KR20070031403A - Inorganic powder-containing resin composition, transfer film and method for producing member for plasma display panel - Google Patents

Abstract

The subject of this invention is providing the inorganic powder containing resin composition excellent in storage stability, the transfer film which has a layer containing this resin composition, and the manufacturing method of the member for PDP using the said transfer film. The inorganic powder-containing resin composition according to the present invention contains (A) an inorganic powder, (B) a polymer having a structural unit represented by the formula (1), (C) a polyfunctional (meth) acrylate, and (D) a photopolymerization initiator. It features.

Inorganic powder, polymer, polyfunctional (meth) acrylate, photoinitiator

Description

The manufacturing method of the inorganic powder containing resin composition, the transfer film, and the member for plasma display panels {INORGANIC POWDER-CONTAINING RESIN COMPOSITION, TRANSFER FILM AND METHOD FOR PRODUCING MEMBER FOR PLASMA DISPLAY PANEL}

This invention relates to the inorganic powder containing resin composition suitable for manufacture of a member for plasma display panels, the transfer film obtained from the said composition, and the manufacturing method of the said member for plasma display panels using the said transfer film.

In recent years, a plasma display panel (hereinafter also referred to as "PDP") has attracted attention as a flat fluorescent display. PDP is a display which displays information by forming a transparent electrode, sealing an inert gas, such as argon or neon, between two adjacent glass plates, making plasma discharge, and making a gas glow, and displaying information.

1 is a schematic diagram showing a cross-sectional shape of a conventionally known AC PDP. In FIG. 1, 101 and 102 are oppositely arranged glass substrates, 103 and 111 are partition walls, and the glass substrate 101, glass substrate 102, back partition 103 and front partition wall 111 The cell is partitioned by (). Numeral 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 lowering the resistance of the transparent electrode 104, and 106 is a glass substrate. An address electrode fixed to 102, 107 is a fluorescent material retained in the cell, and 108 is a dielectric layer formed on the surface of the glass substrate 101 to cover the transparent electrode 104 and the bus electrode 105. 109 is a dielectric layer formed on the surface of the glass substrate 102 so as to cover the address electrode 106, and 110 is a protective film containing magnesium oxide, for example. In addition, in a color PDP, a color filter (red, green, blue), a black matrix, or the like 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 inorganic powder is formed on a substrate, and the resin layer is formed through a photo mask. The photolithographic method etc. which include the process of irradiating an ultraviolet-ray and developing and baking the pattern formed on the board | substrate are used preferably (refer patent document 1-3 below).

As a method of forming the photosensitive resin layer containing an inorganic powder on a board | substrate, the method of transferring this resin layer and forming it using the transfer film which formed this resin layer on the flexible support film is preferable. It is used. Thus, by using a transfer film, the resin layer excellent in the uniformity of thickness can be obtained, and work efficiency can be improved.

However, in the photosensitive resin composition containing an inorganic powder, when the inorganic powder containing a polyvalent metal and / or a polyvalent metal oxide is used, there existed a problem that this resin composition gelatinized. This is because alkali soluble polymers having unsaturated double bonds are usually used as binder resins to impart photosensitivity and alkali solubility to the composition, so that acidic functional groups (such as carboxyl groups) in the polymer and polyvalent metal hydroxides on the surface of the inorganic powder react. Due to

Thus, when the resin composition containing an inorganic powder gelatinizes, not only film | membrane becomes difficult but also a problem, such as developing which becomes unstable even if it could form into a film, could not be preserve | saved for a long time.

<Patent Document 1> Japanese Patent Application Laid-Open No. 9-102273

<Patent Document 2> Japanese Patent Application Laid-Open No. 11-144628

<Patent Document 3> Japanese Patent Application Laid-Open No. 11-162339

An object of this invention is to provide the inorganic powder containing resin composition excellent in storage stability, the transfer film which has a layer containing this resin composition, and the manufacturing method of the member for PDP using the said transfer film.

The 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),

(C) polyfunctional (meth) acrylates, and

(D) photoinitiator

It is characterized by containing.

(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, m ≠ n, a is an integer of 1 to 100, b Is an integer from 0 to 100.)

The transfer film which concerns on this invention is characterized by having an inorganic powder containing resin layer formed using the said inorganic powder containing resin composition.

The manufacturing method of the member for PDPs which concerns on this invention transfers the inorganic powder containing resin layer which comprises the said transfer film on a board | substrate using the said transfer film, and exposes the said inorganic powder containing resin layer by exposure process, and the latent image of a pattern And forming a pattern by developing the inorganic powder-containing resin layer and baking the pattern.

Effect of the Invention

According to the present invention, a resin composition containing an inorganic powder-containing resin composition capable of suppressing a rise in viscosity due to gelation even after long-term storage is obtained.

