WO2005086199A1 - Paste for diaphragm and process for producing plasma display panel - Google Patents

Paste for diaphragm and process for producing plasma display panel Download PDF

Info

Publication number
WO2005086199A1
WO2005086199A1 PCT/JP2005/003537 JP2005003537W WO2005086199A1 WO 2005086199 A1 WO2005086199 A1 WO 2005086199A1 JP 2005003537 W JP2005003537 W JP 2005003537W WO 2005086199 A1 WO2005086199 A1 WO 2005086199A1
Authority
WO
WIPO (PCT)
Prior art keywords
paste
partition
resin
meth
acrylate
Prior art date
Application number
PCT/JP2005/003537
Other languages
French (fr)
Japanese (ja)
Inventor
Masamichi Tanida
Hiroyuki Yamamoto
Toshihiro Takeuchi
Original Assignee
Asahi Glass Company, Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Company, Limited filed Critical Asahi Glass Company, Limited
Priority to JP2006510698A priority Critical patent/JPWO2005086199A1/en
Publication of WO2005086199A1 publication Critical patent/WO2005086199A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
    • C03C3/072—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths

Definitions

  • the present invention relates to a paste used for forming a partition wall of a plasma display panel (PDP), a fluorescent display tube (VFD), and the like.
  • PDP plasma display panel
  • VFD fluorescent display tube
  • the present invention also relates to a method for producing a PDP.
  • One of the features of the panel structure of a PDP or VFD which is a thin flat panel color display device, is a partition formed at equal intervals over the entire screen to separate pixels.
  • a PDP a front glass substrate and a rear glass substrate are overlapped, and a transparent electrode and a dielectric layer covering the transparent electrode are usually formed on the surface of the front glass substrate. The dielectric layer is covered and protected by an MgO film.
  • an address electrode and an insulating coating layer covering the address electrode are usually formed on the surface of the back glass substrate, and a partition is formed on the insulating coating layer.
  • the partition walls are formed in a grid pattern at equal intervals over the entire screen, and the grid interval is typically 200 to 300 m.
  • the width and height of the partition are typically 80 m and 150 / z m, respectively.
  • Partition walls of a PDP are, for example, partition walls obtained by mixing a ceramic filler for maintaining the partition wall shape, a glass powder as a fixing material, and an inorganic powder including a heat-resistant pigment for color tone adjustment with a vehicle. It is formed as follows using a paste for use.
  • a paste for a partition is applied to the entire surface of a glass substrate having a surface on which an address electrode and an insulating coating layer covering the address electrode are formed, and dried.
  • a dry film resist is laminated on the dried coating layer (hereinafter, referred to as a dried film), and an exposure mask having a desired partition pattern is set and exposed, and then an aqueous solution of sodium carbonate or the like is used.
  • a partition pattern on the dried film.
  • Unnecessary portions of the dried film on which the partition wall pattern is formed are cut by sandblasting to obtain unfired partition walls, and the dry film remaining on the unfired partition walls is subjected to sodium hydroxide aqueous solution, ethanolamine solution, and the like. After removal by, for example, baking at 500-620 ° C., partition walls are formed on the glass substrate.
  • the paste for the partition wall has a PbO—SiO—BO glass powder as a glass powder.
  • white pigments such as titania or black pigments such as Cr-Cu composite acids are used.
  • Ceramic ceramic powders such as alumina, zircon, and zirconia are used, respectively.
  • a typical composition of the PbO—SiO—BO system glass expressed in mol% is
  • the paste for the partition walls mainly made of glass powder of PbO—SiO—B O based glass is used.
  • Lead-containing glass represented by 223 has excellent properties as a glass for forming partition walls, but in recent years, low-lead or lead-free glass has been desired, and there are various alternatives to lead-containing glass. Proposed. For example, bismuth-containing glass using BiO instead of PbO, ZnO
  • bismuth is a small amount of material and expensive, it is also desirable that bismuth be low in bismuth or no bismuth.
  • glass powder used for the paste for partition walls is required to have low lead siding and low bismuth.
  • the conventional partition wall paste when the glass powder is replaced with a lead-containing glass powder that does not contain alkali metal oxide, for example, an alkali-containing glass, the dry film obtained from the partition wall paste and the dry film become incompatible. Since the adhesion is greatly reduced, there is a problem that the dry film is peeled off in the developing step and the sandblasting step in the partition wall forming step.
  • the decrease in adhesion between the dry film and the dry film when the alkali-containing glass is replaced is considered to be due in part to elution of the alkali component into the developer and an increase in the pH of the developer. This prevents the dry film from peeling off. It may be possible to lower the pH of the developing solution or to lower the sandblasting speed (blast rate) in order to avoid this, but there are problems such as a longer time required for manufacturing the partition walls.
  • the present invention can maintain good adhesion between a dry film and a dry film without lengthening the time required for sandblasting even when using an alkali-containing glass.
  • the purpose of the present invention is to provide a partition wall paste capable of shortening the time required for sandblasting without reducing the properties.
  • Another object of the present invention is to provide a method for manufacturing a plasma display panel using the partition wall paste.
  • the present invention provides a method for manufacturing a paste for partition walls and a plasma display panel having the following structures.
  • Acrylic polymer strength The polymer for a partition wall according to any one of (1) to (5) above, wherein a monomer having a Tg of 0 ° C. or less when formed into a homopolymer is contained as a polymerization component. Strike.
  • Alkali-containing glass powder power In terms of mol% on the basis of the following Sanigata, essentially B 2 O 3
  • a method for manufacturing a plasma display panel having a rear substrate comprising applying the partition wall paste according to any one of (1) to (8) above on a glass substrate of the rear substrate, followed by drying,
  • a method for producing a plasma display panel comprising a step of processing and firing to form a partition.
  • the adhesion between the dry film and the dry film is maintained well without prolonging the time required for sandblasting.
  • a paste for partition walls, which has little dry film peeling even during sandblasting, or a paste for partition walls, which can reduce the time required for sandblasting without lowering the adhesion, can be obtained.
  • a PDP having high brightness and excellent image quality can be manufactured without particularly increasing or shortening the time required for the sand blasting.
  • FIG. 1 is a schematic sectional view of a typical example of a plasma display.
  • the paste for partition walls of the present invention (hereinafter referred to as the paste of the present invention) is usually prepared by dissolving an inorganic powder such as an alkali-containing glass powder, a ceramic filler, a heat-resistant pigment, a resin as an organic binder, and the resin. And a vehicle containing a solvent.
  • the paste of the present invention is used to form barrier ribs such as PDPs and VFDs, and is usually applied over the entire surface of a glass substrate having an address electrode and an insulating coating layer covering the address electrodes formed thereon, and dried. After being processed into a desired shape by a sand blast method or the like, it is fired.
  • the content of the alkali-containing glass powder in the inorganic powder is preferably 70% by mass or more, more preferably 80% by mass or more.
  • the content is typically not more than 95% by mass or not more than 85% by mass.
  • the softening point T of the alkali-containing glass powder is preferably 450 to 650 ° C. T force 5 s s
  • the glass flows too much during the firing, and a predetermined partition shape cannot be obtained. If the T force exceeds 50 ° C, the glass flow during firing s
  • the mobility may be reduced, and a dense partition wall may not be obtained.
  • the temperature is more preferably 620 ° C or less, and particularly preferably less than 600 ° C.
  • the average linear expansion coefficient of the glass substrate is typically 65 X 10- 7 - is a 85 X 10- 7 / ° C.
  • the alkali-containing glass powder contains R O (R represents an alkali metal) as a component thereof.
  • the alkali-containing glass powder in the paste of the present invention is essentially represented by the following oxide based mol%,
  • the content of PbO + BiO is preferably 10% or less.
  • B 0 0-60% means that B 2 O is not essential but contains up to 60%.
  • the content of PbO + Bi O is more preferably 5% or less.
  • the alkali-containing glass powder may contain other components as long as the object of the present invention is not impaired.
  • the total content of the "other components” is preferably 5% or less! / ,.
  • rare earth oxides such as La O, P O, MnO, Fe O, Co
  • the ceramic filler is not essential, but may be contained as necessary. When a ceramic filler is contained, its typical content is 5-25% by mass. Examples of the ceramic filler include powders of alumina, mullite, zircon, zirconia, cordierite, aluminum titanate, ⁇ -spodumene, ⁇ -quartz, quartz glass, j8-quartz solid solution, and eucryptite. .
  • the heat-resistant pigment is not essential, but may be contained as necessary. When a heat-resistant pigment is contained, its typical content is 0.5 to 10% by mass.
  • heat-resistant pigments include white pigments such as titer, and pigments such as Fe—Mn double oxide, Fe—Co—Cr double oxide, and Fe—Mn—A1 double oxide.
  • the content of the resin in the paste of the present invention is preferably 0.5 to 15 parts by mass based on 100 parts by mass of the inorganic powder. If the content is less than 0.5 part by mass, the adhesion to the dry film may be weak, more preferably 1 part by mass or more, and if it exceeds 15 parts by mass, the blast rate may be too slow, Preferably not more than 10 parts by mass
  • the resin of the paste of the present invention contains an acrylic polymer.
  • the acrylic polymer content in the resin is preferably at least 10% by mass, more preferably at least 20% by mass, and typically at least 40% by mass.
  • the resin of the paste of the present invention contains an acrylic polymer having, as a polymerization component, a monomer having a Tg (glass transition temperature) of 40 ° C. or lower when formed into a homopolymer.
  • a dry film can be formed without increasing the time required for sandblasting. Good adhesion to the dry film can be maintained to reduce the peeling of the dry film in the formation of the partition walls, or the time required for sandblasting can be reduced without lowering the adhesion, In some cases, the phenomenon in which the clear layer (transparent layer) separates to cause non-uniformity can be suppressed.
  • the acrylic polymer is a homopolymer
  • Monomers having a Tg of 40 ° C or less when formed into a homopolymer include n-butyl (meth) acrylate (Tg: 30 ° C) and n-hexyl (meth) acrylate (Tg: —5 ° C), ethylhexyl (meth) acrylate (Tg: -20 ° C), n-dodecyl (meth) acrylate (Tg: -60 ° C), 2-ethylaminoethyl (meth) acrylic acid ( (Tg: 26 ° C) (the temperature in parentheses indicates the Tg of the homopolymer obtained from each monomer).
