JP4639770B2 - Inorganic powder-containing resin composition, transfer film, and method for producing plasma display panel - Google Patents

Description

  The present invention relates to an inorganic powder-containing resin composition and a transfer film obtained using the same. Specifically, the present invention relates to an inorganic powder-containing resin composition and a transfer film suitable for forming a panel material constituting a plasma display panel.

  In recent years, a plasma display has attracted attention as a flat fluorescent display. FIG. 1 is a schematic view showing a cross-sectional shape of an AC type plasma display panel (hereinafter also referred to as “PDP”). In the figure, reference numerals 1 and 2 denote glass substrates arranged opposite to each other, 3 denotes a partition, and cells are defined by the glass substrate 1, the glass substrate 2, and the partition 3. 4 is a transparent electrode fixed on the glass substrate 1, 5 is a bus electrode formed on the transparent electrode 4 for the purpose of reducing the resistance of the transparent electrode 4, 6 is an address electrode fixed on the glass substrate 2, and 7 is Fluorescent material held in the cell, 8 is a dielectric layer formed on the surface of the glass substrate 1 so as to cover the transparent electrode 4 and the bus electrode 5, and 9 is on the surface of the glass substrate 2 so as to cover the address electrode 6. The formed dielectric layers 10 are protective films made of, for example, magnesium oxide. In the 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 manufacturing such a PDP dielectric layer, barrier rib, electrode, phosphor, color filter, black stripe (matrix), etc., a photosensitive inorganic particle-containing resin layer is formed on a substrate, and a photomask is formed on this film. A photolithography method or the like is preferably used in which a pattern is left on the substrate by developing after exposure by a method of irradiating ultraviolet rays through a laser or a method of direct drawing by scanning with laser light, and the like. ing.

Japanese Patent Laid-Open No. 11-162339 JP 2001-84833 A JP 2002-245932 A JP 2003-51250 A

  In principle, the photolithography method is excellent in pattern accuracy. In particular, in a method using a transfer film, a pattern having excellent film thickness uniformity and surface uniformity can be formed. However, in the conventional photolithography method, in order to perform patterning while ensuring the film thickness of the inorganic powder-containing resin layer necessary for the panel material to be formed, the sensitivity of the inorganic powder-containing resin layer is insufficient, There was a problem that the shape of the obtained pattern was difficult to be good. Also, if the photoinitiator is increased in order to ensure sensitivity, the flammability of the organic matter in the firing process is reduced, and when the electrode is formed, the resistance value is high, or when the partition is formed There was a problem that the resulting partition wall was likely to be colored. Further, there has been a problem that the developing speed in the developing process is lowered, and the workability is deteriorated and the pattern is easily cracked.

The present invention has been made based on the above situation.
The first object of the present invention is to make PDP components excellent in pattern shape (for example, dielectric layers, barrier ribs, electrodes, resistors, phosphors, color filters, black matrices, and the like without reducing the combustibility and development speed). Is to provide an inorganic powder-containing resin composition that can be suitably formed.
The second object of the present invention is to provide a transfer film that can form a PDP component excellent in workability and pattern shape.
A third object of the present invention is to provide a method for manufacturing a PDP that is capable of forming a PDP component having excellent workability and excellent pattern shape.
Further objects of the present invention will become apparent from the following description.

  The inorganic powder-containing resin composition of the present invention (hereinafter also simply referred to as “the composition of the present invention”) includes (a) inorganic powder, (b) binder resin, and (c) polyfunctional (meth) acrylate. And (d) a compound represented by the following formula (1) or the following formula (2) (hereinafter also referred to as “compound (I)”).

In [Equation (1) and (2), R ¹ and ^{R 2} are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, alicyclic hydrocarbon group having 3 to 20 carbon atoms (provided that An alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, a phenyl group and a halogen atom, which may be substituted, and a phenyl group (however, an alkyl having 1 to 6 carbon atoms) Group, an alkoxyl group having 1 to 6 carbon atoms, a phenyl group, and a halogen atom may be substituted.), An oxygen-containing heterocyclic group having 4 to 20 carbon atoms, and a group having 4 to 20 carbon atoms A nitrogen-containing heterocyclic group or a sulfur-containing heterocyclic group having 4 to 20 carbon atoms (except when R ¹ and R ² are both hydrogen atoms), and R ³ is a hydrogen atom or 1 carbon atom an 12 alkyl radical, R , ^{R 5} and ^{R 6} are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]

The transfer film of the present invention is characterized in that a layer made of the inorganic powder-containing resin composition of the present invention is formed on a support film.
In the method for producing the PDP of the present invention, an inorganic powder-containing resin layer made of the inorganic powder-containing resin composition of the present invention is formed on a substrate, and the inorganic powder-containing resin layer is exposed to light so as to form a latent image of a pattern. The inorganic powder-containing resin layer is developed to form a pattern layer, and the pattern layer is baked to form a panel member having an inorganic pattern.

