

  In the composition of the present invention, various additives such as a plasticizer, a development accelerator, an adhesion assistant, an antihalation agent, a storage stabilizer, an antifoaming agent, an antioxidant, an ultraviolet absorber, and a filler are optionally included. It may be contained.

<Transfer film>
The transfer film of the present invention is formed by forming a layer made of the inorganic powder-containing resin composition of the present invention on a support film. The inorganic powder-containing resin layer (hereinafter also simply referred to as “resin layer” or “photosensitive resin layer”) is formed by applying the composition to a support film to form a coating film, and then drying the coating film. Can be obtained.

  The support film constituting the transfer film is preferably a resin film having heat resistance and solvent resistance and flexibility. When the support film has flexibility, the paste-like composition can be applied by a roll coater, and the inorganic powder-containing resin layer can be stored and supplied in a state of being wound in a roll. In addition, as thickness of a support film, it should just be a range suitable for use, for example, is 20-100 micrometers.

  Examples of the resin that forms the support film include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, polyfluoroethylene, and other fluorine-containing resins, nylon, and cellulose.

  The method of applying the composition of the present invention on the support film is not particularly limited as long as it is a method capable of efficiently forming a coating film having a large film thickness (for example, 10 μm or more) and excellent uniformity. For example, a coating method using a roll coater, a coating method using a doctor blade, a coating method using a curtain coater, a coating method using a die coater, and a coating method using a wire coater.

  In addition, it is preferable that the mold release process is given to the surface of the support film with which the composition of this invention is apply | coated. Thereby, the peeling operation of a support film can be easily performed in the case of PDP structural member formation.

  What is necessary is just to adjust the drying conditions of a coating film suitably so that the residual ratio of the solvent after drying (solvent content rate in a resin layer) may be within 2 mass%, for example, at the drying temperature of 50-150 degreeC, 0 About 5 to 30 minutes.

  The thickness of the resin layer formed on the support film as described above varies depending on the content and size of the inorganic powder, but is, for example, 5 to 500 μm.

  In addition, as a protective film layer which may be provided on the surface of a resin layer, a polyethylene film, a polyvinyl alcohol-type film, etc. are mentioned.

<Method for producing display panel member>
The production method of the present invention can be used for PDP constituent members, FED constituent members, and the like, but is particularly preferably used for PDP constituent members.

  These members are formed by forming an inorganic powder-containing resin layer on a substrate using the inorganic powder-containing resin composition of the present invention or the transfer film of the present invention, and exposing the resin layer to form a latent image of the pattern. Then, the resin layer is developed to form a pattern layer, and the pattern layer is baked.

(I) Step of forming inorganic powder-containing resin layer The inorganic powder-containing resin layer is formed by applying the inorganic powder-containing resin composition of the present invention on a substrate or using the transfer film of the present invention. It can be formed by transferring an inorganic powder-containing resin layer.

According to the method using a transfer film, a resin layer excellent in film thickness uniformity can be easily formed, and the film thickness of the formed pattern can be made uniform. Moreover, you may form the laminated body which has a resin layer of n layer (n shows an integer greater than or equal to 2) by repeating transcription | transfer n times using the said transfer film. Or you may form the said laminated body by batch-transferring on the board | substrate using the transfer film in which the laminated body which consists of a resin layer of n layers was formed on the support film.

  Examples of the method for applying the composition of the present invention on a substrate include various methods such as screen printing, roll coating, spin coating, and cast coating. After applying the composition by such a method, the resin layer can be formed by drying the coating film. In addition, you may form the laminated body which consists of n layer by repeating the said process n times.

  An example of a transfer process using a transfer film is as follows. After peeling off the protective film layer of the transfer film used as necessary, the transfer film is overlaid so that the surface of the resin layer is in contact with the surface of the substrate, and this transfer film is thermocompression bonded with a heating roller, etc. The support film is peeled off from the layer. As a result, the resin layer is transferred and adhered to the surface of the substrate.

  For example, the surface temperature of the heating roller is 40 to 140 ° C., the roll pressure by the heating roller is 0.1 to 10 kg / cm, and the moving speed of the heating roller is 0.1 to 10 m / min. Moreover, the board | substrate may be preheated and the preheating temperature is 40-140 degreeC, for example.

