CN1926473B - Inorganic paste composition, method for preparing inorganic paste composition, and sheet-shaped unbaked body for producing display panel - Google Patents
Inorganic paste composition, method for preparing inorganic paste composition, and sheet-shaped unbaked body for producing display panel Download PDFInfo
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- CN1926473B CN1926473B CN200580006199.8A CN200580006199A CN1926473B CN 1926473 B CN1926473 B CN 1926473B CN 200580006199 A CN200580006199 A CN 200580006199A CN 1926473 B CN1926473 B CN 1926473B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
Abstract
The present invention provides an inorganic paste composition, containing inorganic powders, a binder resin having a hydroxyl group in a side chain thereof, and an organic solvent having no hydroxyl group, and contains an organic solvent having a hydroxyl group in an amount equal to or less than 5% by weight. The composition gives a film having a uniform dispersion of the inorganic powders therein and uniform thickness. The resulting film does not cause much shrinkage.
Description
Technical field
The present invention relates to a kind of inorganic paste composition and preparation method thereof and a kind of sheet-shaped unbaked body that utilizes inorganic paste composition to produce display board.
Background technology
The mode that plasma scope forms image is to utilize electric discharge phenomena to make a large amount of micro units (finecell) self luminous, and it has excellent characteristics, can form roomy image, thin, lightweight and smooth, and traditional display then can not be realized these characteristics.The popular of plasma scope is intending.
Traditional plasma scope mainly adopts structural unit in upright arrangement; On wherein flank (rib) only is formed at vertically; Yet recently in order to make light be incorporated into the front of plasma scope effectively; Developed the unit with grid (waffle) structure, wherein flank (rib) not only is formed at vertical direction, also is formed at horizontal direction.In the unit, have lattice structure, stoped light leak, light can be transmitted forward with very high efficient from adjacent unit.
Plasma scope with lattice structure type unit is a kind of display device, and it comprises front panel and rear panel, and front panel is made up of the compound electrode that forms parallel to each other, and wherein each compound electrode is made up of a transparency electrode and a bus (bus) electrode; Its rear panel is by parallel to each other and form with the address electrode of compound electrode direction right-angled intersection; Front panel and rear panel are arranged to face one another and combine.Front panel has transparent glass substrate as display plane, and compound electrode is arranged in the inboard of glass substrate, just a real estate side of panel backward.Be formed with dielectric layer in order to cover compound electrode, the wall of patterning is set on the dielectric layer, and the diaphragm of being made up of for example MgO is formed on the surface of dielectric layer and wall.On the other hand, address electrode is arranged on the substrate of rear panel towards a side of front panel, is formed with dielectric layer in order to the overlay address electrode, and the light radiating portion that below will describe is formed on this dielectric layer.
The light radiating portion is made up of a large amount of unit, and each unit all is arranged in the interval that compound electrode and address electrode intersect.Said unit is made up of the flank that vertical direction and horizontal direction are formed on the dielectric layer, and be provided with fluorescence coating and be used to cover the sidewall of flank and the dielectric layer surface in the flank, that is, and the inwall of each unit and bottom.In plasma scope, be applied in the compound electrode of front panel from the predetermined voltage of AC power, between electrode, form electric field, make and produce discharge in the unit.Discharge causes ultraviolet light to generate, and further causes the light emission from fluorescence coating.
In the plasma scope of lattice structure type, a large amount of walls are set on the dielectric layer with the arrangement mode of equidistant intervals straight line.In the plate, wall and flank keep in touch in front, therefore form the gap on each top, unit that is centered on by flank, and rare gas can be introduced each unit through the gap.
Produce this plasma scope, mainly use photoetching process.
Below will describe and use photolithographic production run.At first, on glass substrate, form dielectric layer of forming by the glass lotion film of non-photosensitivity property and the wall of forming by the glass lotion film of photosensitivity, see through photomask, with for example UV-irradiation wall.Then, wall is developed, and to show photoresistance (resist) pattern, 500 to 700 ℃ of bakings, forms dielectric layer and wall thus simultaneously thereafter.
In using photolithographic production run, dielectric layer and wall can toast in a baking operation simultaneously, and therefore the cost required with using method for printing screen aborning compared, and can advantageously reduce production costs.
Summary of the invention
The glass paste composition that is used to form dielectric layer and wall can prepare through in adhesive component, disperseing glass dust, and said adhesive component is that the dissolved adhesive resin obtains in the organic solvent that is fit to.As adhesive resin, consider the purpose that adheres to glass substrate, adopt the resin that contains hydroxyl usually.In organic solvent wherein, consider the main alcohols solvent that uses on industrial-scale production for the dissolving hydroxy-containing resin with the angle of protection Environmental security from obtaining the resolvability of hydroxy-containing resin solvent.
Yet when glass dust added in the adhesive component be made up of hydroxy-containing resin and alcohols solvent, the problem of generation was that glass dust can not evenly disperse and usually forms aggregation.
In order to form uniform films by the glass paste composition, it is extremely important that glass dust is dispersed in the adhesive component.When glass dust is inhomogeneous when being scattered in the adhesive component; Just, when the thick and rare part of glass dust being dispersed with in adhesive component, through the glass paste composition being applied to when forming film on the removable supporting film; A large amount of glass lotions; Thick part in the glass dust of said dispersion just can cause the striped of this film surface quality to be reduced.
Between the hydroxy radical content of the dispersibility of glass dust and adhesive resin, exist contact closely,, can improve the dispersibility of glass dust in adhesive resin through increasing the hydroxy radical content of adhesive resin.Yet when the adhesive resin that uses had great amount of hydroxy group, dielectric layer produced the puzzlement of shrinking in baking step, between substrate and dielectric layer, produce strain, so just another disadvantageous problem occurred, promptly in dielectric layer, formed be full of cracks.
Therefore, for the conventional glass paste composition, be difficult to improve simultaneously the dispersibility of glass dust and the flatness of dielectric layer.
The present invention considers the problems referred to above just and accomplishes; An object of the present invention is to provide a kind of organic paste composition and preparation method thereof; Its advantage is that not only glass dust has excellent dispersibility in composition, and this composition can form the uniform film of thickness.Another object of the present invention provides a kind of sheet-shaped unbaked body that is used to produce display board, and its thickness is even, and can in the process of curing, suppress shrinkage.
The inventor furthers investigate in order to address the above problem.The result finds that the dispersibility for improving glass dust is coming from the hydroxyl that is adsorbed on the glass dust surface moisture, and comes from that to form hydrogen bond between the hydroxyl of adhesive resin very important.Find also that in addition when using the not organic solvent of hydroxyl, and the content that contains the organic solvent of hydroxyl is when being limited in being equal to or less than 5 weight %, can be preferentially between glass dust and the adhesive resin and form hydrogen bond effectively.When using the not organic solvent of hydroxyl; And when the content of organic solvent in composition that contains hydroxyl is limited in preset range; Can suppress to form hydrogen bond between adhesive resin and the organic solvent, thereby improve the dispersibility of glass dust in adhesive resin.
Particularly; Inorganic paste composition of the present invention is a kind of inorganic powder that contains, and side chain has the adhesive resin of hydroxyl; And the composition of the organic solvent of hydroxyl not, the content that contains the organic solvent of hydroxyl in the wherein inorganic paste composition is equal to or less than 5 weight %.
For the organic solvent of said not hydroxyl, it preferably uses by selected at least a organic solvent in ether, ketone and the ester.Have the adhesive resin of hydroxyl for side chain, it preferably uses the acryl resin with hydroxyl.Preferably, attend the average number of institute's hydroxyl in each monomeric unit side chain of adhesive resin, the content of hydroxyl is equal to or less than 0.3 for each monomeric unit in the side chain of binder resin.