  • the acrylic polymer contained in the resin of the paste of the present invention preferably has an acid value or an amine value. Acrylic polymer strength If there is no acid value or amine value, the blast rate will be slow, the adhesion between the dry film and the dry film will be reduced, or the clear layer (transparent layer) will separate from the surface when the paste is used May cause non-uniformity.
  • the acid value of the acrylic polymer is preferably 30 mgKOHZg or less. If the acid value exceeds 30 mgKOH / g, the adhesion between the dried film and the dry film may be reduced.
  • a monomer having a polar group such as a carboxyl group, an amino group, or an amine group is used as a polymerization component in accordance with a desired acid value or an amine value. What is necessary is just to contain. Examples of such a monomer include (meth) acrylic acid, 2-getylaminoethyl (meth) acrylic acid, and the like. The content of these monomer components in the acrylic polymer is preferably 0.5 5 5 mol 0/0.
  • the acrylic polymer impairs the purpose of the present invention by using a monomer having a Tg of 40 ° C or less when the above homopolymer is used, and other monomers other than a monomer for providing an acid value or an amine value. It may be contained as a polymerization component within a range not present.
  • Examples of the above-mentioned other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, stearyl ( (Meta) acrylate, oleyl (meta) acrylate, cyclohexyl Sil (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, Monomers having a polymerizable group other than (meth) acrylate are exemplified.
  • the content of the monomer component having a Tg of 40 ° C or less is 5 mol% or more.
  • the content is less than 5 mol%, a high blast rate can be achieved to achieve good adhesion between the dry film and the dry film, or the talli layer separation phenomenon can easily occur. It is typically at least 40 mol%.
  • the mass average molecular weight of the acrylic polymer is preferably from 40,000 to 200,000, more preferably from 40,000 to 100,000! If the weight average molecular weight is less than 40,000, the adhesion between the dry film and the dry film may be insufficient. If the weight average molecular weight exceeds 200,000, it may be dissolved in an organic solvent such as tavinelone.
  • a resin other than the acrylic polymer for example, ethyl cellulose, may be used as the resin if necessary. Let me contain it.
  • the weight average molecular weight is preferably from 50,000 to 200,000. If the weight average molecular weight is less than 50,000, the adhesion between the dried film and the dry film may be insufficient, and if it exceeds 200,000, it becomes difficult to dissolve in an organic solvent such as turbineol.
  • ethyl cellulose When ethyl cellulose is contained as a resin, the content of the ethyl cellulose in the resin is typically 40% by mass or more.
  • the resin other than the acrylic polymer of the paste of the present invention examples include thermoplastic resins such as polyvinyl butyral in addition to ethyl cellulose.
  • the resin in the paste of the present invention is essentially composed of a thermoplastic resin, but may contain a resin other than the thermoplastic resin as long as the object of the present invention is not impaired!
  • the content ratio of the organic solvent in the paste of the present invention is based on 100 parts by mass of the inorganic powder.
  • the organic solvent of the paste of the present invention includes terbineol, ethylene glycol alkyl ether (eg, ethylene glycol monoethyl ether), diethylene glycol monoether.
  • Alkyl ether for example, diethylene glycol monobutyl ether (butyl carbitol)
  • ethylene glycol monoleno quinoleate enorea acetate diethylene glycol mono oleno alkyl ether acetate (for example, diethylene glycol monobutyl ether acetate (butyl carbitol acetate))
  • a surfactant is not essential, but may be contained as necessary.
  • the surfactant preferably has a polar group in the hydrophilic portion.
  • the polar group include one or more polar groups selected from the group consisting of a carboxyl group, a phosphate group, an amino group, and a hydroxyl group.
  • alkyl is a straight-chain or branched-chain alkyl having 8 to 20 carbon atoms (for example, octyl, Lil, cetyl, stearyl, oleyl, etc. )
  • alkylene is a straight-chain or branched-chain alkylene having 2 to 5 carbon atoms (eg, ethylene, propylene, etc.).
  • R is a linear or branched alkyl group having 8 to 20 carbon atoms, and R is a 2 to 5 carbon atom.
  • n 120
  • X is a carboxyl group or a phosphate group.
  • compounds represented by the above formula 1 include polyoxyethylene lauryl ether carboxylate, polyoxyethylene lauryl ether phosphate and the like, and alkyl phosphates such as lauryl phosphate and hydroxyethyl.
  • alkylamine examples include N-hydroxyethyl laurylamine
  • polyoxyalkylenealkylamine examples include polyoxyethylene laurylamine.
  • Including these surfactants may be preferable in that cracks in the dried film and a decrease in adhesion between the dried film and the substrate can be prevented. Further, it may be effective to shorten the time required for sandblasting and to maintain good adhesion between the dry film and the dry film.
  • the content ratio is preferably 0.2 to 2 parts by mass with 100 parts by mass of the inorganic powder, typically 0.5 parts by mass or more. If the amount is more than 2 parts by mass, there may be problems such as cracking of the dried film by force and reduction in adhesion between the dried film and the substrate.
  • the surfactant of the present invention may contain two or more of these surfactants as necessary.
  • the paste of the present invention may preferably contain a nonionic surfactant when viscosity adjustment or the like is performed.
  • the content ratio of the nonionic surfactant is preferably 0.2 to 2 parts by mass based on 100 parts by mass of the inorganic powder.
  • Non-ionic surfactants include polyethylene glycol alkyl ether, polyethylene glycol alkyl ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene polypropylene alkyl ether, polyethylene glycol alkylamine, hydroxyethyl alkyla Min, phosphate ester, carboxylic acid ester, polyalkyl glycol ether, alkyl polyether Examples thereof include min or alkylammonium salts.
  • alkyl refers to octyl, radial, cetyl, stearyl, oleyl and the like.
  • the PDP is manufactured as follows, for example, in the case of an AC system.
  • an electrode 2 is formed on the front glass substrate la by patterning, a nose line (not shown) is formed, and then a transparent dielectric layer 3 for protecting the electrode is formed.
  • a protective film usually made of MgO, is formed on the transparent dielectric layer 3 to manufacture a front substrate.
  • a patterned address electrode 5 is formed on the rear glass substrate lb, and then an insulating coating layer 8 covering the address electrode is formed.
  • the partition walls 6 are formed by applying the paste of the present invention on the entire surface of the insulating coating layer 8, drying the paste, processing it into a desired partition pattern by sandblasting, and firing.
  • the temperature at which the calcination is performed is usually 500 to 620 ° C. If the temperature is lower than 500 ° C, the resin partially remains on the fired partition walls, and the residual resin is released as a gas when sealing the panel with PDP or VFD or when discharging the panel. If the temperature exceeds 620 ° C, the glass substrate may be deformed
  • the phosphor layer 4 is formed by printing and baking.
  • a sealing material (not shown) is applied to the periphery of the front glass substrate la and the rear glass substrate lb with a dispenser, and the electrodes of the front substrate and the rear substrate manufactured as described above are opposed to each other.
  • the plasma display is evacuated, the discharge space 7 is filled with a discharge gas such as Ne or He—Xe, and the plasma display is manufactured.
  • inorganic powders Al, A2 and B1 were prepared using glass powders A and B. That is, the inorganic powder A1 was prepared by mixing glass powder A: 91.3% by mass, silica powder: 8.0% by mass, and titanium powder: 0.7% by mass. The inorganic powder A2 was prepared by mixing 95.1% by mass of glass powder A and 4.9% by mass of titania powder. The inorganic powder B1 was prepared by mixing glass powder B: 84.5% by mass, silica powder: 15.0% by mass, and titanium powder: 0.5% by mass.
  • Example 11 to 17 the inorganic powder A1 was used, in Examples 18 and 20, the inorganic powder A2 was used, and in Example 19, the inorganic powder B1 was used.
  • a resin (acrylic polymer, ethylcellulose) and an organic solvent (turbineol, ethylene glycol monobutyl ether acetate (DEGBEA), propylene glycol diacetate (PGDA)) were added.
  • the mixture was stirred at 85 ° C. for 4 hours to dissolve the resin and prepare a vehicle.
  • Example 11 The acrylic polymers used in 17, 19, and 20 were n-BMA (n-butyl methacrylate), 2DEAEA (2-dimethylaminoethyl (meth) acrylic acid), and EHMA (ethylhexyl (meta-hexyl)).
  • n-BMA n-butyl methacrylate
  • 2DEAEA 2-dimethylaminoethyl (meth) acrylic acid
  • EHMA ethylhexyl (meta-hexyl)
  • MMA methyl methacrylate (Tg: 110 ° C)
  • iBMA i-butyl methacrylate
  • methacrylic acid in the ratio shown in mol% in the table (The temperature in parentheses indicates the Tg of the homopolymer from which each monomer force is also obtained).
  • Tg represents the glass transition temperature of the acrylic polymer
  • Mw represents the mass average molecular weight of the acrylic polymer.
  • surfactant 1 or 2 was added to the mixture of inorganic powder and vehicle at the ratio shown in parts by mass in the table with respect to 100 parts by mass of inorganic powder, and three rolls were added. And adjust the viscosity to a viscosity of 0 Pa ⁇ s at a shear rate of 4 s- 1 to obtain a paste.
  • Surfactant 1 is N-hydroxyethyllaurylamine (a compound having a structure represented by the following formula (1))
  • Surfactant 2 is an alkylolamine salt of a copolymer containing a phosphate group. "Di sperbykl80j (manufactured by BYK Japan KK) was used.
  • the obtained paste was blade-coated with a 10-cm square glass substrate (PD200 manufactured by Asahi Glass Co., Ltd.) with a 400- ⁇ m spacer, dried for 1.5 hours in a dryer at 120 ° C, and dried. It was a membrane.
  • Examples 11 to 11 are examples of the present invention, Examples 12 to 18 are comparative examples, and Examples 19 and 20 are reference examples. In the paste of Example 20, the clear layer separation phenomenon was remarkable.
  • Example 1-120 the blast rate (unit: ⁇ m / and the cumulative number of dry film peelings (unit: pieces), which is an index of dry film adhesion, was examined as described below. The results are shown in the columns of the blast rate and the number of peeled pieces in the table.
  • Blast rate Using a sand blasting machine (model SCM-1ADE-NH-401P) manufactured by Fuji Seisakusho, suction pressure 150 kPa, pumping air pressure 200 kPa, gun moving speed 4. lm Z minute, roller rotation speed 2 The dried film was blasted once under the condition of .5 rpm, the cutting depth was measured, and this was used as a blast straight.
  • the cumulative number of peeled dry films is preferably less than 35 in total. With 35 or more, the dry film may peel off from the dry film even under the sand blasting condition for forming the partition walls, which is usually performed under milder conditions than the above sand blasting condition. More preferably, it is less than 25, even more preferably less than 20.
  • the blast rate is preferably 40 ⁇ mZ times or more.
  • the blast rate is 70 ⁇ mZ or more, the number of strips is preferably less than 30.
  • Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)
  • Gas-Filled Discharge Tubes (AREA)
  • Cathode-Ray Tubes And Fluorescent Screens For Display (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