The transfer film of this invention which has the photosensitive resin layer formed from the said resin composition is excellent in transferability, and the member for PDP excellent in pattern shape can be formed by using the said transfer film.

1 is a cross-sectional view illustrating the structure of a general PDP.

<Explanation of symbols for the main parts of the drawings>

101: glass substrate 102: glass substrate

103: rear partition 104: transparent electrode

105: bus electrode 106: address electrode

107: phosphor 108: dielectric layer

109: dielectric layer 110: protective film

111: front bulkhead

Best Mode for Carrying Out the Invention

Hereinafter, the inorganic powder containing resin composition concerning this invention, the transfer film which has a layer containing this resin composition, and the manufacturing method of the member for PDP using the said transfer film are demonstrated in detail.

<Inorganic powder containing resin composition>

The inorganic powder containing resin composition of this invention is a paste composition containing (A) inorganic powder, (B) the polymer which has a specific structural unit, (C) polyfunctional (meth) acrylate, and (D) photoinitiator.

(A) inorganic powder

Although the inorganic powder (A) used for the inorganic powder containing resin composition of this invention differs according to the kind of structural member to form, all are inorganic powders containing a metal and / or a metal oxide.

For example, glass powder is mentioned as an inorganic powder used for the composition for forming the "dielectric layer" and the "partition wall" which comprise a PDP. It is preferable that the said soft powder has the softening point in the range of 400-650 degreeC. Since the softening point of glass powder exists in the said range, the baking process at the time of manufacturing the member for PDP can be performed favorably. As a result, since organic substances, such as a binder resin, do not remain in a structural member, it does not cause the lifetime reduction of the fluorescent substance by spreading outgas into a panel, and does not generate distortion of a glass substrate, etc.

As a glass powder used preferably for the resin composition of this invention,

(1) lead oxide, boron oxide, silicon oxide, calcium oxide type (PbO-B ₂ O ₃ -SiO ₂ -CaO type),

(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 type (PbO-B ₂ O ₃ -SiO ₂ -Al ₂ O _{3 type} ),

(4) lead oxide, zinc oxide, boron oxide, silicon oxide type (PbO-ZnO-B ₂ O ₃ -SiO _{2 type} ),

(5) lead oxide, zinc oxide, boron oxide, silicon oxide, titanium oxide type (PbO-ZnO-B ₂ O ₃ -SiO ₂ -TiO _{2 type} ),

(6) bismuth oxide, boron oxide, silicon oxide type (Bi ₂ O ₃ -B ₂ O ₃ -SiO _{2 type} ),

(7) zinc oxide, phosphorus oxide, silicon oxide type (ZnO-P ₂ O ₅ -SiO _{2 type} ),

(8) zinc oxide, boron oxide, potassium oxide type (ZnO-B ₂ O ₃ -K ₂ O type),

(9) phosphorus oxide, boron oxide, aluminum oxide type (P ₂ O ₅ -B ₂ O ₃ -Al ₂ O _{3 type} ),

10, there may be mentioned zinc oxide, phosphorus oxide, titanium (type _{ZnO-P 2 O 5 -TiO 2} ) oxide mixtures.

For example, inorganic oxide powders such as aluminum oxide, chromium oxide, and manganese oxide may be mixed and used with the glass powder.

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

Inorganic powders used in the composition for forming the "electrodes" constituting the PDP, for example, the transparent electrode 104, the bus electrode 105, the address electrode 106, and the like, are Ag, Au, Al. And metal powder containing Ni, Ag-Pd alloy, Cu, Cr, and the like.

Inorganic powder used in the composition for forming a "resistor" constituting a PDP, and inorganic powder such as RuO _2.

Inorganic Powder used in the composition for forming a "fluorescent material" constituting a PDP are _{^{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) BO 3: Eu 3 +, Zn 3 (PO 4) 2: a fluorescent material for red having a tank of the like Mn; Zn ₂ SiO ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, BaMgAl ₁₄ O ₂₃ : Mn, LaPO ₄ : (Ce, Tb), Y ₃ (Al, Ga) ₅ O ₁₂ : Green fluorescent substance with composition ; _{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) The inorganic powder containing the blue fluorescent substance etc. which have compositions, such as S: Ag, is mentioned.

Inorganic powder used in the composition for forming a "color filter" constituting a PDP are a red material for such as _{Fe 2 O 3, Pb 3 O} 4; Green substances such as Cr ₂ O ₃ ; 2 (Al ₂ Na ₂ Si ₃ O ₁₀ ) Na ₂ S ₄ Inorganic powders containing blue substances, such as these, are mentioned.