The preparation method of inorganic paste composition of the present invention is used for preparation to contain inorganic powder; Side chain has the adhesive resin of hydroxyl; The inorganic paste composition of the organic solvent of hydroxyl not; The method comprises the step of at least three kinds of said components of mixing and the gained potpourri of kneading, and wherein, said potpourri comprises the organic solvent with hydroxyl that is equal to or less than 5 weight %.
The sheet-shaped unbaked body that is used to produce display board of the present invention is a kind of flaky material that contains removable supporting film and inorganic lotion film; Inorganic lotion film is formed on the removable supporting film, and inorganic lotion film is made up of inorganic paste composition of the present invention at least.In this manual; Term " is used to produce the sheet-shaped unbaked body of display board " and representes a kind of flaky material that is used to produce display board; The layer that wherein is formed on the removable supporting film can be peeled off from the described supporting film of removing, and is laminated on the glass substrate.
In inorganic paste composition of the present invention; Through using the not organic solvent of hydroxyl; And use organic solvent according to the amount that is equal to or less than 5 weight % with hydroxyl; Can significantly improve the dispersiveness of inorganic powder in adhesive resin, therefore can prevent when applying said composition, to produce striped.
In addition; Through adopting the not organic solvent of hydroxyl; And use organic solvent with hydroxyl according to being equal to or less than 5 weight %, even the hydroxy radical content of adhesive resin is relatively low, the glass dust in the composition still can keep gratifying dispersiveness; Thereby in the average number of each monomeric unit institute's hydroxyl in side chain of adhesive resin, the content that can set hydroxyl in the side chain of adhesive resin is that each monomeric unit is equal to or less than 0.3.Usually, evenly disperse in adhesive resin in order to make inorganic powder, the hydroxy radical content of adhesive resin is adjusted to a higher level inevitably, and this causes shrinkage in the process of curing easily.When the average number that attendes institute's hydroxyl in the side chain of each monomeric unit of adhesive resin, when the hydroxy radical content of adhesive resin was equal to or less than each monomeric unit 0.3, this problem just can solve.That is to say, in inorganic paste composition of the present invention, inorganic powder uniformly dispersed in adhesive resin and comprise that the film character of film flatness can be improved simultaneously.
In inorganic paste composition of the present invention, the acryl resin that has hydroxyl through use is as adhesive resin, can strengthen its bonding to glass substrate.In addition, be selected from least a organic solvent in ether, ketone and the ester as the organic solvent of hydroxyl not through use, the dispersiveness of inorganic powder can be further improved.
In the preparation method of inorganic paste composition of the present invention; Utilizing not, the organic solvent of hydroxyl mixes various compositions; Therefore come from the hydroxyl that is adsorbed on the glass dust surface moisture; And come between the hydroxyl of adhesive resin can be at a relatively high speed (preferentially and effectively) form hydrogen bond, therefore can prepare inorganic paste composition with excellent dispersiveness and excellent film character.
The sheet-shaped unbaked body that is used for producing display board of the present invention can be used for forming the dielectric substance and the layer of spacer material of various displays, like plasma scope, plasma address LCD and Field Emission Display.And can be used to form dielectric layer and layer of spacer material easily, in the plasma scope front panel that needs high precision.
Preferred forms of the present invention
Below will introduce exemplary embodiment of the present invention.
(A) inorganic paste composition
Inorganic paste composition of the present invention comprises inorganic powder at least, and side chain has the adhesive resin of hydroxyl and the organic solvent of hydroxyl not, comprises the organic solvent with hydroxyl that is equal to or less than 5 weight % in the wherein inorganic paste composition.
Inorganic paste composition of the present invention is a kind of lotion that is dispersed in the inorganic powder in the adhesive ingredients that comprises, adhesive ingredients makes through the adhesive resin that has hydroxyl on the dissolving side chain in the organic solvent of hydroxyl not.
In inorganic paste composition of the present invention, as adhesive resin, from obtaining that the excellent cohesive consideration of glass substrate is employed in the hydroxy-containing resin that its side chain terminal has hydroxyl.Hydroxy-containing resin is easy to be dissolved in the organic solvent with hydroxyl, therefore, uses the solvent that contains hydroxyl usually, for example can use alcohols usually.
On the contrary, inorganic paste composition of the present invention is characterised in that the organic solvent that uses hydroxyl not is as solvent.When using the organic solvent of hydroxyl not, between adhesive resin and organic solvent, there is not hydrogen bond to form, therefore used solvent can not suppress inorganic powder and adhesive resin formation hydrogen bond.For this reason, the hydrogen bond quantity between inorganic powder and the adhesive resin is increased, and the dispersiveness of inorganic powder in adhesive resin improved.
(a) organic solvent
Organic solvent about using among the present invention has no particular limits, if dissolved adhesive resin easily, and in the molecule not hydroxyl get final product.As organic solvent, it preferably uses at least a organic solvent that is selected from ethers, ketone and the ester class.
In the present invention; Object lesson with an organic solvent, comprise ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene acetate, ethylene glycol diethyl ether, butyl cellosolve, glycol dimethyl ether, glycol monomethyl phenyl ether acetic acid esters, ethylene glycol ether acetic acid esters, glycerine triacetate, glycerine trilaurin, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol monobutyl ether acetic acid esters, diethylene glycol diacetate, diethylene glycol dimethyl ether acetic acid esters, diethyl carbitol acetic acid esters, diethylene glycol dibutyl ether acetic acid esters, diethylene glycol dibenzoate, triglyme, triethylene glycol monomethyl ether acetic acid esters, propylene-glycol diacetate, Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether, propylene glycol butyl oxide, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetic acid esters, DPG diacetate esters, DPG dimethyl ether, DPG diethyl ether, DPG butyl oxide, dipropylene glycol monomethyl ether acetic acid esters, DPG monoethyl ether acetate, DPG monobutyl ether acetic acid esters, acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone, acetophenone, isophorone, ethyl normal-butyl ketone, diacetone alcohol (4-hydroxy-4-methyl-2 pentanone), diisobutyl ketone, diisobutyl acetone, metacetone, cyclohexanone, two positive acetone, methyl-n-amyl ketone (amyl methyl ketone), methyl cyclohexanone, methyl n-butyl ketone, methyl n-pro-pyl ketone, methyl n hexyl ketone, methyl n heptyl ketone, diethylene adipate, acetyl tributyl citrate trimethyl, ATEC, tributyl 2-acetylcitrate, methyl acetoacetate, ethyl acetoacetate, butyl-acetoacetate, isoamyl benzoate, methyl benzoate, ethyl benzoate, butyl benzoate, propyl benzoate, Ergol, isoamyl formate, iso-butyl formate, ethyl formate, butyl formate, propyl formate, hexyl formate, benzyl formate, methyl formate, triethyl citrate, ATBC, pentyl acetate, allyl acetate, isoamyl acetate, acetate methyl isopentyl ester, methoxy butyl acetate, isobutyl acetate, isopropyl acetate, ethyl acetate, methyl acetate, sec-hexyl acetate, acetate 2-Octyl Nitrite, acetate 2-ethyl butyl ester, cyclohexyl acetate, methylcyclohexyl acetate, n-butyl acetate, sec-butyl acetate, isopropyl acetate, benzyl acetate, methylcyclohexyl acetate, diamyl oxalate, diethy-aceto oxalate, diethy-aceto oxalate, dibutyl oxalate, diethyl tartrate, dibutyl tartrate, amyl stearate, methyl stearate, ethyl stearte, butyl stearate, amyl lactate, methyl lactate, ethyl lactate, butyl lactate, phthalate, gamma-butyrolacton, isoamyl propionate, methyl propionate, ethyl propionate, butyl propionate, benzyl propionate, Diisopropyl malonate, dimethyl malenate, diethyl malonate, dibutyl malonate, isoamyl butyrate, isopropyl isobutyrate, methyl butyrate, ethyl butyrate, butyl butyrate, alkane, toluene, hexane, cyclohexane, cyclohexene, cyclopentane, halogenated hydrocarbons and nitrogen-containing compound.