(Ii) Exposure Step The surface of the inorganic powder-containing resin layer is selectively irradiated (exposed) with radiation such as ultraviolet rays through an exposure mask to form a pattern latent image on the resin layer. The radiation irradiation apparatus used in the exposure is not particularly limited, but an ultraviolet irradiation apparatus generally used in a photolithography method, an exposure apparatus used in manufacturing a semiconductor or a liquid crystal display device, and the like. Can be mentioned.

  In addition, when the inorganic powder-containing resin layer is formed by transfer, it is preferable to perform the exposure without peeling off the support film coated on the resin layer.

(Iii) Development step The exposed resin layer is developed to form a resin layer pattern. Development methods (for example, immersion method, rocking method, shower method, spray method, paddle method, etc.) and development processing conditions (for example, developer type / composition / concentration, development time, development temperature, etc.) are inorganic powders. What is necessary is just to select and set suitably according to the kind of containing resin layer.

(Vi) Firing Step In order to burn off the organic substance in the resin layer remaining portion after development, the pattern of the formed resin layer is subjected to a firing treatment. The firing treatment condition requires that the organic substance in the inorganic powder-containing resin layer (residual part) be burned off, and the firing temperature is usually 400 to 600 ° C. and the firing time is 10 to 90 minutes.

  By the manufacturing method of the present invention including the above steps, PDP components such as partition walls, electrodes, resistors, derivatives, phosphors, color filters, and black matrices can be formed. In particular, the production method of the present invention is preferable as a method for producing a partition wall. The film thickness of the pattern obtained according to the present invention is, for example, 1 to 200 μm, although it varies depending on the use and the content of the inorganic powder.

  Next, materials and various conditions used in the above steps will be described.

(substrate)
Examples of the substrate material used in the present invention include a plate-like member made of an insulating material such as glass, silicone, polycarbonate, polyester, aromatic amide, polyamideimide, and polyimide. If necessary, the surface of the plate-like member may be subjected to chemical treatment with a silane coupling agent or the like; plasma treatment; thin film formation treatment by an ion plating method, a sputtering method, a gas phase reaction method, a vacuum deposition method, or the like. Processing may be performed.

  In the present invention, it is preferable to use glass having heat resistance as the substrate. An example of such a glass substrate is PD200 manufactured by Asahi Glass Co., Ltd.

(Exposure mask)
The exposure pattern of the exposure mask used in the exposure step in the production method of the present invention is generally a stripe having a width of 10 to 500 μm, although it varies depending on the material.

(Developer)
The developer used in the development step in the production method of the present invention is an alkaline developer. Since the inorganic powder contained in the inorganic powder-containing resin layer is uniformly dispersed by the alkali-soluble resin, the inorganic powder is dissolved by washing the alkali-soluble resin, which is the binder resin, with an alkali developer and washing. The body is also removed at the same time.

  As an active ingredient of the alkaline developer, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate , Inorganic such as potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia Alkaline compounds; tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropyl Triethanolamine, and organic alkaline compounds such as ethanol amine.

  The alkaline developer can be prepared by dissolving one or more of the alkaline compounds in water or the like. The density | concentration of the alkaline compound in an alkali developing solution is 0.001-10 mass% normally, Preferably it is 0.01-5 mass%. In addition, after the development process with an alkali developer is performed, a washing process is usually performed.

〔Example〕
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited by these.

In the following, “part” means “part by weight”. Moreover, a weight average molecular weight (Mw) is a weight average molecular weight of polystyrene conversion measured on condition of the following using gel permeation chromatography (GPC).
(Measurement condition)
GPC measuring device: HLC-8220 GPC manufactured by Tosoh Corporation
GPC column: TSKgelSuperHZN-M manufactured by Tosoh Corporation
Measuring solvent: Tetrahydrofuran Measuring temperature: 40 ° C
Moreover, the storage stability of the obtained composition was evaluated by the following method. First, the viscosity of the composition immediately after preparation was measured at 25 ° C using a rotary viscometer (EMD-R type, manufactured by Tokyo Keiki Co., Ltd.), and this was used as the initial viscosity. Next, the viscosity of the composition was periodically measured while being stored at 5 ° C. under light-shielding conditions, and the storage stability was evaluated by the number of days until the viscosity increased by 50% from the initial viscosity.