A paste for diaphragms which comprises alkali-containing glass particles, a resin, and an organic solvent, wherein the resin comprises an acrylic polymer comprising units derived from a monomer which gives a homopolymer having a glass transition temperature of 40°C or lower and the content of the units of the monomer giving a homopolymer having a glass transition temperature of 40°C or lower, in the acrylic polymer, is 5 mol% or higher.

Description

明 細 書  Specification
隔壁用ペーストおよびプラズマディスプレイパネルの製造方法  Partition wall paste and method of manufacturing plasma display panel
技術分野  Technical field
[0001] 本発明は、プラズマディスプレイパネル (PDP)、蛍光表示管 (VFD)等の隔壁形成 に用いられるペーストに関する。また本発明は、 PDPの製造方法に関する。  The present invention relates to a paste used for forming a partition wall of a plasma display panel (PDP), a fluorescent display tube (VFD), and the like. The present invention also relates to a method for producing a PDP.
背景技術  Background art
[0002] 薄型の平板型カラー表示装置である PDPまたは VFDのパネル構造の特徴のひと つとして、画素を区切るために画面全域に等間隔で形成される隔壁が挙げられる。た とえば、 PDPでは、前面ガラス基板と背面ガラス基板が重ね合わされており、前面ガ ラス基板の表面には、通常、透明電極および該透明電極を被覆する誘電体層が形 成されており、該誘電体層は MgO膜で被覆され、保護されている。一方、背面ガラス 基板の表面には、通常、アドレス電極および該アドレス電極を被覆する絶縁被覆層 が形成されており、該絶縁被覆層の上に隔壁が形成されている。隔壁は画面全域に 等間隔で格子状に形成され、その格子間隔は典型的には 200— 300 mである。ま た、隔壁の幅、高さは、典型的にはそれぞれ 80 m、 150 /z mである。  [0002] One of the features of the panel structure of a PDP or VFD, which is a thin flat panel color display device, is a partition formed at equal intervals over the entire screen to separate pixels. For example, in a PDP, a front glass substrate and a rear glass substrate are overlapped, and a transparent electrode and a dielectric layer covering the transparent electrode are usually formed on the surface of the front glass substrate. The dielectric layer is covered and protected by an MgO film. On the other hand, an address electrode and an insulating coating layer covering the address electrode are usually formed on the surface of the back glass substrate, and a partition is formed on the insulating coating layer. The partition walls are formed in a grid pattern at equal intervals over the entire screen, and the grid interval is typically 200 to 300 m. The width and height of the partition are typically 80 m and 150 / z m, respectively.
[0003] PDPの隔壁は、たとえば、隔壁形状を保持するためのセラミックスフイラ一、固着材 であるガラス粉末、色調調整のための耐熱顔料等からなる無機粉末をビヒクルと混合 して得られる隔壁用ペーストを用い、次のようにして形成される。  [0003] Partition walls of a PDP are, for example, partition walls obtained by mixing a ceramic filler for maintaining the partition wall shape, a glass powder as a fixing material, and an inorganic powder including a heat-resistant pigment for color tone adjustment with a vehicle. It is formed as follows using a paste for use.
すなわち、まず、表面にアドレス電極および該アドレス電極を被覆する絶縁被覆層 が形成されたガラス基板の上の全面に隔壁用ペーストを塗布し、乾燥させる。次に、 この乾燥された塗布層（以下、乾燥膜という。）の上にドライフィルムレジストをラミネ一 トし、所望の隔壁パターンの露光マスクをセットして露光後、炭酸ナトリウム水溶液等 を用いて現像し、乾燥膜の上に隔壁パターンを形成する。この隔壁パターンが形成 された乾燥膜の不要部をサンドブラストによって切削し、未焼成隔壁を得た後、この 未焼成隔壁の上に残って 、るドライフィルムを水酸ィ匕ナトリウム水溶液、エタノールァ ミン等によって除去後、 500— 620°Cで焼成しガラス基板上に隔壁を形成する。  That is, first, a paste for a partition is applied to the entire surface of a glass substrate having a surface on which an address electrode and an insulating coating layer covering the address electrode are formed, and dried. Next, a dry film resist is laminated on the dried coating layer (hereinafter, referred to as a dried film), and an exposure mask having a desired partition pattern is set and exposed, and then an aqueous solution of sodium carbonate or the like is used. Develop and form a partition pattern on the dried film. Unnecessary portions of the dried film on which the partition wall pattern is formed are cut by sandblasting to obtain unfired partition walls, and the dry film remaining on the unfired partition walls is subjected to sodium hydroxide aqueous solution, ethanolamine solution, and the like. After removal by, for example, baking at 500-620 ° C., partition walls are formed on the glass substrate.
[0004] 従来、隔壁用ペーストには、ガラス粉末としては PbO— SiO— B O系ガラスの粉末 力 耐熱顔料としてはチタニア等の白色顔料または Cr~Cu複合酸ィヒ物等の黒色顔 料力 セラミックフイラ一としてはアルミナ、ジルコン、ジルコユア等の粉末が、それぞ れ使用されている。前記 PbO— SiO— B O系ガラスのモル％表示の代表的な組成は [0004] Conventionally, the paste for the partition wall has a PbO—SiO—BO glass powder as a glass powder. As heat-resistant pigments, white pigments such as titania or black pigments such as Cr-Cu composite acids are used. Ceramic ceramic powders such as alumina, zircon, and zirconia are used, respectively. A typical composition of the PbO—SiO—BO system glass expressed in mol% is
2 2 3  2 2 3
、B O 15%、 SiO 40%、 PbO 35%、 Al O 5%、 TiO 5%、である。ビヒクル , B O 15%, SiO 40%, PbO 35%, Al O 5%, and TiO 5%. Vehicle
2 3 2 2 3 2 2 3 2 2 3 2
は榭脂と有機溶剤を含み、榭脂としてはェチルセルロース等、有機溶剤としてはター ビネオール等が使用されている（たとえば、特開 2001— 106547号公報参照。；)。ま た、隔壁形成時のサンドブラスト特性の向上やドライフィルムと乾燥膜との密着性向 上等のために、主に PbO— SiO— B O系ガラスのガラス粉末を用いた隔壁用ペース  Contains resin and an organic solvent, and ethyl cellulose and the like are used as the resin, and terbineol and the like are used as the organic solvent (for example, see JP-A-2001-106547;). In addition, in order to improve the sand blast characteristics when forming the partition walls and to improve the adhesion between the dry films, the paste for the partition walls mainly made of glass powder of PbO—SiO—B O based glass is used.
2 2 3  2 2 3
トにおいて、榭脂としてェチルセルロースとともにアクリル重合体を併用する提案もな されている（例えば、特開 2003— 54992号公報参照）。  It has also been proposed that an acrylic polymer is used together with ethyl cellulose as a resin (see, for example, JP-A-2003-54992).
[0005] ところで、これまで隔壁用ペーストに主に使用されてきた PbO— SiO— B O系ガラス [0005] By the way, PbO-SiO-BO-based glass that has been mainly used so far for partition wall pastes
2 2 3 に代表される鉛含有ガラスは、隔壁形成用ガラスとして優れた性質を有して ヽるが、 近年、低鉛または無鉛系のガラスが望まれ、鉛含有ガラスに代替するガラスが種々提 案されている。たとえば、 PbOに替わって Bi Oを用いたビスマス含有ガラスや、 ZnO  Lead-containing glass represented by 223 has excellent properties as a glass for forming partition walls, but in recent years, low-lead or lead-free glass has been desired, and there are various alternatives to lead-containing glass. Proposed. For example, bismuth-containing glass using BiO instead of PbO, ZnO
2 3  twenty three
B O SiO系でアルカリ金属酸化物成分を有するアルカリ含有ガラス等が提案さ Alkali-containing glass with alkali metal oxide component in B O SiO system has been proposed
2 3 2 2 3 2
れている（たとえば、特開 2001— 130926号公報参照)。ただし、ビスマスは、資源と しても少量な物質で、高価なことから、低ビスマスまたは無ビスマスであることも望まれ る。  (See, for example, JP-A-2001-130926). However, since bismuth is a small amount of material and expensive, it is also desirable that bismuth be low in bismuth or no bismuth.
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0006] 上記のとおり、現状、隔壁用ペーストに用いるガラス粉末には、低鉛ィ匕および低ビス マス化が要求されている。しかし、従来の隔壁用ペーストにおいて、ガラス粉末をァ ルカリ金属酸ィ匕物を含有しない鉛含有ガラスカゝらたとえばアルカリ含有ガラスに替え ると、該隔壁用ペーストから得られる乾燥膜とドライフィルムとの密着性が大幅に低下 してしまうため、隔壁形成工程の現像工程およびサンドブラスト工程でドライフィルム が剥離してしまう等の問題がある。アルカリ含有ガラスに替えた場合の乾燥膜とドライ フィルムとの密着性の低下は、現像液中にアルカリ成分が溶出し、現像液の pHが上 昇してしまうことがその一因と考えられる。そのため、ドライフィルムが剥離するのを防 ぐために現像液の pHを低くしたり、またサンドブラストの速度 (ブラストレート)を落とし たりすることも考えられるが、隔壁作製に要する時間が長くなつてしまう等の問題があ る。 [0006] As described above, at present, glass powder used for the paste for partition walls is required to have low lead siding and low bismuth. However, in the conventional partition wall paste, when the glass powder is replaced with a lead-containing glass powder that does not contain alkali metal oxide, for example, an alkali-containing glass, the dry film obtained from the partition wall paste and the dry film become incompatible. Since the adhesion is greatly reduced, there is a problem that the dry film is peeled off in the developing step and the sandblasting step in the partition wall forming step. The decrease in adhesion between the dry film and the dry film when the alkali-containing glass is replaced is considered to be due in part to elution of the alkali component into the developer and an increase in the pH of the developer. This prevents the dry film from peeling off. It may be possible to lower the pH of the developing solution or to lower the sandblasting speed (blast rate) in order to avoid this, but there are problems such as a longer time required for manufacturing the partition walls.
[0007] 本発明は、このような状況に鑑み、アルカリ含有ガラスを用いても、サンドブラストに 要する時間を長くすることなく乾燥膜とドライフィルムとの密着性を良好に保持できる 、または、前記密着性を低下させることなくサンドブラストに要する時間を短くできる隔 壁用ペーストの提供を目的とする。また本発明は、該隔壁用ペーストを用いたプラズ マディスプレイパネルの製造方法の提供も目的とする。  [0007] In view of such circumstances, the present invention can maintain good adhesion between a dry film and a dry film without lengthening the time required for sandblasting even when using an alkali-containing glass. The purpose of the present invention is to provide a partition wall paste capable of shortening the time required for sandblasting without reducing the properties. Another object of the present invention is to provide a method for manufacturing a plasma display panel using the partition wall paste.
課題を解決するための手段  Means for solving the problem
[0008] 上記課題を解決するために、本発明は、下記構成の隔壁用ペーストおよびプラズ マディスプレイパネルの製造方法が提供される。 [0008] In order to solve the above problems, the present invention provides a method for manufacturing a paste for partition walls and a plasma display panel having the following structures.
(1)アルカリ含有ガラス粉末、榭脂および有機溶剤を含有する隔壁用ペーストであつ て、榭脂として、ホモポリマーとしたときにガラス転移温度 (Tg)が 40°C以下となるモノ マーを重合成分として有するアクリル重合体を含有し、アクリル重合体中の前記 Tgが 40°C以下となるモノマー成分の含有量が 5モル％以上であることを特徴とする隔壁 用ペースト。  (1) Partition paste containing alkali-containing glass powder, resin and organic solvent, polymerized as a resin and has a glass transition temperature (Tg) of 40 ° C or lower when homopolymer. A paste for a partition wall, comprising an acrylic polymer as a component, wherein the content of the monomer component in which the Tg is 40 ° C or less in the acrylic polymer is 5 mol% or more.