In these organic solvents; Preferred boiling point is 250 ℃ or lower solvent; Preferred especially boiling point is at 100 ℃ to 200 ℃ organic solvent; Preferred especially solvent is dichloroethyl ether (boiling point: 178.6 ℃), n-butyl ether (boiling point: 140.9 ℃), isoamyl ether (boiling point: 173.2 ℃), methyl phenyl ether (boiling point: 153.9 ℃), ethylphenyl ether (boiling point: 170.1 ℃), tolyl methyl ether (boiling point: 171.8～176.7 ℃), EBE (boiling point: 185 ℃), chloropropylene oxide (boiling point: 117 ℃), diglycidyl ether (boiling point: 103 ℃), 1; 4-dioxane (boiling point: 101.4 ℃), trioxane (boiling point: 114.5 ℃), furfural (boiling point: 162 ℃), cineole (boiling point: 176 ℃ to 177 ℃), diethyl acetal (boiling point: 104.2 ℃), the positive acetone of methyl (boiling point: 102.4 ℃), methyl n-butyl ketone (boiling point: 127.2 ℃), methylisobutylketone (boiling point: 116.7 ℃), MAK (boiling point: 150.2 ℃), the positive hexanone of methyl (boiling point: 174 ℃), diethyl ketone (boiling point: 101.7 ℃), the positive butanone of ethyl (boiling point: 147.4 ℃), two positive acetone (boiling point: 144.2 ℃), diisobutyl ketone (boiling point: 168.2 ℃), acetonyl acetone (boiling point: 191.4 ℃), DAA (boiling point: 163～167.9 ℃), Mesityl oxide (boiling point: 131.4 ℃), phorone (boiling point: 198.2 ℃), cyclohexanone (boiling point: 156 ℃), neighbour-methyl cyclohexanone (boiling point: 165 ℃), n-buty formate (boiling point: 106.8 ℃), amyl formate (boiling point: 130.4 ℃), n-propyl acetate (boiling point: 101.6 ℃), n-butyl acetate (boiling point: 126.3 ℃), isobutyl acetate (boiling point: 118 ℃), sec-butyl acetate (boiling point: 112.2 ℃), n-amyl acetate (boiling point: 149.0 ℃), isoamyl acetate (boiling point: 142.0 ℃), acetate methyl isopentyl ester (boiling point: 146.3 ℃), methoxy butyl acetate (boiling point: 173 ℃), sec-hexyl acetate (boiling point: 146.3 ℃), acetate 2-ethyl butyl ester (boiling point: 162 ℃ to 163 ℃), 2-ethyl hexyl ethanoate (boiling point: 197.5 ℃ to 198 ℃), cyclohexyl acetate (boiling point: 175 ℃ to 176 ℃), methylcyclohexyl acetate (boiling point: 181.5 ℃ to 186.5 ℃),, n-butyl propionate (boiling point: 146.8 ℃), isoamyl propionate (boiling point: 160.3 ℃), methyl butyrate (boiling point: 102.3 ℃), ethyl butyrate (boiling point: 121.3 ℃), the positive butyl ester of butyric acid (boiling point: 164.8 ℃), isoamyl butyrate (boiling point: 179 ℃), ethyl butyrate of hydroxyl iso (boiling point: 147.5 ℃ to 149 ℃), methyl acetoacetate (boiling point: 171.7 ℃), ethyl acetoacetate (boiling point: 180.4 ℃), iso-amyl iso-valeriate (boiling point: 192.7 ℃), methyl lactate (boiling point: 143.8 ℃), ethyl lactate (boiling point: 154.1 ℃), n-butyl lactate (boiling point: 188 ℃), methyl benzoate (boiling point: 199.5 ℃), diethy-aceto oxalate (boiling point: 183.5 ℃) and diethyl malonate (boiling point: 198.9 ℃).Said solvent can separately or make up and use.When multiple solvent combinations was used, the azeotropic temperature of these solvents especially was preferably 100 ℃ to 200 ℃ with 250 ℃ or lower being advisable.
(b) inorganic powder
Preferably use can be through curing the glass dust that forms glass for inorganic powder in the present invention, and the example comprises PbO-SiO
2, PbO-B
2O
3-SiO
2, ZnO-SiO
2, ZnO-B
2O
3-SiO
2, BiO-SiO
2, BiO-B
2O
3-SiO
2, PbO-B
2O
3-SiO
2-Al
2O
3, and PbO-ZnO-B
2O
3-SiO
2Glass dust.
Except that glass dust, can also adopt the inorganic powder that comprises pottery (for example trichroite) or metal.The instantiation of this inorganic powder comprises the oxide of cobalt oxide, iron oxide, chromium oxide, nickel oxide, cupric oxide, manganese oxide, neodymia, vanadium oxide, cerium titania oxide yellow thing, cadmium oxide, ruthenium-oxide and Na, K, Mg, Ga, Ba, Ti, Zr or Al, for example silicon dioxide, magnesium oxide and spinel.
About the particle size of inorganic powder, preferably adopting average particle size particle size is the inorganic powder of 0.1 to 10 μ m, more preferably 0.5 to 8 μ m.When using average particle size particle size greater than the inorganic powder of 10 μ m; The film surface may roughening and comparatively unfavorable when forming high-precision patterns; When using average particle size particle size less than the inorganic powder of 0.1 μ m; In the process of curing, may form pore in the film and comparatively unfavorable, cause failure of insulation.The instance of inorganic powder shape comprises spherical, block, laminar and dendritic, and the inorganic powder of these shapes can separately or make up and use.
As selection, said inorganic powder can be the fine granular potpourri with different physics values.Especially, when using glass dust, can suppress the shrinkage in the process of curing with the ceramic powder that has with the different thermal softening points of glass dust.Said inorganic powder preferably according to the purposes of inorganic paste composition, prepares through the combination that changes different shape and physics value.
(c) adhesive resin
In inorganic paste composition of the present invention, the resin that the use side chain has hydroxyl is as adhesive resin.
Adhesive resin can comprise the material that the following monomer polymerization that provides or copolymerization are obtained, and it can introduce hydroxyl in resulting resin.
The said monomer that can introduce hydroxyl be preferably (methyl) but the monomer of acrylic ester, the undersaturated carbonic acid of ethylenic or another kind copolymerization.The example comprises benzyl acrylate; Benzyl methacrylate; Cyclohexyl acrylate; Cyclohexyl methacrylate; Phenoxyethyl acrylate; The methacrylic acid ethyl phenoxy; Acrylic acid phenoxy group macrogol ester; Methacrylic acid phenoxy group macrogol ester; Styrene; Nonylphenoxy polyglycol mono acrylic ester; The Nonylphenoxy polyethylene glycol monomethacrylate; Nonylphenoxy polypropylene mono acrylic ester; Nonylphenoxy polypropylene monomethacrylates; 2-hydroxyl-3-benzene oxygen propyl group acrylic ester; 2-acrylyl oxy-ethyl phthalic ester; 2-acrylyl oxy-ethyl-2-hydroxyethyl phthalic ester; 2-methylacryoyloxyethyl-2-hydroxypropyl phthalic ester; Methyl acrylate; Ethyl acrylate; Methyl methacrylate; Jia Jibingxisuanyizhi; The acrylic acid n-propyl; N propyl methacrylate; Isopropyl acrylate; Isopropyl methacrylate; N-butyl acrylate; N-BMA; Isobutyl acrylate; Isobutyl methacrylate; Sec-butyl acrylate; The secondary butyl ester of methacrylic acid; Tert-butyl acrylate; The metering system tert-butyl acrylate; Acrylic acid 2-hydroxy methacrylate; 2-hydroxyethyl methacrylate; Acrylic acid 2-hydroxy propyl ester; Methacrylic acid 2-hydroxy propyl ester; Acrylic acid 3-hydroxy propyl ester; Methacrylic acid 3-hydroxy propyl ester; Acrylic acid 2-hydroxyl butyl ester; Methacrylic acid 2-hydroxyl butyl ester; Acrylic acid 3-hydroxyl butyl ester; Methacrylic acid 3-hydroxyl butyl ester; Acrylic acid 4-hydroxyl butyl ester; Methacrylic acid 4-hydroxyl butyl ester; Acrylic acid 3-Octyl Nitrite; Diethylene glycol monoacrylate; Ethylene glycol methacrylate; Acrylic acid glyceride; Glyceral methacrylate; The dipentaerythritol mono acrylic ester; The dipentaerythritol monomethacrylates; Acrylic acid diformazan ammonia ethyl ester; Dimethylaminoethyl acrylate methyl ammonia ethyl ester; The acrylic acid tetrahydro furfuryl ester; The methacrylic acid tetrahydro furfuryl ester; Acrylic acid; Methacrylic acid; Butenoic acid (crotonic acid); Styrene acid (cinnamic acid); Maleic acid; Maleic anhydride; Fumaric acid; Itaconic acid; Itaconic anhydride; Citric acid; Citric anhydride.In these materials, preferably use acrylic acid and methacrylic acid.