  According to the method for producing an inorganic powder-containing resin composition, a transfer film and a plasma display panel of the present invention, it is possible to form an inorganic pattern having excellent workability and excellent pattern shape and good adhesion. it can. The inorganic powder-containing resin composition and transfer film of the present invention can be suitably used for forming a panel member of a plasma display panel.

Hereinafter, the present invention will be described in detail.
<Inorganic powder-containing resin composition>
(A) Examples of the inorganic substance constituting the inorganic powder constituting the composition of the inorganic powder present invention may it to use the metal particles.
Here, the inorganic powder contained in the composition for forming the “dielectric layer” and “partition wall” constituting the PDP has a softening point of 350 to 700 ° C. (preferably 400 to 620 ° C.). The glass powder inside can be mentioned. When the softening point of the glass powder is less than 400 ° C., the glass powder melts at a stage where organic substances such as the binder resin are not completely decomposed and removed in the baking process of the film forming material layer by the composition. Therefore, a part of the organic substance remains in the formed glass sintered body, and as a result, the obtained partition wall (glass sintered body) tends to be colored and its light transmittance tends to decrease. On the other hand, when the softening point of the glass powder exceeds 620 ° C., the glass substrate needs to be baked at a temperature higher than 620 ° C., so that the glass substrate is likely to be distorted.
Specific examples of suitable glass powders include: A mixture of lead oxide, boron oxide and silicon oxide (PbO—B ₂ O ₃ —SiO ₂ system); II. A mixture of zinc oxide, boron oxide and silicon oxide (ZnO—B ₂ O ₃ —SiO ₂ system), III. A mixture of lead oxide, boron oxide, silicon oxide and aluminum oxide (PbO-B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ series), IV. Examples thereof include a mixture of lead oxide, zinc oxide, boron oxide, and silicon oxide (PbO—ZnO—B ₂ O ₃ —SiO ₂ system).
These glass powders may be contained (combined) in a composition for forming components other than the barrier ribs (for example, a dielectric layer, an electrode, a resistor, a phosphor, a color filter, and a black matrix). The content of the glass powder in the inorganic powder-containing resin composition for obtaining these constituent elements is usually 90% by mass or less, preferably 5 to 90% by mass with respect to the total amount of the inorganic powder.

Examples of the inorganic powder contained in the composition for forming the “electrode” constituting the PDP include metal particles composed of Ag, Au, Al, Ni, Ag—Pd alloy, Cu, Cr, and the like. .
Examples of the inorganic powder contained in the composition for forming the “resistor” constituting the PDP include particles made of RuO 2 or the like.
As inorganic powders contained in the composition for forming the “phosphor” constituting the PDP, Y2O3: Eu ₃₊ , Y2SiO5: Eu ₃₊ , Y3Al5O12: Eu ₃₊ , YVO4: Eu ₃₊ , ( Y, Gd) BO3: Eu ₃₊ , Zn3 (PO4) 2: Red fluorescent material such as Mn; Zn2SiO4: Mn, BaAl12O19: Mn, BaMgAl14O23: Mn, LaPO4: (Ce, Tb), Y3 (Al, Ga) 5O12: fluorescent substance for green, such as Tb; Y2SiO5: Ce, BaMgAl10O17: Eu2 ₊ , BaMgAl14O23: Eu2 ₊ , (Ca, Sr, Ba) 10 (PO4) 6Cl2: Eu2 ₊ , (Zn, Cd) S: Examples thereof include particles made of a blue fluorescent material such as Ag.
Inorganic powders contained in the composition for forming the “color filter” constituting the PDP include red materials such as Fe2O3 and Pb3O4, green materials such as Cr2O3, and blue materials such as 2 (Al2Na2Si3O10) and Na2S4. Examples thereof include particles composed of substances for use.
Examples of the inorganic powder contained in the composition for forming the “black matrix” constituting the PDP include particles composed of Mn, Fe, Cr, Co, and the like.