(2)前記モノマーが、 n-ブチル (メタ）アタリレート、 n-へキシル (メタ）アタリレート、ェ チルへキシル (メタ）アタリレート、 n—ドデシル (メタ）アタリレートおよび 2—ジェチルアミ ノエチル (メタ)アタリレートからなる群力も選ばれる 1種以上のモノマーであることを特 徴とする上記（1)に記載の隔壁用ペースト。  (2) When the monomer is n-butyl (meth) acrylate, n-hexyl (meth) acrylate, ethyl hexyl (meth) acrylate, n-dodecyl (meth) acrylate, and 2-ethylethylaminoethyl ( (1) The paste for a partition wall according to the above (1), wherein the paste is one or more monomers selected from the group consisting of (meth) acrylate.
(3)アクリル重合体が、酸価またはアミン価を有することを特徴とする上記（1)または（ 2)に記載の隔壁用ペースト。  (3) The partition wall paste according to the above (1) or (2), wherein the acrylic polymer has an acid value or an amine value.
(4)アクリル重合体の酸価が、 30mgKOHZg以下であることを特徴とする上記（3) に記載の隔壁用ペースト。  (4) The paste for partition walls according to the above (3), wherein the acid value of the acrylic polymer is 30 mgKOHZg or less.
(5)アクリル重合体の質量平均分子量が、 40, 000— 200, 000であることを特徴と する上記（1)一（4)の 、ずれかに記載の隔壁用ペースト。  (5) The partition wall paste according to any one of (1) to (4) above, wherein the acrylic polymer has a mass average molecular weight of 40,000 to 200,000.
(6)アクリル重合体力 ホモポリマーとしたときに Tgが 0°C以下となるモノマーを、重合 成分として含有することを特徴とする上記（1)一（5)のいずれかに記載の隔壁用ぺー スト。 (6) Acrylic polymer strength The polymer for a partition wall according to any one of (1) to (5) above, wherein a monomer having a Tg of 0 ° C. or less when formed into a homopolymer is contained as a polymerization component. Strike.
(7)榭脂としてェチルセルロースを含有し、榭脂中のェチルセルロース含有量が 40 質量％以上である上記（1)一 (6)の 、ずれかに記載の隔壁用ペースト。  (7) The paste for partition walls according to any one of (1) to (6), wherein the paste contains ethyl cellulose as a resin, and the content of the ethyl cellulose in the resin is 40% by mass or more.
(8)アルカリ含有ガラス粉末力 下記酸ィ匕物基準のモル％表示で、本質的に、 B O  (8) Alkali-containing glass powder power In terms of mol% on the basis of the following Sanigata, essentially B 2 O 3
2 3 twenty three
0 60%、SiO 20 65% 0 60%, SiO 20 65%
2 、ZnO 0 60%、 MgO + CaO + SrO + BaO 0—5 2, ZnO 0 60%, MgO + CaO + SrO + BaO 0-5
0%、 Li O+Na O+K Ο 1一 30%、 Al O +TiO +ZrO 0 13%、 CuO + Sn0%, Li O + Na O + K Ο 1-130%, Al O + TiO + ZrO 0 13%, CuO + Sn
2 2 2 2 3 2 2 2 2 2 2 3 2 2
O +CeO 0-5%,からなり、 PbOまたは Bi Oを含有する場合は PbO + Bi O力^ O + CeO 0-5%, PbO + Bi O force when containing PbO or Bi O ^
2 2 2 3 2 32 2 2 3 2 3
0%以下であることを特徴とする上記（1)一（7)のいずれかに記載の隔壁用ペースト The paste for a partition according to any one of the above (1) to (7), which is 0% or less.
(9)背面基板を有するプラズマディスプレイパネルの製造方法であって、該背面基板 のガラス基板上に、上記（1)一（8)のいずれかに記載の隔壁用ペーストを塗布した 後に乾燥し、加工し、焼成して隔壁を形成する工程を有することを特徴とするプラズ マディスプレイパネルの製造方法。 (9) A method for manufacturing a plasma display panel having a rear substrate, comprising applying the partition wall paste according to any one of (1) to (8) above on a glass substrate of the rear substrate, followed by drying, A method for producing a plasma display panel, comprising a step of processing and firing to form a partition.
(10)上記（9)に記載のプラズマディスプレイパネルの製造方法であって、乾燥され た隔壁用ペーストの加工をサンドブラスト法によって行うことを特徴とするプラズマディ スプレイパネルの製造方法。  (10) The method for producing a plasma display panel according to (9), wherein the processing of the dried partition wall paste is performed by a sandblast method.
発明の効果  The invention's effect
[0009] 本発明によれば、アルカリ含有ガラス粉末を用いても、サンドブラストに要する時間 を長くすることなく乾燥膜とドライフィルムとの密着性が良好に保たれ、隔壁形成にお ける現像時やサンドブラスト時にもドライフィルムの剥離が少な 、隔壁用ペースト、ま たは、前記密着性を低下させることなくサンドブラストに要する時間を短くできる隔壁 用ペーストが得られる。また、本発明によれば、高輝度で、画質に優れた PDPを、サ ンドブラスト加工に要する時間を特に長くすることなぐまたはより短くして製造できる 図面の簡単な説明  [0009] According to the present invention, even when an alkali-containing glass powder is used, the adhesion between the dry film and the dry film is maintained well without prolonging the time required for sandblasting. A paste for partition walls, which has little dry film peeling even during sandblasting, or a paste for partition walls, which can reduce the time required for sandblasting without lowering the adhesion, can be obtained. Further, according to the present invention, a PDP having high brightness and excellent image quality can be manufactured without particularly increasing or shortening the time required for the sand blasting.
[0010] [図 1]図 1は、プラズマディスプレイの代表的な一例の概略断面図である。 FIG. 1 is a schematic sectional view of a typical example of a plasma display.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0011] 以下、本発明をさらに詳細に説明する。 本発明の隔壁用ペースト（以下、本発明のペーストという。）は、通常、アルカリ含有 ガラス粉末、セラミックスフイラ一、耐熱顔料等の無機粉末と、有機バインダとしての榭 脂および該榭脂を溶解する溶剤を含むビヒクルとを混練して製造される。 Hereinafter, the present invention will be described in more detail. The paste for partition walls of the present invention (hereinafter referred to as the paste of the present invention) is usually prepared by dissolving an inorganic powder such as an alkali-containing glass powder, a ceramic filler, a heat-resistant pigment, a resin as an organic binder, and the resin. And a vehicle containing a solvent.
本発明のペーストは、 PDPや VFD等の隔壁形成に用いられ、通常、表面にァドレ ス電極および該アドレス電極を被覆する絶縁被覆層が形成されたガラス基板の上の 全面に塗布し、乾燥後サンドブラスト法等により所望の形状に加工された後、焼成さ れる。  The paste of the present invention is used to form barrier ribs such as PDPs and VFDs, and is usually applied over the entire surface of a glass substrate having an address electrode and an insulating coating layer covering the address electrodes formed thereon, and dried. After being processed into a desired shape by a sand blast method or the like, it is fired.
[0012] 無機粉末中のアルカリ含有ガラス粉末の含有量は、 70質量％以上であることが好 ましぐより好ましくは 80質量％以上である。また、同含有量は典型的には 95質量％ 以下または 85質量％以下である。  [0012] The content of the alkali-containing glass powder in the inorganic powder is preferably 70% by mass or more, more preferably 80% by mass or more. The content is typically not more than 95% by mass or not more than 85% by mass.
[0013] アルカリ含有ガラス粉末の軟化点 Tは 450— 650°Cであることが好まし 、。 T力 5 s s [0013] The softening point T of the alkali-containing glass powder is preferably 450 to 650 ° C. T force 5 s s
0°C未満では前記焼成時にガラスが流動しすぎ、所定の隔壁形状が得られな!/、おそ れがあり、より好ましくは 500°C以上である。また T力 50°C超では焼成時のガラス流 s If the temperature is lower than 0 ° C., the glass flows too much during the firing, and a predetermined partition shape cannot be obtained. If the T force exceeds 50 ° C, the glass flow during firing s
動性が低下し、緻密な隔壁が得られないおそれがあり、より好ましくは 620°C以下、 特に好ましくは 600°C未満である。  The mobility may be reduced, and a dense partition wall may not be obtained. The temperature is more preferably 620 ° C or less, and particularly preferably less than 600 ° C.
[0014] アルカリ含有ガラス粉末を焼成して得られる焼成体の 50— 350°Cにおける平均線 熱膨張係数 ocはガラス基板との膨張マッチングの観点から、好ましくは 65 X 10— 7— 9 O X 10— 7/°C、より好ましくは 70 X 10— 7— 80 X 10— 7/°Cである。なお、ガラス基板の 前記平均線膨張係数は典型的には 65 X 10— 7— 85 X 10— 7/°Cである。 [0014] From the viewpoint of expansion matching between the average linear thermal expansion coefficient oc glass substrate in 50- 350 ° C of the sintered body obtained by firing the alkali-containing glass powder, preferably 65 X 10- 7 - 9 OX 10 - 7 / ° C, more preferably 70 X 10- 7 - is a 80 X 10- 7 / ° C. Incidentally, the average linear expansion coefficient of the glass substrate is typically 65 X 10- 7 - is a 85 X 10- 7 / ° C.
[0015] アルカリ含有ガラス粉末とは、その成分として R O (Rは、アルカリ金属を表す。 )を  [0015] The alkali-containing glass powder contains R O (R represents an alkali metal) as a component thereof.
2  2
含有するガラスの粉末であり、 R Oを典型的には合計で 1一 30モル％を含む。  A glass powder containing, typically containing 1 to 30 mole percent of RO.
2  2
本発明のペーストにおけるアルカリ含有ガラス粉末は、下記酸化物基準のモル％ 表示で、本質的に、 B O 0— 60%  The alkali-containing glass powder in the paste of the present invention is essentially represented by the following oxide based mol%,
2 3 、SiO 20— 65%  2 3, SiO 20—65%
2 、ZnO 0— 60%、 MgO + C aO + SrO + BaO 0— 50%、 Li O +Na O +K Ο 1  2, ZnO 0-60%, MgO + CaO + SrO + BaO 0-50%, Li O + Na O + K Ο 1
2 2 2 一 30%、 Al Ο +TiO +ZrO  2 2 2 1 30%, Al Ο + TiO + ZrO
2 3 2 2 3 2
0— 13%、 CuO + SnO + CeO 0—5%,からなり、 PbOまたは Bi Oを含有するConsists of 0-13%, CuO + SnO + CeO 0-5%, contains PbO or BiO
2 2 2 2 3 場合は PbO + Bi Oが 10%以下であることが好ましい。 In the case of 222 2, the content of PbO + BiO is preferably 10% or less.
2 3  twenty three
ここで、たとえば「B O 0— 60%」とは、 B Oは必須ではないが 60%まで含有して  Here, for example, “B 0 0-60%” means that B 2 O is not essential but contains up to 60%.
2 3 2  2 3 2
ちょい、との意である。 [0016] 前記場合において、 PbO + Bi Oの含有量はより好ましくは 5%以下であり、 PbO I mean, a little. [0016] In the above case, the content of PbO + Bi O is more preferably 5% or less.
2 3  twenty three
および Zまたは Bi Oを実質的に含有しないのが最も好ましい。  Most preferably, it is substantially free of Z and BiO.
2 3  twenty three
[0017] アルカリ含有ガラス粉末には、上記成分以外にも、その他の成分を本発明の目的を 損なわない範囲で含有してもよい。その場合、「その他の成分」の含有量の合計は 5 %以下であることが好まし!/、。  [0017] In addition to the above components, the alkali-containing glass powder may contain other components as long as the object of the present invention is not impaired. In that case, the total content of the "other components" is preferably 5% or less! / ,.
前記「その他の成分」として、 La O等の希土類酸化物、 P O、 MnO、 Fe O、 Co  As the “other components”, rare earth oxides such as La O, P O, MnO, Fe O, Co
2 3 2 5 2 3 2 3 2 5 2 3
0、 NiO、 GeO、 Y O、 MoO、 Rh O、 Ag 0、 In O、 TeO、 WO、 ReO、 V O、 0, NiO, GeO, Y O, MoO, Rh O, Ag 0, In O, TeO, WO, ReO, V O,
2 2 3 3 2 3 2 2 3 2 3 2 2 5 2 2 3 3 2 3 2 2 3 2 3 2 2 5
PdO等が例示される。 PdO and the like are exemplified.
[0018] セラミックスフイラ一は必須ではないが必要に応じて含有してもよい。セラミックフイラ 一を含有する場合、その典型的な含有量は 5— 25質量％である。セラミックスフイラ 一として、アルミナ、ムライト、ジルコン、ジルコユア、コージエライト、チタン酸アルミ- ゥム、 β—スポジュメン、 α—石英、石英ガラス、 j8—石英固溶体、 —ユークリプタイト 等の粉末が例示される。 [0018] The ceramic filler is not essential, but may be contained as necessary. When a ceramic filler is contained, its typical content is 5-25% by mass. Examples of the ceramic filler include powders of alumina, mullite, zircon, zirconia, cordierite, aluminum titanate, β-spodumene, α -quartz, quartz glass, j8-quartz solid solution, and eucryptite. .