The instance of other copolymerisable monomer comprises that the instantiation with above-mentioned (methyl) acrylic ester has the compound of same structure, just (methyl) acrylic ester be replaced by fumarate, maleate, butenoate or itaconate, AMS, o-methyl styrene, a methyl styrene, p-methylstyrene, chloro styrene, m-chlorostyrene, to chlorostyrene, O-methoxy styrene, meta-methoxy styrene, to methoxy styrene, vinyl acetate, vinyl butyrate, propionate, acrylic amide, Methacrylamide, vinyl cyanide, methacrylonitrile, isoprene, chlorbutadiene and 3-butadiene.
Among the present invention; The average number of the hydroxyl that comprises in each the monomeric unit side chain in adhesive resin; The content of hydroxyl is preferably each monomeric unit and is equal to or less than 0.3 in the side chain of the adhesive resin that adopts, and more preferably 0.1 to 0.3, be preferably 0.15 to 0.25 especially.When the hydroxy radical content of molecule exceeds each monomeric unit 0.3, in the process of curing will shrinkage appear unfriendly, cause the dielectric layer be full of cracks.
The adhesive resin that side chain has hydroxyl can together use with other adhesive resin.The instance of said operable other adhesive resin comprises cellulose derivative, for example the multipolymer of cellulose, CMC, hydroxyethyl cellulose, hydroxypropyl cellulose, CMC, carboxyethyl cellulose or carboxylic second methylcellulose or cellulose derivative and ethylenic unsaturated carboxylic acid or (methyl) acrylate compounds.
The instance of adhesive resin also comprises polyvinyl alcohol (PVA), and for example the reaction product of polyvinyl alcohol (PVA) and butyraldehyde is gathered butyral resin; The polyester that gets by lactone ring opening polymerization; For example δ-Wu Neizhi, 6-caprolactone, beta-propiolactone, Alpha-Methyl-beta-propiolactone, Beta-methyl-beta-propiolactone, Alpha-Methyl-beta-propiolactone, Beta-methyl-beta-propiolactone, α; Alpha-alpha-dimethyl-beta-propiolactone or β, beta-dimethyl--beta-propiolactone; The polyester that gets by the glycol condensation reaction; Said glycol can be a kind of or more kinds of aklylene glycol; For example monoethylene glycol, propylene glycol, diglycol, triethylene glycol, DPG or neopentyl glycol, and dicarboxylic acid, for example maleic acid, fumaric acid, glutaric acid or hexane diacid; Polyethers, for example polyglycol, polypropylene glycol, gather tetramethylene glycol and polypentamethylene glycol; With the reaction product polycarbonate of glycol, for example bisphenol-A, p-dihydroxy-benzene or dihydroxy cyclohexane, and carbonyls, for example dipheryl carbonate base ester, phosgene or succinic anhydride.Described adhesive resin can use respectively, perhaps uses with the form of two kinds or more eurypalynous adhesive resin potpourri.
In the present invention, be 100 parts with adhesive resin with other adhesive resin general assembly (TW) with hydroxyl, the adhesive resin that side chain has hydroxyl can account for 30 weight portions or more, and other adhesive resin accounts for 70 weight portions or still less.Preferably; The adhesive resin that side chain has hydroxyl accounts for 50 weight portions or more, and other adhesive resin accounts for 50 weight portions or still less, more preferably; The adhesive resin that side chain has hydroxyl accounts for 70 weight portions or more, and other adhesive resin accounts for 30 weight portions or still less.When the amount increase of other adhesive resin, the dispersiveness of inorganic powder in composition be variation very unfriendly.
(d) other component
Inorganic paste composition of the present invention contains above-mentioned (a) not organic solvent of hydroxyl, (b) inorganic powder and (c) side chain have hydroxyl adhesive resin as principal ingredient, and can further comprise other component according to its purposes.
For example; When inorganic paste composition of the present invention is when being used for producing the wall of plasma scope front panel; The said paste composition that contains three kinds of principal ingredients can also further comprise photo polymerization monomer and Photoepolymerizationinitiater initiater as component, makes composition have photosensitivity.
The instance of said photo polymerization monomer comprises abovely listed having the relevant monomer of adhesive resin of hydroxyl with (c) side chain, and is preferably and has two or more polymerisable ethylenic unsaturated links the monomer of (below be referred to as " polyfunctional monomer ").The instance of polyfunctional monomer comprises alkylene glycols, for example the diacrylate of monoethylene glycol or propylene glycol or dimethylacrylate; Polyvalent alcohol, the for example diacrylate of polyglycol or polypropylene glycol or dimethylacrylate; And polyhydric alcohol, the for example polyacrylate of glycerine, trimethylolpropane, pentaerythrite or dipentaerythritol or polymethacrylate; The product that also has its dicarboxylic acid modification.In these monomers, concrete instance comprises ethylene glycol diacrylate, GDMA, diacrylate triethyleneglycol ester, dimethacrylate triethyleneglycol ester, diacrylate tetraethylene glycol ester, dimethacrylate tetraethylene glycol ester, diacrylate propylene glycol ester, dimethyl allene acid propylene glycol ester, diacrylate polypropylene glycol ester, dimethacrylate polypropylene glycol ester, three acrylic acid trihydroxy methyl propyl ester, trimethyl acrylic acid trihydroxy methyl propyl ester, tetrapropylene acid tetra methylol propyl ester, tetramethyl acrylic acid tetra methylol propyl ester, pentaerythritol triacrylate, trimethyl acrylic acid pentaerythritol ester, pentaerythritol tetracrylate, pentaerythritol tetramethacrylate, pentamethyl acrylic acid dipentaerythritol ester, six acrylic acid dipentaerythritol ester and hexamethyl acrylic acid dipentaerythritol ester.
