JP4661388B2 - Inorganic powder-containing resin composition, transfer film, and method for producing plasma display panel member - Google Patents

Description

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

  In recent years, a plasma display panel (hereinafter also referred to as “PDP”) has attracted attention as a flat fluorescent display. 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.

  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 electrode fixed to the glass substrate 102. 107 is a fluorescent material 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. A dielectric layer is formed on the surface of the glass substrate 102 so as to cover it, 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.

  As a method for producing such a PDP member, for example, a dielectric layer, a partition, an electrode, a phosphor, a color filter, and a black matrix, a photosensitive resin layer containing an inorganic powder is formed on a substrate, and the resin A photolithography method or the like including a step of irradiating the layer with ultraviolet rays through a photomask for development and baking a pattern formed on the substrate is suitably used (see Patent Documents 1 to 3).

  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.
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 having excellent storage stability, a transfer film having a layer comprising the resin composition, and a method for producing a member for PDP using the transfer film. .

Inorganic powder-containing resin composition according to the present invention,
(A) inorganic powder,
(B) a polymer having a structural unit represented by the following formula (1),

(In the formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is an alkyl group having 1 to 5 carbon atoms, m and n are integers of 1 to 5 and m ≠ n. a is an integer of 1 to 100, and b is an integer of 0 to 100.)
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.
The method for producing a PDP member according to the present invention includes a step of transferring an inorganic powder-containing resin layer constituting the transfer film onto a substrate using the transfer film, and subjecting the inorganic powder-containing resin layer to an exposure treatment. Forming a latent image of the pattern, developing the inorganic powder-containing resin layer to form a pattern, and baking the pattern.

ADVANTAGE OF THE INVENTION According to this invention, the resin composition containing the inorganic powder containing resin composition which can suppress the raise of the viscosity by gelatinization even if it preserve | saves for a long period of time is obtained.
The transfer film of the present invention having the photosensitive resin layer formed from the resin composition is excellent in transferability, and by using the transfer film, a member for PDP having an excellent pattern shape can be formed.

Hereinafter, an 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 PDP 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 comprises (A) inorganic powder, (B) a polymer having a specific structural unit, (C) a polyfunctional (meth) acrylate, and (D) a photopolymerization initiator. It is the paste-like composition formed.

(A) Inorganic powder The inorganic powder (A) used in the inorganic powder-containing resin composition of the present invention varies depending on the type of constituent member to be formed, but any inorganic containing metal and / or metal oxide. It is a powder.

  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 650 ° C. When the softening point of the glass powder is in the above range, the firing step in producing the PDP 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.

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 .
Examples of the inorganic powder used in the composition for forming the “phosphor” constituting the PDP include Y ₂ O ₃ : Eu ³⁺ , Y ₂ SiO ₅ : Eu ³⁺ , Y ₃ Al ₅ O ₁₂ : Eu. ³⁺ , 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 C ₁₂ : 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) Polymer The polymer (B) used in the present invention is a water-soluble polymer having a structural unit represented by the following formula (1) (hereinafter also referred to as “structural unit (1)”). It has a role as a resin. The “water-soluble” in the present invention refers to a property that is soluble to such an extent that a target development process is performed by a development step in the method for producing a PDP member of the present invention described later.

In said formula (1), R < ¹ > is a hydrogen atom or a methyl group, R < ² > is a C1-C5 alkyl group, for example, a methyl group, an ethyl group, n-propyl group, i-propyl group, An n-butyl group, an i-butyl group, a t-butyl group and the like can be mentioned, and a methyl group is particularly preferable. M and n are integers of 1 to 5, preferably an integer of 1 to 3, and m ≠ n, a is an integer of 1 to 100, preferably an integer of 1 to 20, and b is It is an integer of 0 to 100, preferably an integer of 0 to 20.

  The content of the structural unit (1) in the polymer (B) is not particularly limited, but is preferably 20 to 99.9 mol%, more preferably 25 to 90 mol%, and particularly preferably 30 to 80 mol%. is there.

By using the polymer (B) as described above, since the interaction with the inorganic powder is not too strong as compared with other resins, an inorganic powder-containing resin composition having excellent storage stability can be obtained.
The polymer (B) having the structural unit (1) can be obtained by (co) polymerizing a compound represented by the following formula (2).