[0019] 耐熱顔料は必須ではないが必要に応じて含有してもよい。耐熱顔料を含有する場 合、その典型的な含有量は 0. 5— 10質量％である。耐熱顔料として、チタ-ァ等の 白色顔料、 Fe— Mn複酸化物系、 Fe— Co— Cr複酸化物系、 Fe— Mn— A1複酸化物系 等の顔料が例示される。  [0019] The heat-resistant pigment is not essential, but may be contained as necessary. When a heat-resistant pigment is contained, its typical content is 0.5 to 10% by mass. Examples of heat-resistant pigments include white pigments such as titer, and pigments such as Fe—Mn double oxide, Fe—Co—Cr double oxide, and Fe—Mn—A1 double oxide.
[0020] 本発明のペーストにおける樹脂の含有割合は、無機粉末を 100質量部として 0. 5 一 15質量部であることが好ましい。該含有割合が 0. 5質量部未満ではドライフィルム との密着性が弱くなるおそれがあり、より好ましくは 1質量部以上であり、 15質量部超 ではブラストレートが遅くなりすぎるおそれがあり、より好ましくは 10質量部以下である  [0020] The content of the resin in the paste of the present invention is preferably 0.5 to 15 parts by mass based on 100 parts by mass of the inorganic powder. If the content is less than 0.5 part by mass, the adhesion to the dry film may be weak, more preferably 1 part by mass or more, and if it exceeds 15 parts by mass, the blast rate may be too slow, Preferably not more than 10 parts by mass
[0021] 本発明のペーストの榭脂はアクリル重合体を含有する。榭脂中のアクリル重合体含 有量は、好ましくは 10質量％以上、より好ましくは 20質量％以上、典型的には 40質 量％以上である。 [0021] The resin of the paste of the present invention contains an acrylic polymer. The acrylic polymer content in the resin is preferably at least 10% by mass, more preferably at least 20% by mass, and typically at least 40% by mass.
本発明のペーストの榭脂は、ホモポリマーとしたときに Tg (ガラス転移温度）が 40°C 以下となるモノマーを重合成分として有するアクリル重合体を含有する。該アクリル重 合体を含有させることにより、サンドブラストに要する時間を長くすることなく乾燥膜と ドライフィルムとの密着性を良好に保て隔壁形成におけるドライフィルムの剥離を少な くできる、または、前記密着性を低下させることなくサンドブラストに要する時間を短く できる、さらには、ペーストにしたときに表面にクリア層（透明層）が分離して不均一が 生ずる現象を抑制できる場合がある。該アクリル重合体は、ホモポリマーとしたときにThe resin of the paste of the present invention contains an acrylic polymer having, as a polymerization component, a monomer having a Tg (glass transition temperature) of 40 ° C. or lower when formed into a homopolymer. By including the acrylic polymer, a dry film can be formed without increasing the time required for sandblasting. Good adhesion to the dry film can be maintained to reduce the peeling of the dry film in the formation of the partition walls, or the time required for sandblasting can be reduced without lowering the adhesion, In some cases, the phenomenon in which the clear layer (transparent layer) separates to cause non-uniformity can be suppressed. When the acrylic polymer is a homopolymer,
Tgが o°c以下となるモノマーを重合成分として有することが好ましい。 It is preferable to have a monomer having a Tg of not more than o ° c as a polymerization component.
[0022] ホモポリマーとしたときに Tgが 40°C以下となるモノマーとしては、 n ブチル (メタ）ァ タリレート（Tg： 30°C)、 n—へキシル (メタ）アタリレート（Tg :— 5°C)、ェチルへキシル ( メタ）アタリレート（Tg：— 20°C)、 n—ドデシル (メタ）アタリレート (Tg：— 60°C)、 2—ジェ チルアミノエチル (メタ)アクリル酸 (Tg： 26°C)等が挙げられる（括弧内の温度は、各 モノマーから得られるホモポリマーの Tgを示す）。 [0022] Monomers having a Tg of 40 ° C or less when formed into a homopolymer include n-butyl (meth) acrylate (Tg: 30 ° C) and n-hexyl (meth) acrylate (Tg: —5 ° C), ethylhexyl (meth) acrylate (Tg: -20 ° C), n-dodecyl (meth) acrylate (Tg: -60 ° C), 2-ethylaminoethyl (meth) acrylic acid ( (Tg: 26 ° C) (the temperature in parentheses indicates the Tg of the homopolymer obtained from each monomer).
[0023] 本発明のペーストの榭脂が含有するアクリル重合体は、酸価またはアミン価を有す ることが好ましい。アクリル重合体力 酸価またはアミン価を有していないと、ブラスト レートが遅くなる、乾燥膜とドライフィルムとの密着性が低下する、またはペーストにし たときに表面にクリア層（透明層）が分離して不均一が生ずるおそれがある。 The acrylic polymer contained in the resin of the paste of the present invention preferably has an acid value or an amine value. Acrylic polymer strength If there is no acid value or amine value, the blast rate will be slow, the adhesion between the dry film and the dry film will be reduced, or the clear layer (transparent layer) will separate from the surface when the paste is used May cause non-uniformity.
アクリル重合体が酸価を有する場合、該アクリル重合体の酸価は 30mgKOHZg 以下であることが好ましい。酸価が 30mgKOH/gを超えると、かえって乾燥膜とドラ ィフィルムとの密着性が低下するおそれがある。  When the acrylic polymer has an acid value, the acid value of the acrylic polymer is preferably 30 mgKOHZg or less. If the acid value exceeds 30 mgKOH / g, the adhesion between the dried film and the dry film may be reduced.
アクリル重合体に酸価またはアミン価を持たせるためには、重合成分として、カルボ キシル基、アミノ基、アミン基等の極性基を有するモノマーを所望の酸価またはァミン 価の大きさに応じて含有させればよい。そのようなモノマーとしては、（メタ)アクリル酸 、 2—ジェチルアミノエチル (メタ)アクリル酸等が挙げられる。アクリル重合体における これらのモノマー成分の含有量は、好ましくは 0. 5— 5モル0 /0である。 In order to impart an acid value or an amine value to the acrylic polymer, a monomer having a polar group such as a carboxyl group, an amino group, or an amine group is used as a polymerization component in accordance with a desired acid value or an amine value. What is necessary is just to contain. Examples of such a monomer include (meth) acrylic acid, 2-getylaminoethyl (meth) acrylic acid, and the like. The content of these monomer components in the acrylic polymer is preferably 0.5 5 5 mol 0/0.
[0024] アクリル重合体は、上記のホモポリマーとしたときに Tgが 40°C以下となるモノマー、 酸価またはアミン価を付与するためのモノマー以外のその他のモノマーを、本発明の 目的を損なわない範囲で、重合成分として含有してもよい。 [0024] The acrylic polymer impairs the purpose of the present invention by using a monomer having a Tg of 40 ° C or less when the above homopolymer is used, and other monomers other than a monomer for providing an acid value or an amine value. It may be contained as a polymerization component within a range not present.
上記のその他のモノマーとしては、たとえばメチル (メタ）アタリレート、ェチル (メタ） アタリレート、 n プロピル (メタ）アタリレート、 i ブチル (メタ）アタリレート、 t ブチル (メ タ）アタリレート、ステアリル (メタ）アタリレート、ォレイル (メタ）アタリレート、シクロへキ シル (メタ）アタリレート、ベンジル (メタ）アタリレート、 2—ヒドロキシェチル (メタ)アタリレ ート、 2—ヒドロキシプロピル (メタ)アタリレート、 3—ヒドロキシプロピル (メタ)アタリレート、 さらに、これら (メタ)アタリレート以外の重合性基を有するモノマーが挙げられる。 Examples of the above-mentioned other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, stearyl ( (Meta) acrylate, oleyl (meta) acrylate, cyclohexyl Sil (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, Monomers having a polymerizable group other than (meth) acrylate are exemplified.
[0025] アクリル重合体中の上記ホモポリマーとしたときに Tgが 40°C以下となるモノマー成 分の含有量は、 5モル％以上である。該含有量が 5モル％未満では、高いブラストレ ートゃ乾燥膜とドライフィルムとの良好な密着性を達成しに《なる、または、前記タリ ァ層分離現象が起こりやすくなるおそれがあり、典型的には 40モル％以上である。  [0025] When the above homopolymer in the acrylic polymer is used, the content of the monomer component having a Tg of 40 ° C or less is 5 mol% or more. When the content is less than 5 mol%, a high blast rate can be achieved to achieve good adhesion between the dry film and the dry film, or the talli layer separation phenomenon can easily occur. It is typically at least 40 mol%.
[0026] アクリル重合体の質量平均分子量は、 40, 000— 200, 000であることが好ましく、 40, 000— 100, 000であること力より好まし!/、。該質量平均分子量力40, 000未満 では乾燥膜とドライフィルムの密着性が不足するおそれがあり、 200, 000超ではタ 一ビネオール等の有機溶剤に溶解しに《なる。  [0026] The mass average molecular weight of the acrylic polymer is preferably from 40,000 to 200,000, more preferably from 40,000 to 100,000! If the weight average molecular weight is less than 40,000, the adhesion between the dry film and the dry film may be insufficient. If the weight average molecular weight exceeds 200,000, it may be dissolved in an organic solvent such as tavinelone.
[0027] 本発明のペーストには、その糸引き性や無機粉末沈降性を抑制したい等の場合に は榭脂として、アクリル重合体以外の榭脂、たとえばェチルセルロース等を必要に応 じて含有させてちょい。  [0027] In the paste of the present invention, if it is desired to suppress the stringing property or the inorganic powder sedimentation property, a resin other than the acrylic polymer, for example, ethyl cellulose, may be used as the resin if necessary. Let me contain it.
[0028] ェチルセルロースを含有する場合、その質量平均分子量は 50, 000— 200, 000 であることが好ましい。該質量平均分子量が 50, 000未満では乾燥膜とドライフィル ムの密着性が不足するおそれがあり、 200, 000超ではタービネオール等の有機溶 剤に溶解しにくくなる。  [0028] When ethyl cellulose is contained, the weight average molecular weight is preferably from 50,000 to 200,000. If the weight average molecular weight is less than 50,000, the adhesion between the dried film and the dry film may be insufficient, and if it exceeds 200,000, it becomes difficult to dissolve in an organic solvent such as turbineol.
[0029] 榭脂としてェチルセルロースを含有する場合、榭脂中のェチルセルロースの含有 量は典型的には 40質量％以上である。  [0029] When ethyl cellulose is contained as a resin, the content of the ethyl cellulose in the resin is typically 40% by mass or more.
本発明のペーストのアクリル重合体以外の榭脂として、ェチルセルロース以外にも ポリビニルブチラール等の熱可塑性榭脂が例示される。なお、本発明のペーストにお ける榭脂は本質的に熱可塑性榭脂からなるが、本発明の目的を損なわない範囲で 熱可塑性榭脂以外の榭脂を含有してもよ!/、。  Examples of the resin other than the acrylic polymer of the paste of the present invention include thermoplastic resins such as polyvinyl butyral in addition to ethyl cellulose. The resin in the paste of the present invention is essentially composed of a thermoplastic resin, but may contain a resin other than the thermoplastic resin as long as the object of the present invention is not impaired!
[0030] 本発明のペーストにおける有機溶剤の含有割合は、無機粉末を 100質量部として[0030] The content ratio of the organic solvent in the paste of the present invention is based on 100 parts by mass of the inorganic powder.
35— 65質量部が典型的である。 35-65 parts by weight are typical.