Examples of the inorganic powder used in the composition for forming the "black matrix" constituting the PDP include metal powders containing 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)"), and has a role as a binder resin. In addition, "water solubility" in this invention means the property which has solubility to the extent that the target image development process is performed by the image development process in the manufacturing method of the member for PDPs of this invention mentioned later.

<Formula 1>

In Formula 1, R ¹ is a hydrogen atom or a methyl group, R ² is an alkyl group having 1 to 5 carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i- A butyl group, t-butyl group, etc. are mentioned, A methyl group is especially preferable. M and n are integers of 1 to 5, preferably integers 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 0 to 100 Integer, Preferably it is an integer of 0-20.

Although content in particular of the said structural unit (1) in a polymer (B) is not restrict | limited, Preferably it is 20-99.9 mol%, More preferably, it is 25-90 mol%, Especially preferably, it is 30-80 mol%. .

By using the above-mentioned polymer (B), since the interaction with inorganic powder is not too strong compared with other resin, the inorganic powder containing resin composition excellent in storage stability is obtained.

The polymer (B) having the structural unit (1) is obtained by (co) polymerizing the 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, a is an integer of 1 to 100, b is It is an integer of 0-100.

As the compound represented by 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),

Methoxy poly (ethylene glycol-propylene glycol) mono (meth) acrylate (m = 2, n = 3), and

Methoxy poly (propylene glycol butylene glycol) mono (meth) acrylate (m = 3, n = 4) and the like. Among these, methoxy polyethyleneglycol mono (meth) acrylate is especially preferable.

Commercially available products of the above compounds include the "Bremmer" series manufactured by Nippon Yushi Co., Ltd., and particularly "Bremmer PME-100", "Breath PME-200", "Breath PME-350", and the like. .

As another structural monomer in the polymer (B) used by this invention, (meth) acrylic-acid 2-hydroxyethyl, (meth) acrylic-acid 2-hydroxypropyl, (meth) acrylic-acid 3-hydroxypropyl, for example. Hydroxyl group-containing monomers such as these; acrylates such as phenolic hydroxyl group-containing monomers such as o-hydroxy styrene, m-hydroxy styrene and p-hydroxy styrene; Amide groups, such as (meth) acrylamide, N, N-dimethyl acrylamide, N, N-dimethylaminopropyl acrylamide, N, N-diethyl acrylamide, N-isopropyl acrylamide, and acryloyl morpholine Monomers; Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl trimethyl acetate, vinyl phenyl acetate, etc. are mentioned.

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

Although content of the structural unit derived from the said other structural monomer in a polymer (B) is not specifically limited, Preferably it is 0.1-70 mol%, More preferably, it is 5-65 mol%, Especially preferably, it is 10-60 mol %to be. By containing the structural unit derived from the said other structural monomer in this range, the transfer film which is excellent in both the handleability at the time of making it as a transfer film and the board | substrate to a board | substrate, and is excellent in water developability, pattern adhesiveness, and storage stability of a film is obtained. Can be.

When using hydroxyl group containing monomers as another structural monomer, content of the structural unit derived from the said monomer becomes like this. Preferably it is 40 mol% or less, More preferably, it is 10-30 mol%. By containing the structural unit derived from a hydroxyl-containing monomer in such a range, the composition and the transfer film which are excellent in water developability and pattern adhesiveness can be obtained.

Moreover, when using amide group containing monomers as another structural monomer, content of the structural unit derived from the said monomer becomes like this. Preferably it is 50 mol% or less, More preferably, it is 10-40 mol%. By containing the structural unit derived from an amide group containing monomer in such a range, the composition and transfer film which are excellent in water developability and resolution are obtained.

Moreover, when using hydroxyl group containing monomers and amide group containing monomers together as said other structural monomer, the molar ratio (content of a structural unit derived from a hydroxyl group containing monomer and content of a structural unit derived from an amide group containing monomer) (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 together hydroxyl group containing monomers and amide group containing monomers in such a molar ratio, the composition and the transfer film which are excellent in water developability and pattern adhesiveness are obtained, and there exists an advantage that handleability is excellent when it is set as a transfer film.

The weight average molecular weight (Mw) of the polymer (B) is preferably 5,000 to 5,000,000, particularly preferably 10,000 to 300,000. When Mw exists in the said range, the film formation property at the time of setting it as a transfer film is excellent, and patterning property is also excellent. In addition, said Mw is the weight average molecular weight of polystyrene conversion by GPC measurement.

In addition, the glass transition temperature (Tg) of the polymer (B) is preferably 0 to 70 ° C, more preferably 10 to 50 ° C. When Tg exists in such a range, the handleability, storage stability, and transferability with respect to a board | substrate at the time of making a transfer film become favorable.