In Formula (2), R ¹ is a hydrogen atom or a methyl group, R ² is an alkyl group having 1 to 5 carbon atoms, m and n are integers of 1 to 5, and m ≠ n, Is an integer from 1 to 100, and b is an integer from 0 to 100.

As the compound represented by the above formula (2),
Methoxy polyethylene glycol mono (meth) acrylate (m = 2, b = 0),
Methoxy polypropylene glycol mono (meth) acrylate (m = 3, b = 0),
Methoxypolybutylene glycol mono (meth) acrylate (m = 4, b = 0),
And methoxypoly (ethylene glycol-propylene glycol) mono (meth) acrylate (m = 2, n = 3) and methoxypoly (propylene glycol-butylene glycol) mono (meth) acrylate (m = 3, n = 4). . Of these, methoxypolyethylene glycol mono (meth) acrylate is particularly preferred.

  Examples of commercially available products of the above-mentioned compounds include “Blemmer” series manufactured by Nippon Oil & Fats Co., Ltd., particularly “Blemmer PME-100”, “Same PME-200”, “Same PME-350” and the like.

As other constituent monomers in the polymer (B) used in the present invention, for example,
Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate;
Acrylates such as phenolic hydroxyl group-containing monomers such as o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene;
(Meth) acrylamide, N, N-dimethylacrylamide, N, N-dimethylaminopropylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide,
Amide group-containing monomers such as acryloylmorpholine;
Examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl trimethyl acetate, and vinyl phenyl acetate.

  Among the other constituent monomers, hydroxyl group-containing monomers, phenolic hydroxyl group-containing monomers and amide group-containing monomers are preferred, hydroxyl group-containing monomers and amide group-containing monomers are more preferred, and particularly hydroxyl group-containing monomers and amides. It is preferable to use together with group-containing monomers.

The content of the structural unit derived from the other constituent monomer in the polymer (B) is not particularly limited, but is preferably 0.1 to 70 mol%, more preferably 5 to 65 mol%, and particularly preferably 10 to 60. Mol%. By containing the structural unit derived from the above other constituent monomers in such a range, both handling property when transferred to a transfer film and transfer property to a substrate are excellent, water developability, pattern adhesion, and film storage stability. A transfer film with good properties can be obtained.

  When using a hydroxyl group-containing monomer as another constituent monomer, the content of the constituent unit derived from the monomer is preferably 40 mol% or less, more preferably 10 to 30 mol%. By containing the structural unit derived from a hydroxyl group-containing monomer in such a range, a composition and a transfer film excellent in water developability and pattern adhesion can be obtained.

  Moreover, when using an amide group containing monomer as another structural monomer, content of the structural unit derived from the monomer is preferably 50 mol% or less, more preferably 10 to 40 mol%. By containing a structural unit derived from an amide group-containing monomer in such a range, a composition and a transfer film excellent in water developability and resolution can be obtained.

  Further, when the hydroxyl group-containing monomer and the amide group-containing monomer are used in combination as the other constituent monomer, the moles of the content of the structural unit derived from the hydroxyl group-containing monomer and the content of the structural unit derived from the amide group-containing monomer. The ratio (hydroxyl group: amide group) is 1: 5 to 5: 1, preferably 1: 4 to 4: 1, particularly preferably 1: 3 to 3: 1. By using a hydroxyl group-containing monomer and an amide group-containing monomer in such a molar ratio, a composition and transfer film excellent in water developability and pattern adhesion can be obtained, and further handled when formed into a transfer film. There is an advantage of superiority.

  The polymer (B) has a weight average molecular weight (Mw) of preferably 5,000 to 5,000,000, particularly preferably 10,000 to 300,000. When Mw is in the above range, the film-forming property when the transfer film is formed is good, and the patterning property is also excellent. In addition, said Mw is the weight average molecular weight of polystyrene conversion by GPC measurement.

  Moreover, the glass transition temperature (Tg) of a polymer (B) becomes like this. Preferably it is 0-70 degreeC, More preferably, it is 10-50 degreeC. When Tg is in such a range, handling property, storage stability, and transfer property to a substrate are improved when the transfer film is formed.