(B) Binder Resin As the binder resin constituting the inorganic powder-containing resin composition of the present invention, various resins can be used, but a resin containing an alkali-soluble resin in a proportion of 30 to 100% by mass. Is preferably used. Here, “alkali-soluble” refers to the property of being dissolved in an alkaline developer and having a solubility to such an extent that the intended development processing is performed.
Specific examples of such alkali-soluble resins include (meth) acrylic resins, hydroxystyrene resins, novolac resins, and polyester resins.
Among such alkali-soluble resins, particularly preferred are the following copolymer of monomer (a) and monomer (c), monomer (a), monomer (b) and monomer (c): An acrylic resin such as

Monomer (I): Carboxyl group-containing monomers Acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, succinic acid mono (2- (meth) acryloyloxy) Ethyl), ω-carboxy-polycaprolactone mono (meth) acrylate, and the like.
Monomer (b): OH-containing monomers (hydroxy) -containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate; o-hydroxystyrene, Phenolic hydroxyl group-containing monomers such as m-hydroxystyrene and p-hydroxystyrene.
Monomer (C): Other copolymerizable monomers (meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylate n-butyl, (meth) acrylate 2-ethylhexyl, (meth) acrylic acid (meth) acrylic acid esters other than monomer (ii) such as n-lauryl, benzyl (meth) acrylate, glycidyl (meth) acrylate, and dicyclopentanyl (meth) acrylate; methyl-α- (hydroxymethyl) ) Acrylates, acrylates having an α-hydroxymethyl group such as ethyl-α- (hydroxymethyl) acrylate, n-butyl-α- (hydroxymethyl) acrylate; aromatic vinyl monomers such as styrene and α-methylstyrene; Conjugated dienes such as butadiene and isoprene; polystyrene, poly (meth) a Methyl acrylic acid, poly (meth) acrylate, poly (meth) macromonomers having a polymerizable unsaturated group such as one terminus (meth) acryloyl groups in the polymer chain of benzyl acrylate and the like.

The copolymer of the monomer (a) and the monomer (c) and the copolymer of the monomer (a), the monomer (b) and the monomer (c) are due to the presence of a copolymer component derived from the monomer (a). , Having alkali solubility. Among these, a copolymer of monomer (a), monomer (b) and monomer (c) is particularly preferred from the viewpoint of (A) dispersion stability of inorganic powder and solubility in an alkali developer described later.
The content of the copolymer component derived from the monomer (a) in this copolymer is preferably 5 to 60% by mass, particularly preferably 10 to 40% by mass, and the content of the copolymer component derived from the monomer (b) The content is preferably 1 to 50% by mass, particularly preferably 5 to 30% by mass.

  Particularly preferred compositions for the binder resin used in the composition of the present invention include methacrylic acid / 2-hydroxypropyl methacrylate / n-butyl methacrylate copolymer, and methacrylic acid / succinic acid mono (2- (meth)). Acryloyloxyethyl) / 2-hydroxypropyl methacrylate / n-butyl methacrylate copolymer.

The molecular weight of the alkali-soluble resin is preferably 5,000 to 5,000,000, and more preferably 10,000 to 300,000.
The content ratio of the binder resin in the inorganic powder-containing resin composition of the present invention is usually 1 to 200 parts by mass, preferably 5 to 100 parts by mass with respect to 100 parts by mass of the inorganic powder. Particularly preferably, the amount is 10 to 80 parts by mass.

(C) Polyfunctional (meth) acrylate The polyfunctional (meth) acrylate constituting the composition of the present invention has a property of being polymerized by exposure to render the exposed portion alkali-insoluble or alkali-insoluble.
Specific examples of polyfunctional (meth) acrylates include 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 hydroxylated polymers at both ends, such as hydroxypolybutadiene, hydroxyterminated polyisoprene at both ends, hydroxypolycaprolactone at both ends;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, 1,2,4-butanetriol, trimethylolalkane, tetramethylolalkane, pentaerythritol, dipentaerythritol; Poly (meth) acrylates of polyalkylene glycol adducts; poly (meth) acrylates of cyclic polyols such as 1,4-cyclohexanediol and 1,4-benzenediol; polyester (meth) acrylate, epoxy (meth) Examples thereof include oligo (meth) acrylates such as acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirane resin (meth) acrylate. It can be used in combination on.
Of these, trimethylolpropane triacrylate and the like are particularly preferably used.
The molecular weight of the polyfunctional (meth) acrylate is preferably 100 to 2,000.
The content ratio of the photopolymerizable monomer in the inorganic powder-containing resin composition of the present invention is usually 5 to 50 parts by mass, preferably 10 to 40 parts by mass with respect to 100 parts by mass of the inorganic powder. Is done.

(D) Compound (I)
Compound (I) constituting the composition of the present invention is contained as a photopolymerization initiator. By using the compound (I), a composition having a high sensitivity and a good curing depth can be obtained, and therefore, the resulting component has a good pattern shape. Moreover, since content of the whole photoinitiator can be decreased, the composition excellent in combustibility and developability can be obtained.