本発明のペーストの有機溶剤は、タービネオール、エチレングリコールアルキルェ 一テル（例えばエチレングリコールモノェチルエーテル）、ジエチレングリコールモノア ルキルエーテル（例えばジエチレングリコールモノブチルエーテル（ブチルカルビトー ノレ））、エチレングリコーノレモノァノレキノレエーテノレアセテート、ジエチレングリコーノレモ ノアルキルエーテルアセテート（例えばジエチレングリコールモノブチルエーテルァセ テート（ブチルカルビトールアセテート） )、ジエチレングリコールジアルキルエーテル アセテート、トリエチレングリコールアルキルエーテルアセテート、トリエチレングリコー ノレァノレキノレエーテノレ、プロピレングリコーノレァノレキノレエーテノレ、プロピレングリコーノレ フエニルエーテル、ジプロピレングリコールアルキルエーテル、トリプロピレングリコー ルアルキルエーテル（例えばトリプロピレングリコール n ブチルエーテル）、プロピレ ングリコーノレァノレキノレエーテノレアセテート、ジプロピレングリコーノレァノレキノレエーテノレ アセテート、トリプロピレングリコールアルキルエーテルアセテート、ァセチルトリアルキ ルシトレート、トリアルキルシトレート、 2, 2, 4—トリメチル—1, 3ペンタジオールモノイソ ブチレート、 2, 2, 4 トリメチルー 1, 3ペンタジオールジイソプチレート、フタル酸ジメ チル（ジメチルフタレート）、フタル酸ジェチル（ジェチルフタレート）、およびフタル酸 ジブチル（ジブチルフタレート）（ここでアルキルは、メチル、ェチル、プロピル、ブチル 、へキシルまたは 2—ェチルへキシルを表す）、力 なる群力 選ばれる 1種以上であ ることが好ましい。ターピネオール、ジエチレングリコールモノブチルエーテル、ジェ チレングリコールモノブチルエーテルアセテート、 2, 2, 4 トリメチルー 1, 3ペンタジ オールモノイソブチレートおよびプロプレングリコールフエニルエーテルからなる群か ら選ばれる 1種以上であることがより好ましい。 The organic solvent of the paste of the present invention includes terbineol, ethylene glycol alkyl ether (eg, ethylene glycol monoethyl ether), diethylene glycol monoether. Alkyl ether (for example, diethylene glycol monobutyl ether (butyl carbitol)), ethylene glycol monoleno quinoleate enorea acetate, diethylene glycol mono oleno alkyl ether acetate (for example, diethylene glycol monobutyl ether acetate (butyl carbitol acetate)) , Diethylene glycol dialkyl ether acetate, triethylene glycol alkyl ether acetate, triethylene glycol alcohol, propylene glycol alcohol, propylene glycol phenyl ether, dipropylene glycol alkyl ether, tripropylene glycol Alkyl ethers (eg, tripropylene glycol n-butyl ether), propylene Glycoloneolequinoleate enoleacetate, dipropylene glycololenolequinoleateneoleate acetate, tripropylene glycol alkyl ether acetate, acetyl trialkyl citrate, trialkyl citrate, 2,2,4-trimethyl-1 1,3 pentadiol monoisobutyrate, 2,2,4 trimethyl-1,3 pentadiol diisobutylate, dimethyl phthalate (dimethyl phthalate), getyl phthalate (getyl phthalate), and dibutyl phthalate (dibutyl phthalate) (Here, alkyl represents methyl, ethyl, propyl, butyl, hexyl, or 2-ethylhexyl), and is preferably at least one selected from the group consisting of: It is more preferably at least one selected from the group consisting of terpineol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, 2,2,4 trimethyl-1,3 pentadiol monoisobutyrate, and propylene glycol phenyl ether. preferable.
本発明のペーストにおいて、界面活性剤は必須ではないが、必要に応じて含有し てもよい。界面活性剤としては、親水性部分に極性基を有することが好ましい。極性 基としては、カルボキシル基、リン酸基、アミノ基および水酸基からなる群から選ばれ る 1種以上の極性基が挙げられる。  In the paste of the present invention, a surfactant is not essential, but may be contained as necessary. The surfactant preferably has a polar group in the hydrophilic portion. Examples of the polar group include one or more polar groups selected from the group consisting of a carboxyl group, a phosphate group, an amino group, and a hydroxyl group.
これらの極性基を有する界面活性剤のなかでも、下記式 1で表されるポリオキシァ ルキレンアルキルエーテルのカルボン酸もしくはリン酸エステルまたはその塩、アルキ ルリン酸エステルまたはその塩、ヒドロキシェチルアルキルァミン、ポリオキシアルキレ ンアルキルァミン、あるいはポリエステルのアルキロールァミン塩が好ましい。ここで、 アルキルは炭素数 8— 20の直鎖または分岐鎖のアルキル (たとえば、ォクチル、ラウ リル、セチル、ステアリル、ォレイルなど。）であり、アルキレンは炭素数 2— 5の直鎖ま たは分岐鎖のアルキレン（たとえば、エチレン、プロピレンなど。）である。 Among these surfactants having a polar group, carboxylic acid or phosphoric acid ester of polyoxyalkylene alkyl ether represented by the following formula 1 or a salt thereof, alkyl phosphate ester or a salt thereof, hydroxyethyl alkylamine And polyoxyalkylene alkylamines or polyester alkylolamine salts. Here, alkyl is a straight-chain or branched-chain alkyl having 8 to 20 carbon atoms (for example, octyl, Lil, cetyl, stearyl, oleyl, etc. ) And alkylene is a straight-chain or branched-chain alkylene having 2 to 5 carbon atoms (eg, ethylene, propylene, etc.).
[0032] R O (R O) X · · ·式 1 [0032] R O (R O) X
1 2 n  1 2 n
ここで、 Rは炭素数 8— 20の直鎖または分岐鎖のアルキル基、 Rは炭素数 2— 5の  Here, R is a linear or branched alkyl group having 8 to 20 carbon atoms, and R is a 2 to 5 carbon atom.
1 2  1 2
アルキレン基、 nは 1一 20、 Xはカルボキシル基またはリン酸基である。  An alkylene group, n is 120, and X is a carboxyl group or a phosphate group.
[0033] 具体的には、前記式 1で表される化合物としてポリオキシエチレンラウリルエーテル カルボン酸塩、ポリオキシエチレンラウリルエーテルリン酸エステル等、アルキルリン 酸エステルとしてラウリルリン酸エステル等、ヒドロキシェチルアルキルァミンとして N— ヒドロキシェチルラウリルアミン等、ポリオキシアルキレンアルキルァミンとしてポリオキ シエチレンラウリルアミン等が挙げられる。 Specifically, compounds represented by the above formula 1 include polyoxyethylene lauryl ether carboxylate, polyoxyethylene lauryl ether phosphate and the like, and alkyl phosphates such as lauryl phosphate and hydroxyethyl. Examples of the alkylamine include N-hydroxyethyl laurylamine, and examples of the polyoxyalkylenealkylamine include polyoxyethylene laurylamine.
[0034] これらの界面活性剤を含有することは、乾燥膜の亀裂や乾燥膜と基板との密着性 の低下を防止できる点で好ましいことがある。さらにサンドブラストに要する時間を短 縮し、乾燥膜とドライフィルムとの良好な密着性を保持させるのにも有効であることが ある。 [0034] Including these surfactants may be preferable in that cracks in the dried film and a decrease in adhesion between the dried film and the substrate can be prevented. Further, it may be effective to shorten the time required for sandblasting and to maintain good adhesion between the dry film and the dry film.
本発明のペーストが界面活性剤を含有する場合、その含有割合は、無機粉末を 10 0質量部として 0. 2— 2質量部であることが好ましぐ典型的には 0. 5質量部以上で あり、 2質量部超では、力えって乾燥膜に亀裂が入る、乾燥膜と基板との密着性が低 下する、等の問題が起こるおそれがある。  When the paste of the present invention contains a surfactant, the content ratio is preferably 0.2 to 2 parts by mass with 100 parts by mass of the inorganic powder, typically 0.5 parts by mass or more. If the amount is more than 2 parts by mass, there may be problems such as cracking of the dried film by force and reduction in adhesion between the dried film and the substrate.
本発明のペーストには、必要に応じてこれらの界面活性剤は 2種類以上含有させて ちょい。  The surfactant of the present invention may contain two or more of these surfactants as necessary.
[0035] また、本発明のペーストは、粘度調整等を行!ヽた ヽ場合は、非イオン性界面活性剤 を含有することが好ましいことがある。この場合、非イオン性界面活性剤の含有割合 は、無機粉末を 100質量部として 0. 2— 2質量部であることが好ましい。  [0035] The paste of the present invention may preferably contain a nonionic surfactant when viscosity adjustment or the like is performed. In this case, the content ratio of the nonionic surfactant is preferably 0.2 to 2 parts by mass based on 100 parts by mass of the inorganic powder.
非イオン性界面活性剤としては、ポリエチレングリコールアルキルエーテル、ポリエ チレングリコールアルキルエステル、ポリオキシエチレンアルキルエーテル、ポリオキ シエチレンアルキルエステル、ポリオキシエチレンポリプロピレンアルキルエーテル、 ポリエチレングリコールアルキルァミン、ヒドロキシェチルアルキルァミン、リン酸エステ ル、カルボン酸エステル、ポリアルキルグリコールエーテル、アルキルポリエーテルァ ミンまたはアルキルアンモ-ゥム塩等が例示される。ここで、アルキルは、ォクチル、ラ ゥリル、セチル、ステアリル、ォレイルなどである。 Non-ionic surfactants include polyethylene glycol alkyl ether, polyethylene glycol alkyl ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene polypropylene alkyl ether, polyethylene glycol alkylamine, hydroxyethyl alkyla Min, phosphate ester, carboxylic acid ester, polyalkyl glycol ether, alkyl polyether Examples thereof include min or alkylammonium salts. Here, alkyl refers to octyl, radial, cetyl, stearyl, oleyl and the like.
[0036] 以下で、本発明のペーストを用いた PDPの製造方法を説明する。  Hereinafter, a method for producing a PDP using the paste of the present invention will be described.
本発明において、 PDPは、たとえば交流方式であれば次のようにして製造される。 図 1に示すように、前面ガラス基板 laの上に、電極 2をパターユングして形成し、ノ ス線 (図示せず)を形成した後、電極を保護する透明誘電体層 3を形成し、透明誘電 体層 3の上に通常 MgOカゝらなる保護膜を形成して、前面基板を製造する。  In the present invention, the PDP is manufactured as follows, for example, in the case of an AC system. As shown in FIG. 1, an electrode 2 is formed on the front glass substrate la by patterning, a nose line (not shown) is formed, and then a transparent dielectric layer 3 for protecting the electrode is formed. Then, a protective film, usually made of MgO, is formed on the transparent dielectric layer 3 to manufacture a front substrate.
[0037] 一方、背面基板の作製では、まず、背面ガラス基板 lbの上に、パターユングされた アドレス電極 5を形成したのち、該アドレス電極を被覆する絶縁被覆層 8を形成する。 隔壁 6は、前述した通り、本発明のペーストを絶縁被覆層 8上に全面に塗布し乾燥さ せた後、サンドブラストにより所望の隔壁パターンに加工し、焼成して形成する。  On the other hand, in the production of the rear substrate, first, a patterned address electrode 5 is formed on the rear glass substrate lb, and then an insulating coating layer 8 covering the address electrode is formed. As described above, the partition walls 6 are formed by applying the paste of the present invention on the entire surface of the insulating coating layer 8, drying the paste, processing it into a desired partition pattern by sandblasting, and firing.
[0038] 前記焼成が行われる温度は通常、 500— 620°Cである。該温度が 500°C未満では 焼成後の隔壁に前記樹脂が一部残留し、 PDPまたは VFDにお 、てパネルを封着す る際またはパネル放電時にこれら残留樹脂がガスとなって放出されるおそれがあり、 620°C超ではガラス基板が変形するおそれがある  [0038] The temperature at which the calcination is performed is usually 500 to 620 ° C. If the temperature is lower than 500 ° C, the resin partially remains on the fired partition walls, and the residual resin is released as a gas when sealing the panel with PDP or VFD or when discharging the panel. If the temperature exceeds 620 ° C, the glass substrate may be deformed
[0039] 隔壁パターンを形成後、蛍光体層 4を印刷'焼成して形成する。  After forming the partition pattern, the phosphor layer 4 is formed by printing and baking.
[0040] PDPは、前面ガラス基板 la、背面ガラス基板 lbの周縁にシール材（図示せず)を デイスペンサで塗布し、上記のように作製した前面基板と背面基板を、基板の電極が 対向するように組み立ててパネルイ匕し、焼成して、プラズマディスプレイの内部を排 気して、放電空間 7に Neや He— Xeなどの放電ガスを封入して作製する。  [0040] In the PDP, a sealing material (not shown) is applied to the periphery of the front glass substrate la and the rear glass substrate lb with a dispenser, and the electrodes of the front substrate and the rear substrate manufactured as described above are opposed to each other. The plasma display is evacuated, the discharge space 7 is filled with a discharge gas such as Ne or He—Xe, and the plasma display is manufactured.
なお、上記の例は交流方式について述べた力 本発明は直流方式にも適用できる 実施例  Note that the above example is based on the AC method. The present invention is also applicable to the DC method.
[0041] モル0 /0表示の組成が、 SiO： 33%、 B O : 19. 5%、 ZnO : 18%、 Al O： 10%、 B [0041] Composition of mole 0/0 appears, SiO: 33%, BO: 19. 5%, ZnO: 18%, Al O: 10%, B
2 2 3 2 3 aO : 2. 5%、 Li 0 : 9%, Na 0 : 7. 5%、 SnO : 0. 5%であるガラス粉末 A (アルカリ  2 2 3 2 3 AO: 2.5%, Li 0: 9%, Na 0: 7.5%, SnO: 0.5% Glass powder A (alkaline
2 2 2  2 2 2
含有ガラス。 Ts = 580。C、 a = 85 X 10— 7Z。C)、および、 SiO : 43. 3%、 PbO : 49. Containing glass. Ts = 580. C, a = 85 X 10- 7 Z. C), and SiO: 43.3%, PbO: 49.
2  2
6%、A1 0 : 7. 1%であるガラス粉末 B (アルカリ金属酸化物を含有しない鉛含有ガ 6%, A10: 7.1% glass powder B (lead-free gas without alkali metal oxides)
2 3 twenty three