<Synthesis Example 1>
150 parts of propylene glycol monomethyl ether acetate, 70 parts of methyl-α- (hydroxymethyl) acrylate, 30 parts of 2-ethylhexyl methacrylate, 3 parts of azobisisobutyronitrile and 2,4-diphenyl-4-methyl-1-pentene 2 The portion was charged into an autoclave equipped with a stirrer and stirred at room temperature in a nitrogen atmosphere until uniform. After stirring, the polymerization was carried out at 80 ° C. for 4 hours, and further the polymerization reaction was continued at 100 ° C. for 1 hour, followed by cooling to room temperature to obtain a polymer solution. The obtained polymer solution had a polymerization rate of 87%, and the Mw of the copolymer (resin I) precipitated from this polymer solution was 13,000.

<Synthesis Example 2>
In Synthesis Example 1, a copolymer (resin II) having an Mw of 20,000 was obtained in the same manner as in Synthesis Example 1 except that 30 parts of ethoxyethyl methacrylate was used instead of 30 parts of 2-ethylhexyl methacrylate.

<Synthesis Example 3>
In Synthesis Example 1, 70 parts of methyl-α- (hydroxymethyl) acrylate was changed to 50 parts, and Mw was changed in the same manner as in Synthesis Example 1 except that 50 parts of ethoxyethyl methacrylate was used instead of 30 parts of 2-ethylhexyl methacrylate. Of 31,000 (resin III) was obtained.

<Synthesis Example 4>
In Synthesis Example 1, instead of 70 parts of methyl-α- (hydroxymethyl) acrylate and 30 parts of 2-ethylhexyl methacrylate, 40 parts of methyl-2-ethylhexyl methacrylate, 20 parts of methacrylic acid, 30 parts of n-butyl methacrylate, 2- A copolymer (resin IV) having a Mw of 100,000 was obtained in the same manner as in Synthesis Example 1 except that 10 parts of hydroxypropyl methacrylate was used.

<Example 1>
(1) Preparation of resin composition containing inorganic powder:
(A) 100 parts of PbO—SiO ₂ low melting point glass frit (indefinite shape, softening point 570 ° C.) having an average particle size of 1.7 μm as inorganic powder, (B) synthesis as alkali-soluble resin (binder resin) 14 parts of the resin I obtained in Example 1, (C) As a polyfunctional (meth) acrylate compound, 8 parts of trimethylolpropane triacrylate and 8 parts of polyethylene glycol diacrylate, (D) As a photopolymerization initiator, 2- 4 parts of benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, (E) 20 parts of propylene glycol monomethyl ether acetate as solvent and (F) normal decyltrimethoxy as dispersant After kneading 1 part of silane with a bead mill, filter with a stainless mesh (500 mesh, 25 μm diameter). By doing this, an inorganic powder-containing resin composition was prepared.

  When the storage stability of the obtained composition was evaluated, storage stability of 90 days or more was obtained.

(2) Preparation of transfer film:
The obtained inorganic powder-containing resin composition was applied on a support film (width 200 mm, length 300 m, thickness 38 μm) made of a PET film, which had been subjected to release treatment in advance, using a blade coater, and the coating film was applied at 100 ° C. By drying for 5 minutes to completely remove the solvent, an inorganic powder-containing photosensitive resin layer having an average film thickness of 46 μm was formed. Next, a protective film made of a PET film that had been subjected to a release treatment in advance was thermocompression-bonded on the resin layer to produce a transfer film in which a support film, an inorganic powder-containing photosensitive resin layer, and a protective film were sequentially laminated.