In the above formula (1) and the above formula (2) showing the compound (I), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alicyclic ring having 3 to 20 carbon atoms. A hydrocarbon group (however, it may be substituted with at least one selected from an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, a phenyl group and a halogen atom), a phenyl group (however, And may be substituted with at least one selected from an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, a phenyl group, and a halogen atom.), An oxygen-containing heterocyclic group having 4 to 20 carbon atoms , A nitrogen-containing heterocycle-containing group having 4 to 20 carbon atoms or a sulfur-containing heterocycle-containing group having 4 to 20 carbon atoms (except when R ¹ and R ² are both hydrogen atoms).
Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, a spiroalkyl group, a ter-cycloalkyl group, a terpene skeleton-containing group, and an adamantyl skeleton-containing group. It is done. Examples of the nitrogen-containing heterocycle-containing group having 4 to 20 carbon atoms, the oxygen-containing heterocycle-containing group having 4 to 20 carbon atoms, and the sulfur-containing heterocycle-containing group having 4 to 20 carbon atoms include, for example, thiolanyl group and azepinyl group. , Dihydroazepinyl group, dioxolanyl group, triazinyl group, oxathanyl group, thiazolyl group, oxadiazinyl group, dioxaindanyl group, dihyanaphthalenyl group, furanyl group, thiophenyl group, pyrrolyl group, isoxazolyl group, isoxazolyl group, thiazolyl Group, isothiazolyl group, pyrazolyl group, furazanyl group, pyranyl group, pyridinyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, pyrrolinyl group, morpholinyl group, piperazinyl group, quinuclidinyl group, indolyl group, isoindolyl group, benzofuranyl group, benzo Thiophenyl group, India Zinyl, chromenyl, quinolinyl, isoquinolinyl, purinyl, quinazolinyl, cinnolinyl, phthalazinyl, pteridinyl, carbazolyl, acridinyl, phenanthridinyl, thioxanthenyl, phenazinyl, phenothiazinyl, phenoxy Examples include a sathiinyl group, a phenoxazinyl group, and thiantenyl.

Specific examples of such compound (I) include 1- [9-ethyl-6-benzoyl-9.H.-carbazol-3-yl] -nonane-1,2-nonane-2-oxime-O-benzoate. 1- [9-ethyl-6-benzoyl-9.H.-carbazol-3-yl] -nonane-1,2-nonane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl -9.H.-Carbazol-3-yl] -pentane-1,2-pentane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9.H.-carbazol-3-yl ] -Octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-benzoate 1- [9-ethyl-6- (2-methylbenzo) Yl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (1,3,5-trimethylbenzoyl) -9.H.- Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-butyl-6- (2-ethylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1- Onoxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -bicycloheptylmethane-1-one oxime-O-benzoate, 1- [9-Ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -bicycloheptyl-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methyl Benzoyl) -9.H.-Cal Basol-3-yl] -adamantylmethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -adamantylmethane- 1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -tetrahydrofuranylmethane-1-one oxime-O-benzoate, 1 -[9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -tetrahydrofuranylmethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9.H.-carbazol-3-yl] -thiophenylmethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzo) ) -9.H.-carbazol-3-yl] -thiophenylmethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazole- 3-yl] -Morophonylmethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -morophonyl Methane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-bicycloheptanecarboxylate 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-tricyclodecanecarboxylate, 1- [9-ethyl -6 (2-Methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-adamantane carboxylate and the like. Two or more of these may be used at the same time.
Of these, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate is particularly preferable. The compound is a compound represented by the above formula (1), wherein R ¹ is a methyl group, R ² is a methyl group, R ³ is an ethyl group, R ⁴ is a methyl group, and R ⁵ and R ⁶ are hydrogen atoms. .
As a content rate of compound (I) in the composition of this invention, it is 0.1-50.0 mass parts normally with respect to 100 mass parts of polyfunctional (meth) acrylate, Preferably, it is 1.0. -30.0 parts by mass.

In the composition of the present invention, a photopolymerization initiator other than the compound (I) may be used in combination. Specific examples of other photopolymerization initiators include benzyl, benzoin, benzophenone, camphorquinone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy. 2-phenylacetophenone, 2-methyl- [4 ′-(methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1 Carbonyl compounds such as -one; Azo compounds or azide compounds such as azoisobutyronitrile and 4-azidobenzaldehyde; Organic sulfur compounds such as mercaptan disulfide; Benzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroper Oxide, Kume Organic peroxides such as hydrogen peroxide and paraffin hydroperoxide; 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -1,3,5-triazine, 2- [2- (2- Furanyl) ethylenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine and the like; 2,2′-bis (2-chlorophenyl) 4,5,4 ′, 5′-tetraphenyl Examples thereof include imidazole dimers such as 1,2'-biimidazole. These can be used alone or in combination of two or more.
The content ratio of the other photopolymerization initiator is 50% by mass or less, preferably 30% by mass or less, based on the total amount of the photopolymerization initiator.