ラス。 Ts = 575°C、 a = 81 X 10— 7Z°C)を次のようにして作製した。 [0042] すなわち、原料を上記組成となるように調合して混合し、 1200— 1350°Cの電気炉 中で白金るつぼを用いて 1時間溶解し、溶融ガラスを流し出して薄板状ガラスに成形 した。該薄板状ガラスをボールミルで粉砕して平均粒径が 2. 0 mのガラス粉末とし た。 Russ. It was prepared Ts = 575 ° C, a = 81 X 10- 7 the Z ° C) as follows. [0042] That is, the raw materials are mixed and mixed so as to have the above composition, melted in an electric furnace at 1200-1350 ° C for 1 hour using a platinum crucible, and the molten glass is poured out to form a thin glass. did. The sheet glass was pulverized with a ball mill to obtain glass powder having an average particle size of 2.0 m.
次に、ガラス粉末 A、 Bを用いて無機粉末 Al、 A2、 B1を作製した。すなわち、無機 粉末 A1は、ガラス粉末 A: 91. 3質量％、シリカ粉末: 8. 0質量％、チタ-ァ粉末: 0. 7質量％の割合で混合して作製した。無機粉末 A2は、ガラス粉末 A: 95. 1質量％、 チタニア粉末: 4. 9質量％の割合で混合して作製した。無機粉末 B1は、ガラス粉末 B : 84. 5質量％、シリカ粉末： 15. 0質量％、チタ-ァ粉末: 0. 5質量％の割合で混 合して作製した。  Next, inorganic powders Al, A2 and B1 were prepared using glass powders A and B. That is, the inorganic powder A1 was prepared by mixing glass powder A: 91.3% by mass, silica powder: 8.0% by mass, and titanium powder: 0.7% by mass. The inorganic powder A2 was prepared by mixing 95.1% by mass of glass powder A and 4.9% by mass of titania powder. The inorganic powder B1 was prepared by mixing glass powder B: 84.5% by mass, silica powder: 15.0% by mass, and titanium powder: 0.5% by mass.
例 1一 17では無機粉末 A1を、例 18、 20では無機粉末 A2を、例 19では無機粉末 B1をそれぞれ使用した。  In Examples 11 to 17, the inorganic powder A1 was used, in Examples 18 and 20, the inorganic powder A2 was used, and in Example 19, the inorganic powder B1 was used.
[0043] 次に、榭脂（アクリル重合体、ェチルセルロース）と有機溶剤（タービネオール、ジェ チレングリコールモノブチルエーテルアセテート（DEGBEA)、プロピレングリコール ジアセテート (PGDA) )を、表に無機粉末を 100質量部として質量部で示す割合で 混ぜ、 85°Cで 4時間攪拌し、榭脂を溶解させビヒクルを作製した。ェチルセルロース は質量平均分子量が 180, 000のものを用いた。 Next, a resin (acrylic polymer, ethylcellulose) and an organic solvent (turbineol, ethylene glycol monobutyl ether acetate (DEGBEA), propylene glycol diacetate (PGDA)) were added. The mixture was stirred at 85 ° C. for 4 hours to dissolve the resin and prepare a vehicle. Ethyl cellulose having a mass average molecular weight of 180,000 was used.
例 1一 17、 19、 20で用いたアクリル重合体は、 n— BMA(n ブチルメタタリレート）、 2DEAEA (2—ジェチルアミノエチル (メタ）アクリル酸）、 EHMA (ェチルへキシル (メ タ）アタリレート）、 MMA (メチルメタアタリレート（Tg : 110°C) )、 i BMA(i—ブチルメ タクリレート (Tg: 60°C) )、メタアクリル酸を表にモル％で示す割合で含有する (括弧 内の温度は、各モノマー力も得られるホモポリマーの Tgを示す)。また、表の Tgはァ クリル重合体のガラス転移温度、 Mwはアクリル重合体の質量平均分子量を表す。  Example 11 The acrylic polymers used in 17, 19, and 20 were n-BMA (n-butyl methacrylate), 2DEAEA (2-dimethylaminoethyl (meth) acrylic acid), and EHMA (ethylhexyl (meta-hexyl)). ) Acrylate, MMA (methyl methacrylate (Tg: 110 ° C)), iBMA (i-butyl methacrylate (Tg: 60 ° C)), and methacrylic acid in the ratio shown in mol% in the table (The temperature in parentheses indicates the Tg of the homopolymer from which each monomer force is also obtained). In the table, Tg represents the glass transition temperature of the acrylic polymer, and Mw represents the mass average molecular weight of the acrylic polymer.
[0044] 次に、ビヒクルと無機粉末とを混合してペーストとした。 [0044] Next, the vehicle and the inorganic powder were mixed to form a paste.
なお、例 1一 17、 19、 20では、無機粉末およびビヒクルの混合物に、無機粉末 100 質量部に対して表に質量部で示す割合で、界面活性剤 1または 2を加え、三本ロー ルで混練してずり速度 4s— 1での粘度力 0Pa · sとなるように粘度調整し、ペーストとし 界面活性剤 1は N—ヒドロキシェチルラウリルアミン（下記式（1)で表される構造の化 合物）であり、界面活性剤 2はリン酸基を含む共重合物のアルキロールァミン塩で「Di sperbykl80j (ビックケミー ·ジャパン株式会社製）を用いた。 In Examples 11 to 17, 19 and 20, surfactant 1 or 2 was added to the mixture of inorganic powder and vehicle at the ratio shown in parts by mass in the table with respect to 100 parts by mass of inorganic powder, and three rolls were added. And adjust the viscosity to a viscosity of 0 Pa · s at a shear rate of 4 s- 1 to obtain a paste. Surfactant 1 is N-hydroxyethyllaurylamine (a compound having a structure represented by the following formula (1)), and Surfactant 2 is an alkylolamine salt of a copolymer containing a phosphate group. "Di sperbykl80j (manufactured by BYK Japan KK) was used.
[0045] [化 1]
Figure imgf000014_0001
[0045]
Figure imgf000014_0001
[0046] 得られたペーストを 10cm角のガラス基板（旭硝子社製 PD200)〖こ 400 μ mのスぺ ーサでブレードコートし、 120°Cの乾燥機にて 1. 5時間乾燥させ、乾燥膜とした。例 1 一 11は本発明例、例 12— 18は比較例、例 19、 20は参照例である。なお、例 20の ペーストでは前記クリア層分離現象が顕著であった。 [0046] The obtained paste was blade-coated with a 10-cm square glass substrate (PD200 manufactured by Asahi Glass Co., Ltd.) with a 400-μm spacer, dried for 1.5 hours in a dryer at 120 ° C, and dried. It was a membrane. Examples 11 to 11 are examples of the present invention, Examples 12 to 18 are comparative examples, and Examples 19 and 20 are reference examples. In the paste of Example 20, the clear layer separation phenomenon was remarkable.
[0047] 得られた乾燥膜を目視観察した結果、例 1一 20の 、ずれにっ 、ても亀裂は認めら れなかった。  [0047] As a result of visual observation of the obtained dried film, no crack was observed even in the case of Example 120.
[0048] 次に、例 1一 20の乾燥膜について、以下に述べるようにしてブラストレート（単位： μ m/ およびドライフィルム密着性の指標であるドライフィルム累積剥離本数 (単位： 本)を調べた。結果を表のブラストレートおよび剥離本数の欄に示す。  Next, for the dried film of Example 1-120, the blast rate (unit: μm / and the cumulative number of dry film peelings (unit: pieces), which is an index of dry film adhesion, was examined as described below. The results are shown in the columns of the blast rate and the number of peeled pieces in the table.
[0049] ブラストレート：不二製作所社製サンドブラスト装置（型式 SCM— 1ADE— NH— 40 1P)を用いて、サクシヨン圧 150kPa、圧送エアー圧 200kPa、ガン移動速度 4. lm Z分、ローラー回転数 2. 5rpmの条件で乾燥膜を 1回ブラストし、切削深さを測定し て、これをブラストレートとした。  [0049] Blast rate: Using a sand blasting machine (model SCM-1ADE-NH-401P) manufactured by Fuji Seisakusho, suction pressure 150 kPa, pumping air pressure 200 kPa, gun moving speed 4. lm Z minute, roller rotation speed 2 The dried film was blasted once under the condition of .5 rpm, the cutting depth was measured, and this was used as a blast straight.
[0050] ドライフィルム累積剥離本数：東京応化工業社製のドライフィルム BF704を 4cm X 5cmに切断し、ロール温度 110°C、ロール圧 150kPa、基板搬送速度 0. 45mZ分 の条件で 1回ラミネ—タに通した。その後、線幅 40、 50、 60、 80、 100、 125、 150、 2 00 μ mの 8種類のラインが各 5本、計 40本あるパターンの露光マスクをセットして 250 mjZcm2で露光し、 0. 3%炭酸ナトリウム水溶液の現像液で現像したものを 50°Cの 乾燥機で 15分乾燥させた。これを不二製作所社製サンドブラスト装置 (型式 SCM -1ADE-NH-401P)を用いて、サクシヨン圧 450kPa、圧送エアー圧 225kPa、ガ ン移動速度 2. 7mZ分、ローラー回転数 6. 25rpmの条件でブラストし、ドライフィル ムが線長の半分以上剥がれたラインの本数を累積剥離本数とした。 [0050] Cumulative number of peeled dry films: Dry film BF704 manufactured by Tokyo Ohka Kogyo Co., Ltd. is cut into 4 cm X 5 cm, and the laminating is performed once at a roll temperature of 110 ° C, a roll pressure of 150 kPa, and a substrate transfer speed of 0.45 mZ. Passed through. Thereafter, the line width 40, 50, 60, 80, 100, 125, 150, 2 00 μ 8 kinds of lines present the 5 m, and exposure by setting the exposure mask pattern that total forty at 250 mjZcm 2 The solution developed with a 0.3% aqueous solution of sodium carbonate was dried in a dryer at 50 ° C. for 15 minutes. Using a sand blasting machine (Model SCM-1ADE-NH-401P) manufactured by Fuji Seisakusho, under the conditions of suction pressure 450 kPa, pumping air pressure 225 kPa, gun moving speed 2.7 mZ, roller rotation speed 6.25 rpm Blast and dry fill The number of lines where the film was peeled off by half or more of the line length was defined as the cumulative number of peeled lines.
[0051] ドライフィルム累積剥離本数は、剥がれた本数が合計で 35本未満であることが好ま しい。 35本以上では、上記サンドブラスト条件よりは緩やかな条件で通常行なわれる 隔壁形成時のサンドブラスト条件においてもドライフィルムが乾燥膜から剥離するお それがある。より好ましくは 25本未満、更に好ましくは 20本未満である。  [0051] The cumulative number of peeled dry films is preferably less than 35 in total. With 35 or more, the dry film may peel off from the dry film even under the sand blasting condition for forming the partition walls, which is usually performed under milder conditions than the above sand blasting condition. More preferably, it is less than 25, even more preferably less than 20.
剥離本数が 15本未満ではブラストレートは 40 μ mZ回以上であることが好ましぐ ブラストレートが 70 μ mZ回以上では剥離本数は 30本未満であることが好ましい。  When the number of strips is less than 15, the blast rate is preferably 40 μmZ times or more. When the blast rate is 70 μmZ or more, the number of strips is preferably less than 30.
[0052] [表 1]  [Table 1]
Figure imgf000015_0001
Figure imgf000015_0001
[0053] [表 2] [0053] [Table 2]
例 9 例 10 例 11 例 12 例 13 例 14 例 15 例 16 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16
アクリル重合体 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5  Acrylic polymer 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5
n-BMA 79 65 0 0 0 0 0 0  n-BMA 79 65 0 0 0 0 0 0
2DEAEA 1 0 0 0 0 0 0 0  2DEAEA 1 0 0 0 0 0 0 0
EH A 0 0 49.5 0 0 0 0 0 EH A 0 0 49.5 0 0 0 0 0
MA 20 32 49.5 5 20 49.5 5 5  MA 20 32 49.5 5 20 49.5 5 5
i-BMA 0 0 0 94 79 49.5 94.5 93  i-BMA 0 0 0 94 79 49.5 94.5 93
メタ クリノレ酸 0 3 1 1 1 1 0.5 2  Methacrylic acid 0 3 1 1 1 1 0.5 2
酸価 0 20 8 B 8 a 3 15  Acid value 0 20 8 B 8 a 3 15
アミン価 8 0 0 0 0 0 0 0  Amine value 8 0 0 0 0 0 0 0
Mw 8.7 8.4 10.0 9.7 9.8 9.9 9.9 10.1  Mw 8.7 8.4 10.0 9.7 9.8 9.9 9.9 10.1
Tg 40 50 50 65 65 80 55 55  Tg 40 50 50 65 65 80 55 55
ェチルセルロース 2.5 2.5 2.5 2.5 2.5 2.5 2.5  Ethyl cellulose 2.5 2.5 2.5 2.5 2.5 2.5 2.5
タービネオール 25 25 25 25 25 25 25 25  Turbineol 25 25 25 25 25 25 25 25
DEGBEA 25 25 25 25 25 25 25 25  DEGBEA 25 25 25 25 25 25 25 25
界面活性剤 1 1.6 1.6 1.6 0 0 0 0 0  Surfactant 1 1.6 1.6 1.6 0 0 0 0 0
界面活性剤 2 0 0 0 0.8 0.8 ο.β 0.8 0,8  Surfactant 2 0 0 0 0.8 0.8 ο.β 0.8 0,8
ブラス卜レー卜 46 64 75 64 66 64 63 54  Brass plate 46 64 75 64 66 64 63 54
刺離本数 12 12 12 27 24 21 IB 15 表 3] Number of punctures 12 12 12 27 24 21 IB 15 Table 3]
Figure imgf000016_0001
なお、本出願の優先権主張の基礎となる日本特許願 2004-061843号（2004年 3月 5曰に日本特許庁に出願）の全明細書の内容をここに引用し、本発明の明細書 の開示として、取り入れるものである。
Figure imgf000016_0001
The contents of the entire specification of Japanese Patent Application No. 2004-061843 (filed on March 5, 2004, filed with the Japan Patent Office), which is the basis of the priority claim of the present application, are cited here, Is incorporated as disclosure.