  The content of the polymer (B) in the composition of the present invention is usually 1 to 50 parts by weight, preferably 10 to 45 parts by weight, particularly preferably 20 to 40 parts by weight based on 100 parts by weight of the inorganic powder. Parts by weight. When the content of the polymer (B) is in the above range, the effects of the present invention are sufficiently exhibited.

In the composition of the present invention, as the binder resin, a polymer other than the polymer (B) is used in combination as long as the effect of the present invention is not impaired and water development is possible when forming the PDP member. May be.
(C) Polyfunctional (meth) acrylate The polyfunctional (meth) acrylate (C) constituting the composition of the present invention is polymerized by exposure, and the exposed portion becomes insoluble or hardly soluble in the developer. Have

Examples of the polyfunctional (meth) acrylate (C) used in the present invention include di (meth) acrylates of alkylene glycol such as ethylene glycol and propylene glycol; di (meth) acrylate of polyalkylene glycol such as polyethylene glycol and polypropylene glycol ( (Meth) acrylates; di (meth) acrylates of hydroxylated polymers at both ends such as both ends hydroxypolybutadiene, both ends hydroxypolyisoprene, and both ends hydroxypolycaprolactone; glycerin, 1,2,4-butanetriol, trimethylol Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as alkane, tetramethylolalkane, pentaerythritol, dipentaerythritol, etc .; polyalkylenes of trihydric or higher polyhydric alcohols Poly (meth) acrylates of recall adducts; 1,4
-Poly (meth) acrylates of cyclic polyols such as cyclohexanediol and 1,4-benzenediol; polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone Examples include oligo (meth) acrylates such as resin (meth) acrylate and spiraline resin (meth) acrylate. These may be used alone or in combination of two or more. The molecular weight of the polyfunctional (meth) acrylate (C) is preferably 100 to 2,000.

  The content of the polyfunctional (meth) acrylate (C) in the composition of the present invention is usually 0.1 to 50 parts by weight, preferably 1 to 100 parts by weight with respect to 100 parts by weight of the inorganic powder (A). 40 parts by weight.

(D) Photopolymerization initiator As the photopolymerization initiator (D) 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-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) -butan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2, Carbonyl compounds such as 4,6-trimethylbenzoyl-diphenyl-phosphine oxide; azoisobutyronitrile, 4- Azo compounds or azide compounds such as azidobenzaldehyde; organic sulfur compounds such as mercaptan disulfide; organic compounds such as benzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, and paraffin hydroperoxide Peroxide; 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -1,3,5-triazine, 2- [2- (2-furanyl) ethylenyl] -4,6-bis (trichloromethyl) ) Trihalomethanes such as 1,3,5-triazine; imidazole dimers such as 2,2′-bis (2-chlorophenyl) 4,5,4 ′, 5′-tetraphenyl1,2′-biimidazole And so on.

  The said photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more type. Content of the said photoinitiator (D) in the composition of this invention is 0.01-100 weight part normally with respect to 100 weight part of said polyfunctional (meth) acrylate (C), Preferably it is 0.00. 1 to 50 parts by weight.

(E) Dissolution Accelerator The composition of the present invention preferably contains a dissolution accelerator (E) for the purpose of expressing sufficient solubility in a developer described later. As the dissolution accelerator (E), a surfactant is preferably used. Examples of such surfactants include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

  Examples of the fluorosurfactant include “BM-1000” and “BM-1100” manufactured by BM CHIMIE, “Megafac F142D”, “Same F172”, and “Same F172” manufactured by Dainippon Ink & Chemicals, Inc. "F173", "F183", "Florard FC-135", "FC-170C", "FC-430", "FC-431" manufactured by Sumitomo 3M Limited, "Asahi Glass Co., Ltd." “Surflon S-112”, “S-113”, “S-131”, “S-141”, “S-145”, “S-382”, “SC-101”, “Same” Commercial products such as “SC-102”, “SC-103”, “SC-104”, “SC-105”, and “SC-106” can be mentioned.