Content of the said polymer (B) in the composition of this invention is 1-50 weight part normally with respect to 100 weight part of said inorganic powders, Preferably it is 10-45 weight part, Especially preferably, it is 20-40 weight part. When content of a polymer (B) exists in the said range, the effect of this invention is fully expressed.

On the other hand, the composition of this invention can use together polymers other than a polymer (B) in the range in which the effect of this invention is impaired as a binder resin, and a water development is possible at the time of forming a member for PDP.

(C) polyfunctional (meth) acrylates

The polyfunctional (meth) acrylate (C) constituting the composition of the present invention is polymerized by exposure, so that the exposed portion is insoluble or poorly soluble in the developer.

As a polyfunctional (meth) acrylate (C) used by this invention, For example, 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 terminal hydroxylated polymers such as both terminal hydroxypolybutadiene, both terminal hydroxypolyisoprene and both terminal hydroxypolycaprolactone; Poly (meth) acrylates of trivalent or higher polyhydric alcohols such as glycerin, 1,2,4-butanetriol, trimethylolalkane, tetramethylolalkane, pentaerythritol, dipentaerythritol; Poly (meth) acrylates of polyalkylene glycol adducts of trivalent or higher polyhydric alcohols; Poly (meth) acrylates of cyclic polyols such as 1,4-cyclohexanediol and 1,4-benzenediols; Oligos, such as polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spiran resin (meth) acrylate ( Meth) acrylates and the like. These may be used independently and may be used in combination of 2 or more type.

It is preferable that the molecular weight of the said polyfunctional (meth) acrylate (C) is 100-2,000.

Content of the said polyfunctional (meth) acrylate (C) in the composition of this invention is 0.1-50 weight part normally with respect to 100 weight part of said inorganic powders (A), Preferably it is 1-40 weight part.

(D) photoinitiator

As a photoinitiator (D) which comprises the composition of this invention, benzyl, benzoin, benzophenone, camphorquinone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl Ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propaneone, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) -butan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1- Carbonyl compounds such as on, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; Azo compounds or azide compounds such as azoisobutyronitrile and 4-azide benzaldehyde; Organic sulfur compounds such as mercaptan disulfide; Organic peroxides such as benzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide and paramethane hydroperoxide; 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -1,3,5-triazine, 2- [2- (2-furanyl) ethylenyl] -4,6-bis Trihalo methanes such as (trichloromethyl) -1,3,5-triazine; And imidazole dimers such as 2,2'-bis (2-chlorophenyl) 4,5,4 ', 5'-tetraphenyl 1,2-biimidazole.

The said photoinitiator may be used individually by 1 type, and 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) acrylates (C), Preferably it is 0.1-50 weight part.

(E) dissolution accelerator

It is preferable that the composition of this invention contains a dissolution promoter (E) for the purpose of expressing sufficient solubility to the developing solution mentioned later. As the dissolution accelerator (E), a surfactant is preferably used. As such surfactant, a fluorine-type surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned, for example.

As said fluorine-type surfactant, "BM-1000" by the BM CHIMIE company, "BM-1100", "Megapack F142D" by Dainippon Ink & Chemicals Co., Ltd. F172 "," East F173 "," East F183 "," Florard FC-135 "," East FC-170C "," East FC-430 "," East FC-431 "by Sumitomo 3M Co., Ltd., Asahi Glass Co., Ltd. "Surfron S-112", "Dong S-113", "Dong S-131", "Dong S-141", "Dong S-145", "Dong S-382" And commercially available products such as "SC-101," SC-102 "," SC-103 "," SC-104 "," SC-105 ", and" SC-106 ".

As said silicone type surfactant, "SH-28PA", "SH-190", "SH-193", "SZ-6032", "SF-8428", "" made by Toray Dow Corning Silicone Co., Ltd., for example. DC-57 "," DC-190 "," KP341 "by Shin-Etsu Chemical Co., Ltd.," F-Top EF301, "EF E303", "EF352" by Shin-Kaida Kasei Co., Ltd., etc. Commercially available products are mentioned.

As said nonionic surfactant, For example, polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene distylated phenyl ether, polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Polyoxyethylene dialkyl ester, such as polyoxyethylene dilaurate and polyoxyethylene distearate, etc. are mentioned.

As a commercial item of the said nonionic surfactant, "Emulgen A-60", "A-90", "A-500", "B-66", "PP-290" by Kao Corporation, for example. "(Meth) acrylic-acid copolymer polyflow No. 57" by Kyosei Chemical Co., Ltd., "No. 90", etc. are mentioned.

Among the above-mentioned surfactants, nonionic surfactants, specifically polyoxyethylene aryl ethers, are preferable in that the inorganic powder-containing resin layer of the unexposed portion is easily removed at the time of development. Compound is preferred.