The instance of Photoepolymerizationinitiater initiater can comprise 1-hydroxycyclohexylphenylketone, 2; 2-dimethoxy-1; 2-diphenyl-1-ethyl ketone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2; 4; 6-trimethylbenzene formyl diphenyl phosphine oxide, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-acetone, 2; 4-diethyl thioxanthone, 2-clopenthixal ketone, 2; 4-dimethyl thioxanthones, 3; 3-dimethyl-4-methoxybenzene ketone, Benzophenone, 1-chloro-4-propoxyl group thioxanthones, 1-(4-isopropyl phenyl)-2-hydroxyl-2 methyl isophthalic acids-acetone, 1-(4-dodecylphenyl)-2-hydroxyl-2 methyl isophthalic acids-acetone, 4-benzoyl-4 '-methyl dimethoxy base sulfide, 4-dimethylamino benzene (first) acid, 4-dimethylaminobenzoic acid methyl esters, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid butyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, 4-dimethylaminobenzoic acid 2-isopentyl ester, 2; 2-diethoxy acetophenone, 2; 2-dimethoxy-2-phenyl acetophenone, benzyl dimethyl ketal, benzyl-'beta '-methoxy ethyl acetals, 1-phenyl-1; 2-propanedione, 2-(adjacent ethoxy carbonyl) oxime, o-benzoyl yl benzoic acid methyl esters, two (4-dimethylamino phenyl) ketone, 4,4 '-two lignocaine Benzophenones, 4,4 '-dichloro-benzenes ketone, hexichol (base) second diketone, benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin n-butylether, benzoin isobutyl ether, to the dimethylamino acetophenone, to tert-butyl group trichloroacetophenone, to tert-butyl group dichloroacetophenone, thioxanthones, 2-methyl thioxanthones, 2-isopropyl thioxanthone, Dibenzosuberone, α; α-two chloro-metaphenoxy acetophenone, 4-dimethylaminobenzoic acid pentyl ester, 9-phenylacridine, 1; 7-pair-(9-acridinyl) heptane, 1,5-pair-(9-acridinyl) pentane and 1,3-pair-(9-acridinyl) propane.Use can distinguished or make up to these Photoepolymerizationinitiater initiaters.
When inorganic paste composition of the present invention is used for producing the dielectric layer of plasma scope front panel; Said dielectric layer can comprise absorber of light; It can absorb the light of certain wavelength coverage; The light of wavelength coverage makes the wall photoactivate, and just, optical activation is included in the Photoepolymerizationinitiater initiater in the wall.For this kind absorber of light; It preferably uses and can absorb 300 to those of 450nm wavelength light, and instance comprises azo dyes (azo dyes), aminoketone dye, xanthene dyestuff, quinoline dye, benzophenone dyestuff, triasine dyes, benzotriazole dyestuff and anthraquinone dye.
But the absorber of light that contains when dielectric layer can absorbing wavelength scope optical activation be included in the light time of the Photoepolymerizationinitiater initiater in the wall; Make wall with dielectric layer and the range upon range of each other state exposure of wall; Be patterned in the process of predetermined form;, stoped the incident ray scattering on ground floor owing to the inorganic powder in the dielectric layer.In other words; If dielectric layer does not contain absorber of light; Light maybe be owing to the inorganic powder grains in the dielectric layer be scattered, so wall can be exposed to the light that gets into from the indefinite direction of dielectric layer, will be difficult to the pattern that has pinpoint accuracy according to photomask formation.In order to prevent this problem, must form said wall and exposure,, cures dielectric layer after curing then, so that it becomes the clear glass state, in other words, need two to go on foot independently baking step.On the contrary, when dielectric layer contained absorber of light, the curing of dielectric layer and wall can be carried out simultaneously and formed the pattern that needs.
In order to make film have plasticity, can add plastifier in the composition.Can adopt conventional known plastifier, preferred boiling point is the good plastifier of liquid state and transparency under the room temperature at 200 ℃ or higher.The example comprises phthalic compounds, for example repefral, diethyl phthalate, dibutyl phthalate, dibutyl phthalate (DHP), di-2-ethylhexyl phthalate, diisononyl phthalate, diisooctyl phthalate, phthalic acid dibutyl benzyl ester, dioctyl phthalate and phthalyl Ji Dingji Glycolic acid butyl ester; Adipate compound, for example diisobutyl adipate, diisononyl adipate, diisodecyl adipate (DIDA) and dibutoxyethyl adipate; Decanedioic acid compound, for example dibutyl sebacate, Diisooctyl Sebacate; Phosphate cpd, for example triethyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate (xylene) ester and tricresyl phosphate base phenyl ester; Fatty acid cpds, for example di-n-octyl sebacate and castor oil acid methyl acetonyl ester; Epoxy compound, for example 4,5-epoxy tetrahydrophthalic acid two isodecyl esters; Trimellitic acid compound, for example tributyl trimellitate, tri trimellitate-2-Octyl Nitrite, tri trimellitate n-octyl and triisodecyl trimellitate; With butyl oleate, chlorinated paraffin, polybutylene and polyisobutylene.These plastifier can use separately, perhaps two kinds in them or more kinds ofly can mix use as required.
(e) composition ratios
Inorganic paste composition of the present invention is characterised in that it contains the organic solvent with hydroxyl that is equal to or less than 5 weight %.Said instance with organic solvent of hydroxyl comprises the organic solvent that dilutes usefulness, alcohols for example, and the amount of its interpolation does not in the present invention weaken with the dispersiveness that strengthens inorganic powder is advisable.Instance with organic solvent of hydroxyl also comprises the hydroxyl organic solvent that contained originally in any additives.This instantiation with organic solvent of hydroxyl comprises alcohols, for example methyl alcohol, ethanol, monoethylene glycol, diglycol, propylene glycol and 3-methoxyl-3-methyl butanol; With the alkyl ether of polyvalent alcohol, for example glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether and dihydroxypropane single-ether.When the organic solvent content that has hydroxyl in the inorganic paste composition surpasses 5 weight %, between organic solvent with hydroxyl and adhesive resin, will disadvantageously form hydrogen bonded, and suppress adhesive resin and inorganic powder formation hydrogen bond.In the inorganic paste composition of the present invention, the content with organic solvent of hydroxyl is preferably and is equal to or less than 1 weight %, more preferably is equal to or less than 0.1 weight %.
In the inorganic paste composition of the present invention, be equal to or less than 5 weight % as long as have the content of the organic solvent of hydroxyl, the ratio of various compositions can be done suitably adjustment according to the purposes of composition.Below will be described in detail the ratio of various compositions, especially be used to form the composition of dielectric layer in the plasma scope front panel and the composition that (2) are used to form plasma scope front panel intermediate interlayer for (1).
Composition (1)
When inorganic paste composition of the present invention is used to form dielectric layer; The side chain of per 100 weight portions has the adhesive resin of hydroxyl; The organic solvent of the not hydroxyl that is added is comparatively favourable with 30 to 500 weight portions, is preferably 50 to 300 weight portions, more preferably 100 to 250 weight portions.
The total amount of whole organic components of per 100 weight portions (comprising organic solvent, adhesive resin and other composition), the inorganic powder amount that is added is advisable with 100 to 1000 weight portions.The side chain of per 100 weight portions has the adhesive resin of hydroxyl, and the plasticising dosage that is added is preferably 5 to 100 weight portions, more preferably 10 to 80 weight portions with 200 weight portions or more being advisable more.
The total amount of the inorganic powder of per 100 weight portions, adhesive resin and absorber of light, the absorber of light of being mixed with 30 weight portions or more being advisable more.When the amount of absorber of light surpasses 30 weight portions, the composition that obtains is absorbing light too much, and the wall near the interface is made public unsatisfactorily, and this will cause that for example film peels off problems such as maybe can not forming pattern.
Composition (2)
When inorganic paste composition of the present invention is used to form wall; The side chain of per 100 weight portions has the adhesive resin of hydroxyl; The organic solvent of used not hydroxyl is advisable with 30 to 700 weight portions, is preferably 50 to 500 weight portions, more preferably 100 to 300 weight portions.
Whole organic components of per 100 weight portions (comprising organic solvent, adhesive resin, photopolymerizable monomer, Photoepolymerizationinitiater initiater and other composition) total amount, the inorganic powder amount that is added is advisable with 100 to 1000 weight portions.
The side chain of per 100 weight portions has the adhesive resin of hydroxyl, and the amount of used photo polymerization monomer is advisable with 10 to 500 weight portions, is preferably 30 to 300 weight portions, further is preferably the scope of 50 to 200 weight portions.