(3) Formation of members
(i) Transfer process of inorganic powder-containing resin layer:
After the protective film of the obtained transfer film is peeled and removed, the transfer film is superposed on the dielectric layer (20 μm) formed on the surface of the 6-inch panel glass substrate so that the resin layer surface comes into contact therewith. The film was thermocompression bonded with a heating roller. The pressure bonding conditions at this time were such that the surface temperature of the heating roller was 90 ° C., the roll pressure was 2 kg / cm ² , and the moving speed of the heating roller was 0.5 m / min. As a result, the photosensitive resin layer containing the inorganic powder was transferred and adhered to the surface of the glass substrate.

(ii) Exposure process and development process of photosensitive resin layer:
The photosensitive resin layer formed as described above is irradiated with i-line (ultraviolet light having a wavelength of 365 nm) through an exposure mask (a stripe pattern having a width of 400 μm) with an ultrahigh pressure mercury lamp at a dose of 400 mJ / cm ^2. Irradiated with.

  After completion of the exposure process, the support film is peeled off from the resin layer, and then developed by a shower method using a 0.1 N aqueous sodium hydroxide solution (30 ° C.) as a developer for the exposed resin layer. Processing was carried out for 1 minute. Next, a water washing treatment with ultrapure water was performed, whereby the uncured resin layer that was not irradiated with ultraviolet rays was removed, and a resin layer pattern containing inorganic powder was formed.

(iii) Resin layer pattern firing step:
The glass substrate on which the resin layer pattern was formed on the dielectric layer was baked for 50 minutes in a 590 ° C. temperature atmosphere in a baking furnace. When the cross-sectional shape of the partition wall in the obtained panel material was observed with a scanning electron microscope and the width and height of the bottom surface of the cross-sectional shape were measured, the width of the bottom surface was 400 μm and the height was 20 μm. A fired pattern was obtained. As a result, a panel material in which partition walls were formed on the dielectric layer was obtained.

<Examples 2 and 3, Comparative Example 1>
Except having changed alkali-soluble resin into what is shown in Table 1, it carried out similarly to Example 1, and prepared the inorganic powder containing resin composition, and evaluated the storage stability. Next, a transfer film was produced using the composition, a panel material was produced using the transfer film, and transferability and pattern shape were evaluated. The results are shown in Table 1.

<Example 4>
(1) Preparation of resin composition containing inorganic powder:
(A) 100 parts of PbO—SiO ₂ low melting point glass frit (indefinite shape, softening point 560 ° C.) having an average particle size of 1.1 μm as inorganic powder, (B) synthesis as alkali-soluble resin (binder resin) 14 parts of the resin I obtained in Example 1, (C) As a polyfunctional (meth) acrylate compound, 8 parts of trimethylolpropane triacrylate and 8 parts of polyethylene glycol diacrylate, (D) As a photopolymerization initiator, 2- 4 parts of benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, (E) 20 parts of propylene glycol monomethyl ether acetate as solvent and (F) normal decyltrimethoxy as dispersant After kneading 1 part of silane with a bead mill, filter with a stainless mesh (500 mesh, 25 μm diameter). By doing this, an inorganic powder-containing resin composition was prepared.

(2) Preparation of transfer film:
The obtained inorganic powder-containing resin composition was applied onto a support film (width 200 mm, length 300 mm, thickness 38 μm) made of a PET film which had been subjected to release treatment in advance using a blade coater, and the coating film was applied at 100 ° C. By drying for 10 minutes to completely remove the solvent, an inorganic powder-containing photosensitive resin layer having an average film thickness of 200 μm was formed. Next, a protective film made of a PET film that had been subjected to a release treatment in advance was thermocompression-bonded on the resin layer to produce a transfer film in which a support film, an inorganic powder-containing photosensitive resin layer, and a protective film were sequentially laminated.

(3) Formation of members
(i) Transfer process of inorganic powder-containing resin layer:
After the protective film of the obtained transfer film was peeled and removed, the transfer film was superposed on a 6-inch panel glass substrate so that the resin layer surface was in contact, and this transfer film was thermocompression bonded with a heating roller. The pressure bonding conditions at this time were such that the surface temperature of the heating roller was 90 ° C., the roll pressure was 2 kg / cm ² , and the moving speed of the heating roller was 0.5 m / min. As a result, the photosensitive resin layer containing the inorganic powder was transferred and adhered to the surface of the glass substrate.