In formula (I), R ³ is an alkyl group having 1 to 5 carbon atoms, preferably methyl group, p is an integer of 1 to 5, s is an integer of 1 to 5, preferably 2, t is 1 to 100 Integer, Preferably it is an integer of 10-20.

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 0.1 to 10 parts by weight based on 100 parts by weight of the binder resin. It is wealth. When content of a dissolution accelerator (E) exists in the said range, the composition excellent in the solubility to a developing solution is obtained.

(F) other ingredients

The composition of the present invention usually contains a solvent in order to impart proper fluidity or plasticity and good film formability. The solvent used in the present invention is preferably a solvent having good affinity with the inorganic powder and solubility of the binder resin, imparting suitable viscosity to the present composition, and being easily evaporated and removed by drying. .

The solvent used in the present invention is not particularly limited as long as it is a solvent having 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 and hydroxy Acetic acid esters, alkoxyacetic acid 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 compounds Ketones, acyclic ketones, acetoacetic acid esters, pyruvic acid esters, N, N-dialkylformamides, N, N-dialkylacetamides, N-alkylpyrrolidones, γ-lactones, dialkylsulfonates Foxids, dialkyl sulfones, terpineol, N-methyl-2-pyrrolidone, etc. are mentioned. These may be used independently and may be used in combination of 2 or more type.

Content of the said solvent in the composition of this invention can be suitably selected within the range from which favorable film formation property (fluidity or plasticity) is obtained.

It is preferable that the composition of this invention contains the ultraviolet absorber further. As a ultraviolet absorber, since it does not remain in a member after baking, and does not reduce a member characteristic, it is preferable to include an organic type dye, and the organic type dye which has a high UV absorption coefficient in 400-500 nm wavelength range is especially used preferably. .

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, and fulgide Compounds, imidazole compounds, perylene compounds, phenazine compounds, phenothiazine compounds, polyene compounds, diphenylmethane compounds, triphenylmethane compounds, polymethine compounds, acridine compounds, acridinone compounds, carbostyryls Compounds, coumarin compounds, diphenylamine compounds, quinacridone compounds, quinophthalone compounds, phenoxazine compounds, phthaloperinone compounds, phthalocyanine compounds and the like can be used. Among them, an azo compound represented by 1-phenylazo-2-naphthol, 1-phenyl-3-methyl-4- (4-methylphenylazo) -5-oxypyrazole, or the like, and 1,4-dimylaminoanthraquinone Representative quinone compounds and phenol compounds represented by curcumin are particularly preferred.

When using an organic dye, the addition amount thereof is 0.05 to 10% by weight, preferably 0.5 to 5% by weight based on the total content of the polymer (B), the polyfunctional (meth) acrylate (C) and the photopolymerization initiator (D). It is enough. When the addition amount is smaller than the above range, the effect of adding the ultraviolet absorber is not so low, and when the above range is exceeded, the characteristics of the member for PDP obtained may be lowered.

The composition of the present invention may further contain various additives such as a dispersant, a plasticizer, a development accelerator, an adhesion aid, an antihalation agent, a storage stabilizer, an antifoaming agent, an antioxidant, and a filler as an optional component.

<Transfer film>

In the transfer film of the present invention, a layer containing the inorganic powder-containing resin composition of the present invention is formed on a supporting film. The said inorganic powder containing resin layer (henceforth simply a "resin layer" or a "photosensitive resin layer") is obtained by apply | coating the said composition on a support film, forming a coating film, and drying the coating film.

It is preferable that the support film which comprises a transfer film is a resin film which has heat resistance and solvent resistance, and has flexibility. When a support film has flexibility, a paste composition can be apply | coated with a roll coater, and an inorganic powder containing resin layer can be preserve | saved in the state wound by roll shape, and can be supplied. On the other hand, the thickness of the support film may be in a suitable range for use, for example 20 to 100 ㎛.

Examples of the resin forming the support film include fluorine-containing resins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, nylon, and cellulose. Etc. can be mentioned.

The method of applying the composition of the present invention onto the support film is not particularly limited as long as it is a method capable of efficiently forming a coating film having a high film thickness (for example, 10 μm or more) and uniformity, for example, a roll The coating method with a coater, the coating method with a doctor blade, the coating method with a curtain coater, the coating method with a die coater, the coating method with a wire coater, etc. are mentioned.

On the other hand, it is preferable that the mold release process is given to the surface of the support film to which the composition of this invention is apply | coated. Thereby, peeling operation of a support film can be performed easily at the time of formation of a PDP structural member.

The drying conditions of a coating film can be suitably adjusted so that the residual ratio (solvent content rate in a resin layer) of the solvent after drying may be less than 2 mass%, for example, it is about 0.5 to 30 minutes at the drying temperature of 50-150 degreeC.