The side chain of per 100 weight portions has the adhesive resin of hydroxyl, and the amount of used Photoepolymerizationinitiater initiater is advisable with 0.01 to 50 weight portion, more preferably the scope of 0.1 to 20 weight portion.When the amount of Photoepolymerizationinitiater initiater is lower than 0.01 weight portion, the curable variation of composition.On the other hand, when the amount of Photoepolymerizationinitiater initiater exceeds 50 weight portions, because the absorption of initiating agent, possibly observe in the bottom and to solidify failure.
(B) method of the inorganic paste composition of preparation
The present invention prepares inorganic paste composition method and is characterised in that it comprises a step that three kinds of components are mixed and knead; Three kinds of components comprise that inorganic powder, side chain have the bonding resin of hydroxyl and the organic solvent of hydroxyl not, and the composition in the step of wherein kneading contains the organic solvent with hydroxyl that is equal to or less than 5 weight %.
In the present invention, for the not special restriction of the order by merging of described adhesive resin, organic solvent and inorganic powder.For example, comprise that three kinds of components of adhesive resin, organic solvent and inorganic powder can mix simultaneously, also can inorganic powder be added and sneak in advance perhaps that adhesive resin is dissolved in the organic solvent in the formed adhesive component.Take a kind of method in back as an example, below will narrate the preparation method of inorganic paste composition of the present invention, but the order of mixing said component is not limited to this instance.
At first, through stirrer will be not organic solvent and the adhesive resin of hydroxyl mix, so that adhesive resin is dissolved in the organic solvent, in order to prepare adhesive component.In this step, can add photo polymerization monomer, light gathers initiating agent and adjuvant, for example plastifier, spreading agent, tackifier, surface tension modifier, stabilizing agent or foam-breaking agent.
After the adhesive component preparation is accomplished, add inorganic powder therein and process potpourri, and potpourri is through kneading to disperse inorganic powder.When inorganic powder stored under normal operation, it absorbed airborne moisture, therefore had the hydroxyl of the surperficial adsorbed moisture that stems from inorganic powder.So just need not be in order to introduce hydroxyl on the inorganic powder surface and to make it through some special processings.Yet if inorganic powder long-time storage under drying condition, preferred mode is before using, and randomly makes it absorb moisture, then it is joined in the said adhesive component.
Among the present invention, in the potpourri of the step of kneading, the content with organic solvent of hydroxyl is advisable with as far as possible for a short time.Especially, the content of organic solvent in potpourri that has a hydroxyl be limited in 5 weight % or lower be necessary.Can comprise organic solvent in the potpourri, as adjuvant or mishmash with hydroxyl.In this case, if having the too high levels of organic solvent in potpourri of hydroxyl, between organic solvent with hydroxyl and adhesive resin, form disadvantageous hydrogen bond, and inhibition adhesive resin and inorganic powder form hydrogen bond jointly.In the step of kneading, the organic solvent content that has hydroxyl in the potpourri is preferably and is equal to or less than 5 weight %, more preferably is equal to or less than 1 weight %, further is preferably and is equal to or less than 0.1 weight %.
In the present invention, have the organic solvent of hydroxyl, alcohols for example, can be before disperseing inorganic powder or after add, as long as effect is enhancing and do not weaken the dispersiveness of inorganic powder.
If before disperseing inorganic powder; Just, before forming hydrogen bond between inorganic powder and the adhesive resin, the hydroxyl solvent is added in the potpourri; Adhesive resin and hydroxyl solvent can form disadvantageous hydrogen bond jointly, cause the dispersiveness of inorganic powder to reduce.If yet the total content that has the organic solvent of hydroxyl in the potpourri is equal to or less than 5 weight %, just do not have problem, even potpourri contains a certain amount of hydroxyl solvent.
The potpourri that disperses inorganic powder to obtain through the step of kneading can be used as inorganic paste composition of the present invention.
Through disperseing can to add annexing ingredient again in the potpourri that inorganic powder obtains, the potpourri that obtains at last can be used as inorganic paste composition.For example, inorganic powder is disperseed with after the formation hydrogen bond between inorganic powder and adhesive resin, and the hydrogen bond between inorganic powder and the adhesive resin keeps relative stability.Therefore, in this situation, even add the organic solvent with hydroxyl in the potpourri, for example alcohols also can influence the hydrogen bonded between inorganic powder and the adhesive resin sharply.So after the step of kneading, can randomly add the organic solvent of hydroxyl, alcohols for example is to regulate the concentration of inorganic paste composition.
(C) be used to produce the sheet-shaped unbaked body of display board
Sheet-shaped unbaked body of the present invention comprises removable supporting film and inorganic lotion film, and said inorganic lotion film is to be coated on said the removal on the supporting film with inorganic paste composition of the present invention, and dry gained film forms.For example; Use the sheet-shaped unbaked body of the inorganic paste composition of non-photosensitivity property can be used to form the dielectric layer in the plasma scope front panel, use the sheet-shaped unbaked body of the inorganic paste composition of photosensitivity can be used to form the wall in the plasma scope front panel.Sheet-shaped unbaked body of the present invention can be protected the surface of inorganic lotion film with the film removed that is easy to peel off, so is easy to store, transports and carrying.
Sheet-shaped unbaked body of the present invention utilizes inorganic paste composition of the present invention to form, and wherein inorganic powder evenly disperses, and therefore has excellent flatness.In addition, can also suppress the shrinkage in the process of curing, thus thickness is even, do not have be full of cracks dielectric layer or wall can be obtained, therefore can production high-quality display plate.
In addition, one of sheet-shaped unbaked body of the present invention is characterised in that and can produces and store one section preset time in advance, though be a limited time, it just can be applied to produce display board at once like this, thereby improves display board production efficiency.
Preferably, sheet-shaped unbaked body of the present invention should all have the form of the film the removed protection that is easy to peel off to provide with the two sides of inorganic lotion film.Particularly, be formed at the dielectric layer that to remove on the supporting film and be coated with diaphragm as protective seam.
About producing the used supporting film of sheet-shaped unbaked body of the present invention,, just there is not particular restriction as long as it for can remove film, makes the rete that is formed on the supporting film be easy to peel off and transfers on the glass substrate.Its instance can be that the thickness that synthetic resin film constitutes is the elastic membrane of 15 to 125 μ m, for example polyethylene terephthalate, tygon, polypropylene, polycarbonate or PVC.If necessary, preferably, supporting film can consider to pass through processing for convenient the removal.
On supporting film, form inorganic lotion film the time; Inorganic paste composition of the present invention is produced, and said inorganic paste composition is coated on the supporting film through using applicator, bar coater, wired bar coater, roll coater or curtain flow coater.Preferred especially roll coater is because its film that can effectively form excellent uniform thickness and have satisfied big thickness.
Film is after drying, and preferably, the surface of inorganic lotion film covers stably to protect inorganic lotion film before use with diaphragm.As diaphragm, it is preferably that polyethylene terephthalate film, polypropylene screen or polyethylene film etc. have a silicon coating or is about the film of 15 to 125 μ m through what cure with thickness.
In producing the display board process; Diaphragm can be peeled off from sheet-shaped unbaked body of the present invention; Gained not baked body can be arranged on the glass substrate; Make after the exposure inorganic lotion film with above be formed with electrode glass baseplate surface contact, and hot cylinder moves on supporting film, with the hot pressing of inorganic lotion film on substrate surface.
Preferably, it is to carry out under 80 to 140 ℃ the condition that hot pressing is heated to surface temperature at substrate, and rolling pressure is 1 to 5kg/cm
2, translational speed is 0.1 to 10.0 meter/minute.Glass substrate can pass through preheating, and preheat temperature can be selected, and for example, scope is 40 to 100 ℃.