  Examples of the silicone surfactant include “SH-28PA”, “SH-190”, “SH-193”, “SZ-6032”, and “SF-8428” manufactured by Toray Dow Corning Silicone Co., Ltd. ”,“ DC-57 ”,“ DC-190 ”,“ KP341 ”manufactured by Shin-Etsu Chemical Co., Ltd.,“ Ftop EF301 ”,“ same EF303 ”,“ same EF352 ”manufactured by Shin-Akita Kasei Co., Ltd., etc. Can be mentioned.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene distyrenated phenyl ether, polyoxyethylene octyl Examples include polyoxyethylene aryl ethers such as phenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate.

Examples of commercially available nonionic surfactants include “Emulgen A-60”, “A-90”, “A-500”, “B-66”, and “PP-290” manufactured by Kao Corporation. Manufactured by Kyoeisha Chemical Co., Ltd.
Acrylic acid copolymer polyflow no. 57 "," No. 90 ", and the like.

  Among the above surfactants, nonionic surfactants, specifically polyoxyethylene aryl ethers, are preferred, since the removal of the unexposed portion of the inorganic powder-containing resin layer is easy during development. A compound represented by formula (i) is preferred.

In said formula (i), R < ³ > is a C1-C5 alkyl group, Preferably it is a methyl group, p is an integer of 1-5, s is an integer of 1-5, Preferably it is 2, t is an integer of 1 to 100, preferably an integer of 10 to 20.

  The content of the dissolution accelerator (E) in the composition of the present invention is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, particularly preferably 100 parts by weight of the binder resin. Preferably it is 0.1-10 weight part. When the content of the dissolution accelerator (E) is in the above range, a composition excellent in solubility in a developer can be obtained.

(F) Other components 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. Lactones, sulfoxides, sulfones, hydrocarbons, halogenated hydrocarbons and the like.

  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.
The composition of the present invention preferably further contains an ultraviolet absorber. The ultraviolet absorber is preferably made of an organic dye because it does not remain in the fired member and does not deteriorate the member characteristics. Among them, an organic dye having a high UV absorption coefficient in the wavelength range of 400 to 500 nm is preferable. Preferably used.

  Specifically, azo compounds, triazine compounds, amino ketone compounds, xanthene compounds, quinoline compounds, quinone compounds, benzophenone compounds, benzoic acid compounds, cyanoacrylate compounds, spiro compounds, fluorenone compounds, fulgide compounds, imidazole compounds, perylene compounds, phenazines Compound, phenothiazine compound, polyene compound, diphenylmethane compound, triphenylmethane compound, polymethine compound, acridine compound, acridinenon compound, carboostyryl compound, coumarin compound, diphenylamine compound, quinacridone compound, quinophthalone compound, phenoxazine compound, phthaloperinone compound, A phthalocyanine compound can be used. Among them, azo compounds represented by 1-phenylazo-2-naphthol, 1-phenyl-3-methyl-4- (4-methylphenylazo) -5-oxypyrazole and the like, represented by 1,4-diamilaminoanthraquinone Particularly preferred are quinone compounds and phenolic compounds represented by curcumin.

  When using organic dye, the addition amount is 0.05-10 with respect to the total content of a polymer (B), a polyfunctional (meth) acrylate (C), and a photoinitiator (D). % By weight, preferably about 0.5 to 5% by weight. If the addition amount is less than the above range, the effect of adding the ultraviolet absorber is not so much. If the addition amount exceeds the above range, the characteristics of the obtained PDP member may be deteriorated.

  The composition of the present invention further includes various additives such as a dispersant, a plasticizer, a development accelerator, an adhesion assistant, an antihalation agent, a storage stabilizer, an antifoaming agent, an antioxidant, and a filler as optional components. 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, it is 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 member for PDP>
The manufacturing method of the present invention is preferably used for manufacturing a PDP component. 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.