Although the thickness of the resin layer formed on a support film as mentioned above also changes with content rate, size, etc. of an inorganic powder, it is 5-500 micrometers, for example.

On the other hand, as a protective film layer which can be provided in the surface of a resin layer, a polyethylene film, a polyvinyl alcohol-type film, etc. are mentioned.

<Method for Manufacturing PDP Member>

It is preferable to use the manufacturing method of this invention for manufacture of a PDP structural member. These members form an inorganic powder containing resin layer on a board | substrate using the inorganic powder containing resin composition of this invention or the transfer film of this invention, and expose this resin layer to form a latent image of a pattern, It forms by developing and forming a pattern layer, and baking the said pattern layer.

(i) Formation process of inorganic powder containing resin layer

An inorganic powder containing resin layer can be formed by apply | coating the inorganic powder containing resin composition of this invention on a board | substrate, or transferring the inorganic powder containing resin layer of the said transfer film using the transfer film of this invention.

According to the method using a transfer film, the resin layer excellent in the film thickness uniformity can be easily formed, and the film thickness uniformity of the pattern formed can be aimed at. Moreover, by repeating n times transfer using the said transfer film, the laminated body which has a resin layer of n layer (n represents an integer of 2 or more) can be formed. Or the said laminated body can be formed by carrying out collective transfer of the laminated body which consists of n layer of resin layers on a board | substrate using the transfer film formed on the support film.

As a method of apply | coating the composition of this invention on a board | substrate, various methods, such as the screen printing method, the roll coating method, the rotation coating method, the flexible coating method, are mentioned. After apply | coating a composition by such a method, a resin layer can be formed by drying a coating film. On the other hand, by repeating the above steps n times, a laminate composed of n layers can be formed.

An example of the transfer process using the transfer film is as follows. After peeling off the protective film layer of the transfer film used as needed, the transfer film is superposed so that the surface of a resin layer may contact the surface of a board | substrate, and this transfer film is thermocompression-bonded with a heating roller etc., and is then supported by a resin layer. The film is peeled off. As a result, the resin layer is transferred to and adhered to the surface of the substrate.

As transfer conditions, the surface temperature of a heating roller is 40-140 degreeC, the roll pressure by a heating roller is 0.1-10 kg / cm <2>, and the moving speed of a heating roller is 0.1-10 m / min. In addition, the board | substrate may be preheated and a preheating temperature is 40-140 degreeC, for example.

(ii) exposure process

The surface of the inorganic powder-containing resin layer is selectively irradiated (exposed) with radiation such as ultraviolet rays through a mask for exposure to form a latent image of a pattern on the resin layer. Although it does not specifically limit as a radiation irradiation apparatus used at the time of exposure, The exposure apparatus etc. which are used at the time of manufacturing the ultraviolet irradiation apparatus, semiconductor, or liquid crystal display device which are generally used by the photolithographic method are mentioned.

On the other hand, when an inorganic powder containing resin layer is formed by transfer, it is preferable to perform exposure in the state which has not peeled the support film coat | covered on this resin layer.

(iii) developing process

The exposed resin layer is developed to form a pattern of the resin layer. Developing methods (e.g., immersion method, rocking method, shower method, spray method, puddle method, etc.) and developing processing conditions (e.g., type, composition, concentration, developing time, developing temperature, etc. of the developer) It can select and set suitably according to the kind of containing resin layer.

(vi) firing process

In order to lose the organic substance in the resin layer residual part after image development, the pattern of the formed resin layer is baked. The firing treatment conditions require that the organic substance in the inorganic powder-containing resin layer (residual portion) disappear, and the firing temperature is usually 400 to 600 ° C. and the firing time is 10 to 90 minutes.

By the manufacturing method of this invention including the above process, PDP members, such as a partition, an electrode, a resistor, a dielectric, fluorescent substance, a color filter, and a black matrix, can be formed. On the other hand, the manufacturing method of this invention is preferable as a method of forming a partition, a dielectric, and an electrode among these, and especially as a method of forming a front partition. Although the film thickness of the pattern obtained by this invention differs also according to a use, content rate of an inorganic powder, etc., it is 1-200 micrometers, for example.

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

(Board)

As a board | substrate material used by this invention, the plate-shaped member which consists of insulating materials, such as glass, silicone, polycarbonate, polyester, aromatic amide, polyamideimide, polyimide, is mentioned, for example. Chemical treatment by a silane coupling agent or the like on the surface of the plate member; Plasma treatment; Pretreatment, such as a thin film formation process by the ion plating method, sputtering method, vapor phase reaction method, vacuum deposition method, etc., can be performed.

In addition, in this invention, it is preferable to use the glass substrate which has heat resistance as a board | substrate. As such a glass substrate, PD200 of Asahi Glass Co., Ltd. product is mentioned, for example.