The diaphragm of peeling off from inorganic lotion film can adjoining land by the rolling of a rolling cylinder and with the reel stores, can reuse.
Thermal is to substrate surface by this method for inorganic lotion film, and supporting film can make the face exposure of the inorganic lotion film on substrate from inorganic lotion film sur-face peeling then.The supporting film that inorganic lotion film from substrate is peeled off also can adjoining land by the rolling of a rolling cylinder and with the reel stores, can reuse.
This being formed at peeled off the lip-deep inorganic lotion film of substrate, can cure at 500 to 700 ℃, and the glass dust that comprises in the inorganic lotion film of sintering forms any one in dielectric layer and/or the wall.At baking step, organic substance contained in the inorganic lotion film can volatilize and decompose, to such an extent as in fact there is not organic component to be retained in dielectric layer or the wall.Therefore, display board of the present invention has just been accomplished.
After such method production display board, preferably, the dielectric layer of exposure covers with the diaphragm that for example MgO forms.
Embodiment
Below will combine embodiment that the present invention is carried out more concrete explanation.It should be noted that the present invention is not limited by these embodiment.
Embodiment 1 to 7 and comparative example 1
(1) glass lotion preparation of compositions
According to the proportion of composing (unit: weight portion) shown in the following table 1; Adhesive resin, solvent and other component were stirred 3 hours and mix; 50%) and (PbO-SiO of 80 weight portions the preparation organic principle is then with this kind organic principle of 40 weight portions (solids content:
2) glass dust mixes and knead into the glass paste composition.
(2) production of sheet-shaped unbaked body
The glass paste composition that obtains is coated on the supporting film of polyethylene terephthalate formation with flanging coater (lip coater); The gained film was 100 ℃ of dryings 6 minutes; Remove solvent fully, on supporting film, form the glass lotion film of thickness 60 μ m like this.At the polyethylene film of glass lotion film laminated thickness 25 μ m, make sheet-shaped unbaked body then.
(3) formation of dielectric layer
Peel off in the above-mentioned steps (2) when forming the polyethylene film in the sheet-shaped unbaked body, under 105 ℃, make glass lotion film lamination have bus electrode above that and be preheating on 80 ℃ the glass substrate with hot rolling layer press.Air pressure is 3kg/cm
3, laminate speed is 1.0 meters/minute.
(4) assessment of glass lotion film
In order to estimate the performance of every kind of glass lotion film in embodiment 1 to 7 and the comparative example 1, carried out following evaluation test.The result sees the following form 1.
(outward appearance of peeling off behind the supporting film is observed)
In peeling off above-mentioned steps (3), form behind the polyethylene terephthalate of dielectric layer kind as supporting film, observed the outward appearance of glass lotion film.
G: the defective of not finding striped for example or pit.
NG: the defective of finding striped for example or pit.
(curing front surface roughness Rmax)
Measure the surfaceness of glass lotion film with the contact pin type surface roughness instruments.
(curing back surfaceness Rmax)
In order to estimate the glass lotion film character after curing, said film then 580 ℃ of operational processes of keeping 30 minutes, is used the surfaceness of contact pin type surfaceness detector measures gained film according to 1.0 ℃/minute speed rising temperature again.
(resistance to pressure)
Cure the back and measure resistance to pressure.
G: the resistance to pressure that the surface records is uniform.
NG: the resistance to pressure that the surface records is uneven.
Table 1
Annotate:
(A-1): the adhesive resin that has hydroxyl on the side chain
Isobutyl methacrylate/Hydroxyethyl Acrylate=90/10 (weight %) multipolymer (molecular weight: 70,000)
(A-2): the adhesive resin that has hydroxyl on the side chain
Styrene/methacrylic acid hydroxy methacrylate=55/45 (weight %) multipolymer (molecular weight: 40,000)
(A-3): the adhesive resin that has hydroxyl on the side chain
Hydroxypropyl cellulose
(B-1): solvent ethyl acetate
(B-2): the solvent acetic acid butyl ester
(B-3): solvent acetic acid 3-methoxyl butyl ester
(B-4): the positive butanone of solvent ethyl
(B-5): the positive butanone of solvent ethyl acetate/ethyl=50/50 (weight %)
(B-6): solvent 3-methoxyl-3-methyl butanol
(C-1): monomer phthalic acid 2-methylacryoyloxyethyl-2-hydroxy propyl ester
(C-2): Photoepolymerizationinitiater initiater
2,2-dimethoxy-2-phenyl acetophenone
(C-3): absorber of light
Azo dyes (trade name: Dye SS; Daito Chemix manufactured) (prevents halation) (C-4): the plasticizer phthalic acid dibutyl ester
In embodiment 1 to 5 and 7; The organic solvent that uses hydroxyl not is as solvent; Make the dispersiveness of glass dust very outstanding; From table 1 showed about cure preceding and cure after surfaceness Rmax data and resistance to pressure evaluation result uniformly, can see accurately smooth glass lotion film.In addition, in embodiment 6, a part of organic solvent is the organic solvent (3-methoxyl-3-methyl butanol) with hydroxyl; But total amount for whole organic solvents (that account for the glass paste composition is 0.0167 weight %); Therefore this solvent has only 0.1 weight % seldom, and in embodiment 1 to 5 and 7 for example, dispersiveness is very good; Can form glass lotion film with excellent flatness, and measured resistance to pressure uniformity.
On the contrary, in comparative example 1, compare glass dust dispersed unsatisfactory with embodiment 1 to 7.Its reason is; Use organic solvent (3-methoxyl-3-methyl butanol) as organic solvent in the comparative example 1 with hydroxyl; And the weight of relative glass paste composition, said organic solvent content is 16.7 weight %, is higher than the essential value (5 weight %) of defined among the present invention.Can see from the evaluation result shown in the table 1, according to cure preceding and cure after surfaceness Rmax data, compare with embodiment 1 to 7, its film flatness is poor, and the surface withstand voltage property that records is inhomogeneous.
Embodiment 8
(1) sheet-shaped unbaked body production
To produce sheet-shaped unbaked body 1 with embodiment 1 identical mode, difference is to add the azo dyes (trade name: Dye SS of 0.5 weight portion; Daito Chemix manufactured), as absorber of light.
Then, to produce sheet-shaped unbaked body 2 with embodiment 7 identical modes, difference is that the thickness of glass lotion film is 40 μ m.
(2) formation of sheet-shaped unbaked layered product
Polyethylene film in peeling off sheet-shaped unbaked body 1 under 105 ℃, makes baked body 1 lamination not have bus electrode on it and is preheating on 80 ℃ the glass substrate with hot rolling layer press simultaneously.Air pressure is 3kg/cm
3, laminate speed is 1.0 meters/minute.Be stripped from as the polyethylene terephthalate of supporting film then.
Then, polyethylene film in peeling off sheet-shaped unbaked body 2 at room temperature, makes not with the roll laminating machine that baked body 2 is laminated on not baked body 1 surface on the glass substrate simultaneously, and said glass substrate is preheating to 80 ℃.Air pressure is 3kg/cm
3, laminate speed is 1.0 meters/minute.So just form the sheet-shaped unbaked layered product that contains sheet-shaped unbaked body 1 and sheet-shaped unbaked body 2 on the glass substrate.In this stage, the surface coverage of layered product has supporting film.
(3) do not cure evaluation and dielectric generation of sheet layered product
Not cure the sheet layered product be 300mj/cm in irradiation energy through being formed with the test pattern photomask of predetermined pattern, making to utilize extra-high-pressure mercury vapour lamp
2Down exposure of ultraviolet ray.Then, peel off polyethylene terephthalate as supporting film.Gained sheet layered product is through a nozzle injection pressure 30kg/cm
3, temperature is that 30 ℃ water carried out spray developing 30 seconds, can be to remove by the unexposed portion of the photosensitive film of water development, thus form pattern.