As the transfer conditions, 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 ² , 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 steps described above, PDP members such as partition walls, electrodes, resistors, dielectrics, phosphors, color filters, and black matrices can be formed. In addition, the manufacturing method of this invention is preferable as a method of forming a partition, a dielectric material, and an electrode among these, and is especially preferable as a method of forming a front partition. 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, a glass substrate having heat resistance is preferably used 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)
As the developer used in the development step in the production method of the present invention, water, particularly ultrapure water is preferably used. Since the inorganic powder contained in the inorganic powder-containing resin layer is uniformly dispersed by the binder resin, the polymer (B) constituting the binder resin is dissolved in the developer and washed. The inorganic powder is also removed at the same time. Further, an alkaline developer may be used as the developer.

  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, dihydrogen phosphate Ammonium, 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, etc. Inorganic alkaline compounds: tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropyl Piruamin, and organic alkaline compounds such as ethanol amine. The alkaline developer may contain additives such as nonionic surfactants and organic solvents. 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 to these Examples. In the following, “part” means “part by weight”, and the weight average molecular weight (Mw) is a polystyrene equivalent weight average molecular weight measured under the following conditions using gel permeation chromatography (GPC). The method for evaluating the storage stability of the obtained composition is as follows.

(GPC measurement conditions)
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
(Storage stability)
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 shading 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>
Methoxypolyethylene glycol monomethacrylate (“Blemmer PME-100” manufactured by NOF Corporation) m = 2, a = 2, b = 0 represented by formula (2) 80 mol, methyl methacrylate 10 mol, 2-hydroxypropyl 10 mol of methacrylate and 0.5 part of N, N′-azobisisobutyronitrile were charged into an autoclave equipped with a stirrer and stirred at room temperature in a nitrogen atmosphere until uniform. After stirring, the mixture is polymerized at 70 ° C. for 3 hours, further added with 0.25 part of N, N′-azobisisobutyronitrile, polymerized for 1 hour, and the polymerization reaction is continued at 70 ° C. for 1 hour, and then to room temperature. Upon cooling, a polymer solution was obtained. The obtained polymer solution had a polymerization rate of 100%, and the Mw of the copolymer [resin (1)] precipitated from this polymer solution was 160,000.

<Synthesis Example 2>
A copolymer [resins (2) to (10)] was obtained in the same manner as in Synthesis Example 1 except that the monomer composition in Synthesis Example 1 was changed to the monomer composition shown in Table 1 below. In Table 1, HPMA is 2-hydroxypropyl methacrylate, MMA is methyl methacrylate, ACMO is acryloylmorpholine, MAm is methacrylamide, and DMAA is N, N-dimethylacrylamide.

<Synthesis Example 3>
Except that the monomer composition in Synthesis Example 1 was changed to 40 parts of methyl-2-ethylhexyl methacrylate, 20 parts of methacrylic acid, 30 parts of n-butyl methacrylate, and 10 parts of 2-hydroxypropyl methacrylate, the same as in Synthesis Example 1. Thus, a copolymer [resin (11)] having Mw of 100,000 was obtained.

<Example 1>
(1) Preparation of Resin Composition Containing Inorganic Powder As inorganic powder (A), 100 parts of ZnO—B ₂ O ₃ —SiO ₂ low melting point glass frit (indefinite shape, softening point 570 ° C.),
As water-soluble resin (B), 35 parts of resin (1) obtained in Synthesis Example 1;
As the polyfunctional (meth) acrylate compound (C), 7 parts of ethylene oxide-modified trimethylolpropane triacrylate (“Aronix M-360” manufactured by Toagosei Co., Ltd.),
As a photopolymerization initiator (D), 1- [4- (2-hydroxyethoxy) -phenyl] -2-
1.5 parts hydroxy-2-methyl-1-propan-1-one,
As a solvent, 40 parts of propylene glycol monomethyl ether acetate,
As a dispersant, 1.5 parts of normal decyltrimethoxysilane,
As a dissolution accelerator (surfactant) (E), 2 parts of “Emulgen A-60” manufactured by Kao Corporation,
As a UV absorber, 0.1 part of 1-phenyl-3-methyl-4- (4-methylphenylazo) -5-oxypyrazole was kneaded with a bead mill, and then filtered with a stainless mesh (400 mesh, 38 μm diameter). Thus, 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 onto a support film (width 200 mm, length 30 m, thickness 38 μm) made of a PET film using a blade coater, and the coating film was coated with 100 By drying at 5 ° C. 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, thereby preparing a transfer film in which a support film, an inorganic powder-containing photosensitive resin layer, and a protective film were laminated in this order.