The inorganic powder-containing resin composition of the present invention usually contains a solvent for imparting appropriate fluidity or plasticity and good film-forming properties. As a solvent to be used, the affinity with inorganic powder and the solubility of the binder resin are good, and it can impart an appropriate viscosity to the inorganic powder-containing resin composition and is easily dried. It is preferable that it can be removed by evaporation.
Particularly preferred solvents include ketones, alcohols and esters (hereinafter referred to as “specific solvents”) having a normal boiling point (boiling point at 1 atm) of 100 to 200 ° C.

Specific examples of the specific solvent include ketones such as diethyl ketone, methyl butyl ketone, dipropyl ketone, and cyclohexanone; alcohols such as n-pentanol, 4-methyl-2-pentanol, cyclohexanol, and diacetone alcohol. Ether ether alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether; saturated aliphatic monocarboxylic acids such as n-butyl acetate and amyl acetate Alkyl esters; lactic acid esters such as ethyl lactate and lactic acid-n-butyl; methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl acetate Examples include ether esters such as diacetate and ethyl-3-ethoxypropionate. Among these, methyl butyl ketone, cyclohexanone, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, lactic acid Ethyl, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate and the like are preferable. These specific solvents can be used alone or in combination of two or more.
Specific examples of solvents other than the specific solvent include turpentine oil, ethyl cellosolve, methyl cellosolve, terpineol, butyl carbitol acetate, butyl carbitol, isopropyl alcohol, benzyl alcohol and the like.
The content ratio of the solvent in the inorganic powder-containing resin composition of the present invention can be appropriately selected within a range in which good film forming properties (fluidity or plasticity) are obtained.

In addition, the inorganic powder-containing resin composition of the present invention includes, as optional components, plasticizers, dispersants, development accelerators, adhesion assistants, antihalation agents, leveling agents, storage stabilizers, antifoaming agents, and antioxidants. Various additives such as an agent, an ultraviolet absorber, a sensitizer, and a chain transfer agent may be contained.
The inorganic powder-containing resin composition of the present invention comprises the above-mentioned inorganic powder, binder resin, photopolymerizable monomer, photopolymerization initiator and solvent and, if necessary, the above optional components, a roll kneader, a mixer, a homomixer It can be prepared by kneading using a kneader such as a ball mill or a bead mill.
The inorganic powder-containing resin composition prepared as described above is a paste-like composition having fluidity suitable for coating, and its viscosity is usually 100 to 1,000,000 cp, preferably 500 to 300,000 cp.

<Transfer film>
The transfer film of the present invention is obtained by forming a layer obtained by applying the inorganic powder-containing resin composition of the present invention on a support film and drying the coating film. 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. Examples of the resin forming 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 thickness of the support film is, for example, 20 to 100 μm.

As a method of applying the inorganic powder-containing resin composition on the support film, it is possible to efficiently form a coating film having a large film thickness (for example, 10 μm or more) excellent in film thickness uniformity. Specifically, 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, a coating method using a wire coater, and the like can be mentioned as preferable examples.
The surface of the support film to which the inorganic powder-containing resin composition is applied is preferably subjected to a release treatment. Thereby, the peeling operation of a support film can be easily performed in the case of PDP component formation.

As drying conditions of a coating film, it is set as about 0.5 to 30 minutes, for example at 50-150 degreeC, and the residual ratio (content rate in an inorganic powder containing resin layer) after drying is 2 mass% normally. It is assumed to be within.
The thickness of the inorganic powder-containing resin layer formed on the support film as described above is, for example, 5 to 500 μm, although it varies depending on the content and size of the inorganic powder.
Examples of the protective film layer that may be provided on the surface of the inorganic powder-containing resin layer include a polyethylene film and a polyvinyl alcohol film.

<Manufacturing method of PDP>
In the method for producing the PDP of the present invention, an inorganic powder-containing resin layer is formed on a substrate using the inorganic powder-containing resin composition of the present invention or the transfer film of the present invention, and the inorganic powder-containing resin layer is exposed. Forming a pattern latent image, developing the inorganic powder-containing resin layer to form a pattern layer, and baking the pattern layer to form a panel member having an inorganic pattern. Features. Below, each process is demonstrated.