The gained pattern is estimated according to pattern form, the result, and minimum feature is 60 μ m in the lines of all formation.Then, pattern is cured processing, wherein temperature improves with 10 ℃/minute speed, and keeps 30 minutes at 580 ℃.Obtain excellent dielectric layer pattern at last.
Practicality
As stated, inorganic paste composition of the present invention not only advantageously makes inorganic powder in composition, have excellent dispersiveness, and advantageously generates the uniform film of thickness.In addition; Shrinkage after can also suppressing to cure; Therefore in multilayer circuit and various display; For example plasma scope, plasma address LCD and Field Emission Display, particularly in needing the plasma front panel of high precision, said inorganic paste composition is very useful as the material that forms dielectric layer and wall.
Claims (7)
1. the inorganic paste composition of non-photosensitive contains inorganic powder, has the adhesive resin of hydroxyl on the side chain, and the organic solvent of hydroxyl not,
It is characterized in that according to the mean value that comprises hydroxy radical content in aforementioned adhesion each monomer side chain with resin, the content of hydroxyl is each monomer 0.1 to 0.3 in the side chain of the adhesive resin that adopts,
Said inorganic paste composition contains the organic solvent with hydroxyl that is equal to or less than 5 weight %.
2. the inorganic paste composition of non-photosensitive according to claim 1 is characterized in that, the organic solvent of said not hydroxyl is to be selected from least a in one group of organic solvent that ether, ketone and ester constitute.
3. the inorganic paste composition of non-photosensitive according to claim 1 is characterized in that the adhesive resin that has hydroxyl on the said side chain is the acryl resin with hydroxyl.
4. the preparation method of the inorganic paste composition of non-photosensitive, said inorganic paste composition contains inorganic powder, has the adhesive resin of hydroxyl on the side chain, and the organic solvent of hydroxyl not,
Said method comprises mixing and comprises inorganic powder, has the adhesive resin of hydroxyl and not three kinds of compositions of the organic solvent of hydroxyl and the step of kneading gained potpourri on the side chain,
According to the mean value that comprises hydroxy radical content in aforementioned adhesion each monomer side chain with resin; The content of hydroxyl is each monomer 0.1 to 0.3 in the side chain of the adhesive resin that adopts; Wherein, the said potpourri in the kneading step contains the organic solvent with hydroxyl that is equal to or less than 5 weight %.
5. a sheet-shaped unbaked body that is used to produce display board comprises substrate and is formed at the dielectric layer on this substrate, and said sheet-shaped unbaked body is used for producing the dielectric layer of display board,
It is characterized in that said sheet-shaped unbaked body comprises removable support rete and is formed at this can remove the inorganic lotion film on the supporting film, said inorganic lotion film is made up of the inorganic paste composition of the described non-photosensitive of claim 1 at least.
6. a sheet-shaped unbaked body that is used to produce display board comprises substrate and is formed at the dielectric layer on this substrate, and said sheet-shaped unbaked body is used for producing the dielectric layer of display board,
It is characterized in that said sheet-shaped unbaked body comprises removable supporting film and is formed at this can remove the inorganic lotion film on the supporting film, said inorganic lotion film is made up of the inorganic paste composition of the described non-photosensitive of claim 2 at least.
7. a sheet-shaped unbaked body that is used to produce display board comprises substrate and is formed at the dielectric layer on this substrate, and said sheet-shaped unbaked body is used for producing the dielectric layer of display board,
It is characterized in that said sheet-shaped unbaked body comprises removable supporting film and is formed at this can remove the inorganic lotion film on the supporting film, inorganic lotion film is made up of the inorganic paste composition of the described non-photosensitive of claim 3 at least.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004053738A JP3938919B2 (en) | 2004-02-27 | 2004-02-27 | INORGANIC PASTE COMPOSITION, MANUFACTURING METHOD FOR INORGANIC PASTE COMPOSITION, AND SHEET-LIKE BUNCHED PRODUCT |
| JP053738/2004 | 2004-02-27 | ||
| PCT/JP2005/001648 WO2005083520A1 (en) | 2004-02-27 | 2005-01-28 | Inorganic paste composition, method for preparing inorganic paste composition, and sheet-shaped unbaked body for producing display panel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1926473A CN1926473A (en) | 2007-03-07 |
| CN1926473B true CN1926473B (en) | 2012-03-21 |
Family
ID=34908760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200580006199.8A Expired - Fee Related CN1926473B (en) | 2004-02-27 | 2005-01-28 | Inorganic paste composition, method for preparing inorganic paste composition, and sheet-shaped unbaked body for producing display panel |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP3938919B2 (en) |
| KR (1) | KR100849976B1 (en) |
| CN (1) | CN1926473B (en) |
| TW (1) | TWI279415B (en) |
| WO (1) | WO2005083520A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4760641B2 (en) * | 2006-09-19 | 2011-08-31 | Ｔｄｋ株式会社 | Electrode step absorbing printing paste and method for producing multilayer ceramic electronic component |
| JPWO2018021439A1 (en) * | 2016-07-28 | 2019-05-23 | 株式会社クラレ | Ceramic green sheet and coated sheet |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1157042A (en) * | 1995-06-12 | 1997-08-13 | 东丽株式会社 | Photosensitive paste, plasma display and process for production thereof |
| CN1448792A (en) * | 2002-03-29 | 2003-10-15 | 住友化学工业株式会社 | Photosensitive paste |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5749106A (en) * | 1980-09-05 | 1982-03-20 | Nippon Electric Co | Insulating paste composition |
| JPS5749105A (en) * | 1980-09-05 | 1982-03-20 | Nippon Electric Co | Insulating paste composition |
| JP3567591B2 (en) * | 1995-06-12 | 2004-09-22 | 東レ株式会社 | Manufacturing method of plasma display |
| JP3239759B2 (en) * | 1995-06-12 | 2001-12-17 | 東レ株式会社 | Photosensitive paste |
| JP3402070B2 (en) * | 1995-06-12 | 2003-04-28 | 東レ株式会社 | Plasma display |
| JP3716469B2 (en) * | 1995-06-12 | 2005-11-16 | 東レ株式会社 | Photosensitive paste for pattern processing |
| JPH09110466A (en) * | 1995-10-12 | 1997-04-28 | Toray Ind Inc | Photosensitive insulating glass paste |
| JPH1124262A (en) * | 1997-07-03 | 1999-01-29 | Tokyo Ohka Kogyo Co Ltd | Undercoat material composition for sandblasting and method for manufacturing plasma display panel by using same |
-
2004
- 2004-02-27 JP JP2004053738A patent/JP3938919B2/en not_active Expired - Fee Related
-
2005
- 2005-01-28 KR KR1020067016628A patent/KR100849976B1/en not_active IP Right Cessation
- 2005-01-28 CN CN200580006199.8A patent/CN1926473B/en not_active Expired - Fee Related
- 2005-01-28 WO PCT/JP2005/001648 patent/WO2005083520A1/en active Application Filing
- 2005-02-16 TW TW094104520A patent/TWI279415B/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1157042A (en) * | 1995-06-12 | 1997-08-13 | 东丽株式会社 | Photosensitive paste, plasma display and process for production thereof |
| CN1448792A (en) * | 2002-03-29 | 2003-10-15 | 住友化学工业株式会社 | Photosensitive paste |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2003-287883A 2003.10.10 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2005083520A1 (en) | 2005-09-09 |
| TW200602416A (en) | 2006-01-16 |
| JP2005239952A (en) | 2005-09-08 |
| CN1926473A (en) | 2007-03-07 |
| KR20060114015A (en) | 2006-11-03 |
| TWI279415B (en) | 2007-04-21 |
| KR100849976B1 (en) | 2008-08-01 |
| JP3938919B2 (en) | 2007-06-27 |
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