(Exposure mask)

Although the exposure pattern of the exposure mask used at the exposure process in the manufacturing method of this invention changes with materials, it is generally 10-500 micrometers wide streaks.

(developer)

As the developing solution used in the developing step in the production method of the present invention, water, particularly ultrapure water, is preferably used. Since the inorganic powder contained in the said inorganic powder containing resin layer is disperse | distributed uniformly by binder resin, the inorganic powder is also removed simultaneously by melt | dissolving and wash | cleaning the polymer (B) which comprises binder resin with the said developing solution. As the developer, an alkaline developer can be used.

As an active ingredient of alkaline developing solution, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, for example Inorganic alkaline compounds such as lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate and ammonia; Tetramethylammonium Hydroxide, Trimethylhydroxyethylammonium Hydroxide, Monomethylamine, Dimethylamine, Trimethylamine, Monoethylamine, Diethylamine, Triethylamine, Monoisopropylamine, Diisopropylamine, Ethanolamine Organic alkaline compounds, such as these, etc. are mentioned. The alkaline developer may contain additives such as nonionic surfactants and organic solvents. On the other hand, after the development process by alkaline developing solution is performed, the water washing process is performed normally.

Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples. In addition, "part" shows a "weight part" below, and a weight average molecular weight (Mw) is the weight average molecular weight of polystyrene conversion measured on the following conditions using the gel permeation chromatography (GPC), The evaluation method of storage stability is as follows.

(GPC measurement conditions)

GPC measuring device: HLC-8220GPC manufactured by Tosoh Corp.

GPC column: TSKgelSuperHZN-M manufactured by Toso Kabushiki Kaisha

Measuring solvent: tetrahydrofuran

Measuring temperature: 40 ℃

(Preservation stability)

First, the viscosity of the composition immediately after manufacture was measured at 25 degreeC using the rotational viscometer (EMD-R type by Tokyo Keiki), and made this an initial viscosity. Next, the viscosity was measured regularly while preserving the said composition at 5 degreeC and light-shielding conditions, and storage stability was evaluated by the number of days until a viscosity increases 50% from an initial viscosity.

Synthesis Example 1

80 mol of methoxy polyethyleneglycol monomethacrylate ("Bremer PME-100" by Nippon Yushi Co., Ltd., the compound represented by General formula (2), a = 2, b = 0)), methyl methacrylate 10 mol, 10 mol of 2-hydroxypropyl methacrylate and 0.5 part of N, N'-azobisisobutyronitrile were placed in an autoclave with a stirrer and stirred until uniform at room temperature under a nitrogen atmosphere. After stirring, the mixture was polymerized at 70 ° C for 3 hours, further 0.25 parts of N, N'-azobisisobutyronitrile was polymerized for 1 hour, the polymerization reaction was continued at 70 ° C for 1 hour, and then cooled to room temperature to polymer solution. Got. Polymerization rate of the obtained polymer solution was 100%, and Mw of the copolymer [resin (1)] which precipitated from this polymer solution was 160,000.

Synthesis Example 2

A copolymer [resin (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 acryloyl morpholine, MAm is methacrylamide, and DMAA is N, N-dimethylacrylamide.

Synthesis Example 3

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. In the same manner as in Synthesis example 1, a copolymer [resin (11)] having a Mw of 100,000 was obtained.

<Example 1>

(1) Preparation of Inorganic Powder-Containing Resin Composition

100 parts of ZnO-B ₂ O ₃ -SiO ₂ based low melting glass frit (an amorphous type, a softening point of 570 ° C.) as the inorganic powder (A),

35 parts of resin (1) obtained in Synthesis Example 1 as water-soluble resin (B),

7 parts of ethylene oxide modified trimethylolpropane triacrylate ("Alonix M-360" manufactured by Toagosei Co., Ltd.) as a polyfunctional (meth) acrylate compound (C),

1.5 parts of 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one as a photoinitiator (D),

40 parts of propylene glycol monomethyl ether acetate as a solvent,

1.5 parts of normaldecyltrimethoxysilane as a dispersant,

2 parts of "Emulgen A-60" manufactured by Cao Corporation as dissolution accelerator (surfactant) (E),

0.1 part of 1-phenyl-3-methyl-4- (4-methylphenylazo) -5-oxypyrazole as an ultraviolet absorber

After kneading with a bead mill, an inorganic powder-containing resin composition was prepared by filtering with a stainless mesh (400 mesh, 38 μm diameter). As a result of evaluating storage stability of the obtained composition, 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 (200 mm wide, 30 m long, 38 μm thick) made of PET film using a blade coater, and the coating film was dried at 100 ° C. for 5 minutes to completely remove the solvent. And an inorganic powder-containing photosensitive resin layer having an average film thickness of 46 μm. Subsequently, the protective film which consists of PET films which carried out the mold release process previously on the said resin layer was thermo-compressed, and the transfer film which laminated | stacked the support film, the inorganic powder containing photosensitive resin layer, and the protective film in this order was produced.