(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 on the substrate. It can form by transferring the inorganic powder containing resin layer in a transfer film. According to the method using a transfer film, an inorganic powder-containing resin layer excellent in film thickness uniformity can be easily formed, and the film thickness of the formed pattern can be made uniform. Furthermore, you may form the laminated body which has an inorganic powder containing 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. Alternatively, the laminate may be formed by collectively transferring a laminate comprising n layers of inorganic powder-containing resin layers onto a substrate using a transfer film formed on a support film.
Examples of the coating method of the inorganic powder-containing resin composition include various methods such as a screen printing method, a roll coating method, a spin coating method, and a casting coating method, and the inorganic powder-containing resin composition of the present invention was applied. Then, the inorganic powder containing resin layer A can be formed by the method of drying a coating film. Note that an n-layer stack may be formed by repeating the above steps 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 on the surface of the substrate so that the surface of the resin layer containing the inorganic powder comes into contact with the transfer film. Then, the support film is peeled and removed from the inorganic powder-containing resin layer. As a result, the inorganic powder-containing resin layer is transferred and adhered to the surface of the substrate. Here, 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, and the moving speed of the heating roller is 0.1 to 10 m / min. be able to. Moreover, the board | substrate may be preheated and can be 40-140 degreeC as preheating temperature, for example.

(Ii) Exposure process The latent image of the pattern by a method of selectively irradiating (exposure) radiation such as ultraviolet rays to the surface of the inorganic powder-containing resin layer through an exposure mask or a method of scanning with laser light. Form. Here, as the radiation irradiation apparatus, an ultraviolet irradiation apparatus generally used in a photolithography method, an exposure apparatus used when manufacturing a semiconductor and a liquid crystal display device, a laser apparatus, etc. are used. It is not limited.
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 inorganic powder-containing resin layer is developed to form a pattern of the inorganic powder-containing resin layer. Here, as development processing conditions, depending on the type of the inorganic powder-containing resin layer, the type / composition / concentration of the developer, the development time, the development temperature, the development method (for example, dipping method, rocking method, shower method, A spray method, a paddle method, etc.), a developing device, and the like can be appropriately selected.

(Vi) Firing Step The pattern of the inorganic powder-containing resin layer is fired to burn off the organic material in the remaining portion of the inorganic powder-containing resin layer. By this step, PDP components such as a dielectric layer, partition walls, electrodes, resistors, phosphors, color filters, and a black matrix are formed from the pattern of the inorganic powder-containing resin layer.
Here, the temperature of the baking treatment needs to be a temperature at which the organic substance in the inorganic powder-containing resin layer (residual portion) is burned off, and is usually 400 to 600 ° C. The firing time is usually 10 to 90 minutes.

Hereinafter, materials used in the above steps, various conditions, and the like will be described.
<Board>
Examples of the substrate material include plate-like members made of an insulating material such as glass, silicone, polycarbonate, polyester, aromatic amide, polyamideimide, and polyimide. For the surface of the plate-like member, chemical treatment with a silane coupling agent or the like, if necessary, plasma treatment; thin film formation treatment by an ion plating method, a sputtering method, a gas phase reaction method, a vacuum deposition method, etc. Such an appropriate pretreatment may be performed.
In the present invention, it is preferable to use glass having heat resistance as the substrate. As a glass substrate, Asahi Glass Co., Ltd. product PD200 can be mentioned as a preferable thing, for example.

<Exposure mask>
The exposure pattern of the exposure mask used in the exposure process according to the manufacturing method of the present invention is 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 according to the production method of the present invention, an alkali developer can be preferably used.
In addition, since the inorganic powder contained in the inorganic powder-containing resin layer is uniformly dispersed by the alkali-soluble resin, the inorganic soluble resin, which is the binder resin, is dissolved in an alkaline solution and washed to obtain an inorganic powder. The powder is also removed at the same time.
As an active ingredient of the alkaline developer, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate , Inorganic such as potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia Alkaline compounds; tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropyl Triethanolamine, and organic alkaline compounds such as ethanol amine.
The alkaline developer can be prepared by dissolving one or more of the alkaline compounds in water. Here, the concentration of the alkaline compound in the alkaline developer is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass. In addition, after the development process with an alkali developer is performed, a washing process is usually performed.

Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following, “part” means “part by mass”.
Moreover, Mw is the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) (brand name HLC-802A) by Tosoh Corporation.