(ii) Exposure process and development process of photosensitive resin layer:
The photosensitive resin layer formed as described above is irradiated with i-line (ultraviolet light having a wavelength of 365 nm) through an exposure mask (a stripe pattern having a width of 40 μm) with an ultrahigh pressure mercury lamp at a dose of 400 mJ / cm ^2. Irradiated with.

  After completion of the exposure process, the support film is peeled off from the resin layer, and then developed by a shower method using a 0.1 N aqueous sodium hydroxide solution (30 ° C.) as a developer for the exposed resin layer. Treatment was carried out for 3 minutes. Next, a water washing treatment with ultrapure water was performed, whereby the uncured resin layer that was not irradiated with ultraviolet rays was removed, and a resin layer pattern containing inorganic powder was formed.

(iii) Resin layer pattern firing step:
The glass substrate on which the resin layer pattern was formed was baked for 15 minutes in a 560 ° C. temperature atmosphere in a baking furnace. When the cross-sectional shape of the partition wall in the obtained panel material was observed with a scanning electron microscope and the width and height of the bottom surface of the cross-sectional shape were measured, the width of the bottom surface was 40 μm ± 2 μm, and the height was 120 μm ± 3 μm, The dimensional accuracy was extremely high, and residues, pattern peeling, and deformation were not observed. Thereby, the panel material in which a partition was formed on the glass substrate was obtained.

It is sectional drawing for description which shows a general PDP. It is sectional drawing for description which shows a general FED.

Explanation of symbols

DESCRIPTION OF SYMBOLS 101 Glass substrate 102 Glass substrate 103 Back partition 104 Transparent electrode 105 Bus electrode 106 Address electrode 107 Phosphor 108 Dielectric layer 109 Dielectric layer 110 Protective film 111 Front partition 201 Glass substrate 202 Glass substrate 203 Insulating layer 204 Transparent electrode 205 Emitter 206 Cathode electrode 207 Phosphor 208 Gate 209 Spacer

Claims (10)

(A) inorganic powder,
(B) a binder resin containing an alkali-soluble resin having a structural unit represented by the following general formula (1);

(In the formula, R represents a monovalent organic group.)
An inorganic powder-containing resin composition comprising (C) a polyfunctional (meth) acrylate, and (D) a photopolymerization initiator.   The inorganic powder-containing resin composition according to claim 1, wherein the structural unit represented by the formula (1) is a structural unit derived from an acrylate having an α-hydroxymethyl group.   The acrylate having an α-hydroxymethyl group is at least one selected from methyl-α- (hydroxymethyl) acrylate, ethyl-α- (hydroxymethyl) acrylate and n-butyl-α- (hydroxymethyl) acrylate. The resin composition containing inorganic powder according to claim 2.   The alkali-soluble resin is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, ethoxyethyl (meth) acrylate And a copolymer of at least one (meth) acrylate selected from the group consisting of dicyclopentanyl (meth) acrylate and an acrylate having an α-hydroxymethyl group. An inorganic powder-containing resin composition according to any one of the above.   The inorganic powder-containing resin composition according to any one of claims 1 to 4, wherein the alkali-soluble resin contains 40 to 90 mol% of a structural unit represented by the formula (1).   The inorganic powder-containing resin composition according to any one of claims 1 to 5, wherein the inorganic powder is a glass powder having a softening point of 400 to 600 ° C.   A transfer film comprising an inorganic powder-containing resin layer formed using the inorganic powder-containing resin composition according to claim 1. Transferring the inorganic powder-containing resin layer constituting the transfer film according to claim 7 onto a substrate;
A step of exposing the inorganic powder-containing resin layer to form a latent image of a pattern,
A method for producing a member for a display panel, comprising: a step of developing the inorganic powder-containing resin layer to form a pattern; and a step of baking the pattern.   The method for manufacturing a display panel member according to claim 8, wherein the display panel member is a plasma display panel member.   The plasma display panel according to claim 9, wherein the plasma display panel member is at least one member selected from a partition, an electrode, a resistor, a dielectric, a phosphor, a color filter, and a black matrix. Method for manufacturing a member.

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