(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 superimposed on the dielectric layer (film thickness of 20 micrometers) formed in the surface of the glass substrate for 6-inch panels so that the resin layer surface may contact, and this transfer film is heated by a heating roller. Thermocompression. In the crimping conditions at this time, 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. Thereby, the photosensitive resin layer containing inorganic powder was transferred to the surface of the glass substrate, and it was in the state in which it adhered.

(ii) Exposure process and development process of photosensitive resin layer

With respect to the photosensitive resin layer formed as mentioned above, i line | wire (ultraviolet light of wavelength 365nm) was irradiated with the irradiation amount of 100 mJ / cm <2> by the ultrahigh pressure mercury lamp through the exposure mask (400 micrometers wide stripe pattern).

After completion | finish of an exposure process, after peeling off the support film from the resin layer, the image development process by the shower method which used ultrapure water (30 degreeC) as a developing solution was performed for 40 second with respect to the exposed resin layer. Thereby, the uncured resin layer which was not irradiated with ultraviolet rays was removed, and the pattern of the resin layer containing inorganic powder was formed.

(iii) Firing Process of Resin Layer Pattern

The glass substrate in which the resin layer pattern was formed on the dielectric layer was baked over 50 minutes in the baking furnace in the temperature atmosphere of 580 degreeC. 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. As a result, the width of the bottom surface was 400 µm and the height was 15 µm. The firing pattern of the shape was obtained. As a result, a panel material having a partition formed on the dielectric layer was obtained.

<Examples 2 to 10, Comparative Example 1>

Except having changed alkali-soluble resin (B) into what was shown in Table 1, it carried out similarly to Example 1, and prepared the inorganic powder containing resin composition, and evaluated the storage stability. Subsequently, a transfer film was prepared using the composition, and a panel material was produced in the same manner as in Example 1 except that the developing time was changed as shown in Table 1 using the transfer film, and the developability and pattern were obtained. The shape was evaluated. The results are shown in Table 1. In addition, the evaluation method and evaluation criteria of developability and a pattern shape are as follows.

(Developing)

Evaluation method: The water image development was performed in the range for 30 to 180 second by the shower method.

Evaluation criteria: It was set as CC and the thing in which BB and the unexposed part were insoluble was AA and the thing which melt | dissolved residue of an unexposed part was made.

(Pattern shape)

Evaluation method: The cross-sectional shape of the pattern was observed using the electron microscope.

Evaluation Criteria: AA and an inverse taper shape with side edges were BB as good ones (cross section is trapezoidal shape and forward tapered shape).

Claims (10)

(A) inorganic powder, (B) a polymer having a structural unit represented by the following formula (1), (C) polyfunctional (meth) acrylates, and (D) photoinitiator An inorganic powder-containing resin composition, comprising: <Formula 1>

(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, m ≠ n, a is an integer of 1 to 100, b Is an integer from 0 to 100.) The inorganic powder-containing resin composition according to claim 1, further comprising (E) a dissolution accelerator. The inorganic powder-containing resin composition according to claim 2, wherein the dissolution accelerator (E) is polyoxyethylene aryl ether. The inorganic powder-containing resin composition according to claim 1, wherein the inorganic powder (A) is a glass powder having a softening point of 400 to 650 ° C. The inorganic powder-containing resin composition according to claim 1, wherein the polymer (B) further has a structural unit derived from an amide group-containing monomer. The inorganic powder-containing resin composition according to claim 1, wherein the polymer (B) further has a structural unit derived from a hydroxyl group-containing monomer. The inorganic powder-containing resin composition according to claim 1, wherein the polymer (B) further has a structural unit derived from an amide group-containing monomer and a structural unit derived from a hydroxyl group-containing monomer. It has an inorganic powder containing resin layer formed using the inorganic powder containing resin composition of any one of Claims 1-7, The transfer film characterized by the above-mentioned. Transferring the inorganic powder containing resin layer which comprises the said transfer film on a board | substrate using the transfer film of Claim 8, Exposing the inorganic powder-containing resin layer to form a latent image of the pattern, Developing the inorganic powder-containing resin layer to form a pattern, and Firing the pattern Method of manufacturing a member for a plasma display panel comprising a. The method of manufacturing a member for a plasma display panel according to claim 9, wherein the member for a plasma display panel is at least one member selected from partitions, electrodes, resistors, dielectrics, phosphors, color filters, and black matrices.

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