<Example 1>
(1) Preparation of resin composition containing inorganic powder (a) As inorganic powder, 100 parts of Ag powder (average particle size 2.2 μm) and glass frit (Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ system) Average particle diameter 3 μm, irregular shape, softening point 520 ° C., thermal expansion coefficient α ₃₀₀ = 87 × 10 ⁻⁷ / ° C.) 10 parts, (b) Binder resin as methacrylic acid / 2-hydroxypropyl methacrylate / methacrylic acid -N-butyl = 25/25/50 (mass%) copolymer (Mw = 50,000) 30 parts, (c) 30 parts of trimethylolpropane triacrylate as polyfunctional (meth) acrylate, (d) 1- [9-Ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-oneoxime-O-acetate 3 parts as compound (I), oleic acid as dispersant 1 part and solvent Then, 100 parts of propylene glycol monomethyl ether was kneaded with a bead mill, and then filtered with a stainless mesh (500 mesh, 25 μm diameter) to prepare an inorganic powder-containing resin composition (I).
(2) Formation of inorganic powder-containing resin layer After coating the inorganic powder-containing resin composition (I) on a glass substrate with a thickness of 10 μm by screen printing, it is dried in a clean oven at 100 ° C. for 5 minutes to make inorganic A powder-containing resin layer was formed.
(3) Inorganic powder-containing resin layer exposure step Ultrahigh pressure is applied to the inorganic powder-containing resin layer formed on the glass substrate through a striped negative exposure mask having a line width of 100 μm and a space width of 400 μm. A mixed light of g-line (436 nm), h-line (405 nm) and i-line (365 nm) was irradiated with a mercury lamp. The exposure amount at that time was 400 mJ / cm ^{2 in} terms of illuminance measured by a 365 nm sensor.
(4) Development process The exposed inorganic powder-containing resin layer is subjected to a development process by a shower method using a 0.3% by mass sodium carbonate aqueous solution at a liquid temperature of 30 ° C. for 60 seconds, followed by Then, it was washed with ultrapure water. Thereby, the uncured inorganic powder-containing resin layer not irradiated with ultraviolet rays was removed, and an inorganic powder-containing resin layer pattern was formed.
(5) Firing step The glass substrate on which the pattern of the inorganic powder-containing resin layer was formed was baked for 30 minutes in a 590 ° C. temperature atmosphere in a firing furnace. Thus, a panel material in which an electrode having a pattern width of 100 μm and a thickness of 6 μm was formed on the surface of the glass substrate could be obtained. The obtained electrode was excellent in pattern shape and shape uniformity, and no cracks were observed.

<Example 2>
(1) Preparation of resin composition containing inorganic powder (a) Glass frit (Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ system, average particle size 3 μm, amorphous, softening point 520 ° C., heat as inorganic powder (Expansion coefficient α ₃₀₀ = 87 × 10 ⁻⁷ / ° C.) 100 parts, (b) As binder resin, methacrylic acid / 2-hydroxypropyl methacrylate / n-butyl methacrylate = 25/25/50 (mass%) 20 parts of copolymer (Mw = 50,000), (c) 20 parts of trimethylolpropane triacrylate as polyfunctional (meth) acrylate, (d) 1- [9-ethyl-6 as compound (I) -(2-Methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate 3 parts, di-2-ethylhexylazelate 4 parts as plasticizer and propylene glycol as solvent After 100 parts of recall monomethyl ether was kneaded with a bead mill, an inorganic powder-containing resin composition (II) was prepared by filtering with a stainless mesh (500 mesh, 25 μm diameter).
(2) Formation of inorganic powder-containing resin layer An inorganic powder-containing resin composition (II) was applied on a glass substrate by screen printing at a thickness of 200 μm, and then dried in a clean oven at 100 ° C. for 30 minutes to make inorganic A powder-containing resin layer was formed.
(3) Inorganic powder-containing resin layer exposure step Ultrahigh pressure is applied to the inorganic powder-containing resin layer formed on the glass substrate through a striped negative exposure mask having a line width of 100 μm and a space width of 400 μm. A mixed light of g-line (436 nm), h-line (405 nm), and i-line (365 nm) was irradiated with a mercury lamp. The exposure amount at that time was 1 J / cm ^{2 in} terms of illuminance measured by a 365 nm sensor.
(4) Development step Development treatment of the inorganic powder-containing resin layer by a shower method using a 1.0% by mass sodium carbonate aqueous solution having a liquid temperature of 30 ° C. as a developer for the exposed inorganic powder-containing resin layer For 450 seconds, followed by washing with ultrapure water. Thereby, the uncured inorganic powder-containing resin layer not irradiated with ultraviolet rays was removed, and an inorganic powder-containing resin layer pattern was formed.
(5) Firing step The glass substrate on which the pattern of the inorganic powder-containing resin layer was formed was baked for 30 minutes in a 590 ° C. temperature atmosphere in a firing furnace. As a result, a panel material in which partition walls having a pattern width of 100 μm and a thickness of 135 μm were formed on the surface of the glass substrate could be obtained. The obtained partition wall was excellent in pattern shape and shape uniformity, and no crack was observed.

<Comparative Example 1>
Inorganic powder except that 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one is used in place of the component (d) of the inorganic powder-containing resin composition (I) By preparing in the same manner as the containing resin composition (I), an inorganic powder-containing resin composition (III) was prepared.
An inorganic powder-containing resin layer is formed in the same manner as in Example 1 except that the inorganic powder-containing resin composition (III) is used instead of the inorganic powder-containing resin composition (I), and exposure and development are performed. As a result, the pattern portion (ultraviolet irradiation portion) was dissolved in the development step, and a pattern could not be obtained.