(3) Formation of members
(i) Transfer process of inorganic powder-containing resin layer After peeling off and removing the protective film of the obtained transfer film, the transfer film is applied to the dielectric layer (film thickness 20 μm) formed on the surface of the glass substrate for 6-inch panels. Were laminated so that the surface of the resin layer 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 subjected to i-line by an ultrahigh pressure mercury lamp through an exposure mask (a stripe pattern having a width of 400 μm). (Ultraviolet light having a wavelength of 365 nm) was irradiated at an irradiation amount of 100 mJ / cm ² .

  After completion of the exposure step, the support film was peeled off from the resin layer, and then the exposed resin layer was subjected to a development process by a shower method using ultrapure water (30 ° C.) as a developer for 40 seconds. . Thereby, the uncured resin layer that was not irradiated with ultraviolet rays was removed, and a pattern of the resin layer containing inorganic powder was formed.

(iii) Baking process of resin layer pattern The glass substrate on which the resin layer pattern was formed on the dielectric layer was baked in a baking furnace in a temperature atmosphere of 580 ° C for 50 minutes. 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 15 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 to 10, Comparative Example 1>
Except for changing the alkali-soluble resin (B) to that shown in Table 1, an inorganic powder-containing resin composition was prepared in the same manner as in Example 1, and the storage stability was evaluated. Next, a transfer film was produced using the composition, and a panel material was produced in the same manner as in Example 1 except that the development time was changed as shown in Table 1 using the transfer film. And the pattern shape was evaluated. The results are shown in Table 1. The developing method and pattern shape evaluation methods and evaluation criteria are as follows.

(Developability)
Evaluation method: Water development was performed in the range of 30 to 180 seconds by the shower method.
Evaluation criteria: AA was good, BB was undissolved unexposed part, and CC was unexposed part insoluble.

(Pattern shape)
Evaluation method: The cross-sectional shape of the pattern was observed using an electron microscope.
Evaluation criteria: AA having a good cross section (trapezoidal shape and forward tapered shape) was designated as AA, and a reverse tapered shape having side edges was designated as BB.

It is sectional drawing for description which shows the structure of a general PDP.

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

Claims (8)

(A) inorganic powder,
(B) possess a structural unit represented by the following formula (1), and at least one structural unit selected from the group consisting of structural units and hydroxyl group-containing monomer-derived constituent units derived from the amide group-containing monomer, wherein hydroxyl group-containing monomer is 2-hydroxyethyl (meth) acrylate, (meth) acrylate, 2-hydroxypropyl and (meth) polymers Ru is selected from the group consisting of acrylic acid 3-hydroxypropyl,

(In the formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is an alkyl group having 1 to 5 carbon atoms, m and n are integers of 1 to 5 and m ≠ n. a is an integer of 1 to 100, and b is an integer of 0 to 100.)
An inorganic powder-containing resin composition comprising (C) a polyfunctional (meth) acrylate and (D) a photopolymerization initiator. The polymer (B) has a structural unit represented by the formula (1), a structural unit derived from an amide group-containing monomer, and a structural unit derived from a hydroxyl group-containing monomer. 2. The inorganic powder-containing resin composition according to claim 1, wherein the resin composition is selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate. object. Further (E) inorganic powder-containing resin composition according to claim 1 or 2, characterized in that it contains a solubility enhancer. The inorganic powder-containing resin composition according to claim 3 , wherein the dissolution accelerator (E) is a polyoxyethylene aryl ether. The inorganic powder-containing resin composition according to any one of claims 1 to 4, wherein the inorganic powder (A) is a glass powder having a softening point of 400 to 650 ° C. Transfer film characterized by having an inorganic powder-containing resin layer formed by using an inorganic powder-containing resin composition according to any one of claims 1-5. A step of transferring the inorganic powder-containing resin layer constituting the transfer film onto the substrate using the transfer film according to claim 6 ;
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 plasma display panel, comprising: a step of developing the inorganic powder-containing resin layer to form a pattern; and a step of baking the pattern. 8. The plasma display panel according to claim 7 , 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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