<Comparative Example 2>
Inorganic powder except that 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one is used in place of the component (d) of the inorganic powder-containing resin composition (II) An inorganic powder-containing resin composition (IV) was prepared by preparing in the same manner as the containing resin composition (II).
An inorganic powder-containing resin layer is formed in the same manner as in Example 1 except that the inorganic powder-containing resin composition (IV) is used instead of the inorganic powder-containing resin composition (II), and exposure and development are performed. As a result, the pattern portion (ultraviolet irradiation portion) was dissolved in the development step, and a pattern could not be obtained.

<Example 3>
(1) Production process of transfer film Using a direct reverse coater on a support film (width 200 mm, length 30 m, thickness 38 μm) made of a PET film which has been pre-molded with the inorganic powder-containing resin composition (II). The transfer film (I) having an inorganic powder-containing resin layer with a thickness of 25 μm was formed by applying and drying the coating film at 100 ° C. for 5 minutes to completely remove the solvent. (2) Transfer process of transfer film The transfer film (I) was superposed on the glass substrate so that the surface of the inorganic powder-containing resin layer was in contact with the glass substrate, and thermocompression bonded with a heating roller. Here, as pressure bonding conditions, the surface temperature of the heating roller was 90 ° C., the roll pressure was 2 kg / cm, and the moving speed of the heating roller was 0.5 m / min.
(3) Exposure process The transfer film (I) pressure-bonded onto the glass substrate is subjected to g-line (436 nm), h with an ultrahigh pressure mercury lamp through a striped negative exposure mask having a line width of 100 μm and a space width of 400 μm. A mixed light of a line (405 nm) and i line (365 nm) was irradiated. The exposure amount at that time was 1 J / cm ^{2 in} terms of illuminance measured by a 365 nm sensor. After the exposure, the support film on the inorganic powder-containing resin layer was peeled off.
(4) Development step Development treatment of the inorganic powder-containing resin layer by a shower method using a 1.0% by mass sodium carbonate aqueous solution at a liquid temperature of 30 ° C. as a developer for the exposed inorganic powder-containing resin layer. For 450 seconds, followed by washing with ultrapure water. Thereby, the uncured inorganic powder-containing resin layer not irradiated with ultraviolet rays was removed, and an inorganic powder-containing resin layer pattern was formed.
(5) Firing step The glass substrate on which the pattern of the inorganic powder-containing resin layer was formed was baked for 30 minutes in a 590 ° C. temperature atmosphere in a firing furnace. As a result, a panel material in which partition walls having a pattern width of 100 μm and a thickness of 120 μm were formed on the surface of the glass substrate could be obtained. The obtained partition wall was excellent in pattern shape and shape uniformity, and no crack was observed.

<Comparative Example 3>
A transfer film was formed in the same manner as in Example 3 except that the inorganic powder-containing resin composition (IV) was used instead of the inorganic powder-containing resin composition (II), and transfer, exposure and development were performed. However, the pattern portion (ultraviolet irradiation portion) was dissolved in the development process, and a pattern could not be obtained.

It is a schematic diagram which shows the cross-sectional shape of an alternating current type plasma display panel.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Glass substrate 3 Partition 4 Transparent electrode 5 Bus electrode 6 Address electrode 7 Fluorescent substance 8 Dielectric layer 9 Dielectric layer 10 Protective layer

Claims (3)

(A) Metal particles , (b) binder resin, (c) polyfunctional (meth) acrylate and (d) a compound represented by the following formula (1) or the following formula (2) for electrode formation Resin composition.

[In Formula (1) and Formula (2), R1 and R2 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms (provided that An alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, a phenyl group and a halogen atom, which may be substituted with at least one selected from the above, a phenyl group (however, an alkyl group having 1 to 6 carbon atoms, May be substituted with at least one selected from an alkoxyl group having 1 to 6 carbon atoms, a phenyl group, and a halogen atom.), An oxygen-containing heterocyclic group having 4 to 20 carbon atoms, and a nitrogen-containing group having 4 to 20 carbon atoms A heterocycle-containing group or a sulfur-containing heterocycle-containing group having 4 to 20 carbon atoms (except when R1 and R2 are both hydrogen atoms), and R3 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms R4, 5 and R6 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ] A transfer film, wherein a layer made of the electrode forming resin composition according to claim 1 is formed on a support film. An inorganic powder-containing resin layer comprising the resin composition for forming an electrode according to claim 1 is formed on a substrate, the inorganic powder-containing resin layer is exposed to light to form a latent image of the pattern, and the inorganic powder A method for producing a plasma display panel, comprising: forming a pattern layer by developing a resin layer, and baking the pattern layer to form a panel member having an inorganic pattern.

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