Claims

請求の範囲 The scope of the claims
[1] アルカリ含有ガラス粉末、榭脂および有機溶剤を含有する隔壁用ペーストであって、 榭脂として、ホモポリマーとしたときにガラス転移温度が 40°C以下となるモノマーを 重合成分として有するアクリル重合体を含有し、  [1] A partition paste containing an alkali-containing glass powder, a resin, and an organic solvent, wherein the resin has a monomer having a glass transition temperature of 40 ° C or lower when formed into a homopolymer as a resin. Containing a polymer,
アクリル重合体中の前記ガラス転移温度力 S40°C以下となるモノマー成分の含有量 力 モル％以上であることを特徴とする隔壁用ペースト。  A paste for partition walls, wherein the content of the monomer component in the acrylic polymer which becomes the glass transition temperature force S40 ° C. or less is force mol% or more.
[2] 前記モノマーが、 n—ブチル (メタ）アタリレート、 n—へキシル (メタ）アタリレート、ェチ ルへキシル (メタ）アタリレート、 n—ドデシル (メタ）アタリレートおよび 2—ジェチルァミノ ェチル (メタ)アタリレートからなる群力も選ばれる 1種以上のモノマーであることを特 徴とする請求項 1に記載の隔壁用ペースト。 [2] The monomers are n-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-hexyl (meth) acrylate, n-dodecyl (meth) acrylate, and 2-ethylethylaminoethyl 2. The paste for partition walls according to claim 1, wherein the paste is one or more monomers selected from the group consisting of (meth) acrylate.
[3] アクリル重合体が、酸価またはアミン価を有することを特徴とする請求項 1または 2に 記載の隔壁用ペースト。 3. The partition wall paste according to claim 1, wherein the acrylic polymer has an acid value or an amine value.
[4] アクリル重合体の酸価が、 30mgKOHZg以下であることを特徴とする請求項 3に 記載の隔壁用ペースト。 4. The paste for partition walls according to claim 3, wherein the acid value of the acrylic polymer is 30 mgKOHZg or less.
[5] アクリル重合体の質量平均分子量が、 40, 000— 200, 000であることを特徴とす る請求項 1一 4のいずれかに記載の隔壁用ペースト。 [5] The partition wall paste according to any one of [14] to [14], wherein the mass average molecular weight of the acrylic polymer is from 40,000 to 200,000.
[6] アクリル重合体力 ホモポリマーとしたときにガラス転移温度が 0°C以下となるモノマ 一を、重合成分として含有することを特徴とする請求項 1一 5のいずれかに記載の隔 壁用ペースト。 [6] The diaphragm according to any one of [15] to [15], wherein a monomer having a glass transition temperature of 0 ° C or less when formed into a homopolymer is contained as a polymerization component. paste.
[7] 榭脂としてェチルセルロースを含有し、榭脂中のェチルセルロース含有量力 0質 量％以上である請求項 1一 6のいずれかに記載の隔壁用ペースト。  [7] The paste for a partition according to any one of [16] to [16], wherein ethyl cellulose is contained as the resin, and the ethyl cellulose content in the resin is 0% by mass or more.
[8] アルカリ含有ガラス粉末が、下記酸ィ匕物基準のモル％表示で、本質的に、 [8] The alkali-containing glass powder is essentially expressed in mol% based on the following sardine,
B O 0— 60%  B O 0—60%
2 3 、  twenty three ,
SiO 20— 65%  SiO 20— 65%
2 、  2,
ZnO 0— 60%、  ZnO 0—60%,
MgO + CaO + SrO + BaO 0— 50%、  MgO + CaO + SrO + BaO 0—50%,
Li O + Na O+K O 1— 30%  Li O + Na O + K O 1— 30%
2 2 2 、  2 2 2,
Al O +TiO +ZrO 0— 13%、 CuO + SnO +CeO 0—5% Al O + TiO + ZrO 0-13%, CuO + SnO + CeO 0-5%
2 2 、  twenty two ,
からなり、 PbOまたは Bi Oを含有する場合は PbO + Bi O力^ 0%以下であることを  If PbO or BiO is contained, the PbO + BiO force must be less than 0%
2 3 2 3  2 3 2 3
特徴とする請求項 1一 7の 、ずれかに記載の隔壁用ペースト。  The paste for partition walls according to claim 17, wherein the paste for a partition wall.
[9] 背面基板を有するプラズマディスプレイパネルの製造方法であって、該背面基板の ガラス基板上に、請求項 1一 8のいずれかに記載の隔壁用ペーストを塗布した後に 乾燥し、加工し、焼成して隔壁を形成する工程を有することを特徴とするプラズマディ スプレイパネルの製造方法。 [9] A method for manufacturing a plasma display panel having a back substrate, comprising applying the partition wall paste according to any one of claims 118 to a glass substrate of the back substrate, followed by drying and processing. A method for manufacturing a plasma display panel, comprising a step of forming a partition by firing.
[10] 請求項 9に記載のプラズマディスプレイパネルの製造方法であって、乾燥された隔 壁用ペーストの加工をサンドブラスト法によって行うことを特徴とするプラズマディスプ レイパネルの製造方法。 [10] The method for manufacturing a plasma display panel according to claim 9, wherein the processing of the dried partition wall paste is performed by a sandblast method.
PCT/JP2005/003537 2004-03-05 2005-03-02 Paste for diaphragm and process for producing plasma display panel WO2005086199A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2006510698A JPWO2005086199A1 (en) 2004-03-05 2005-03-02 Barrier paste and plasma display panel manufacturing method

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004061843 2004-03-05
JP2004-061843 2004-03-05

Publications (1)

Publication Number Publication Date
WO2005086199A1 true WO2005086199A1 (en) 2005-09-15

Family

ID=34918088

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2005/003537 WO2005086199A1 (en) 2004-03-05 2005-03-02 Paste for diaphragm and process for producing plasma display panel

Country Status (3)

Country Link
JP (1) JPWO2005086199A1 (en)
TW (1) TW200531951A (en)
WO (1) WO2005086199A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011213526A (en) * 2010-03-31 2011-10-27 Nihon Yamamura Glass Co Ltd Glass composition

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10241580A (en) * 1997-02-27 1998-09-11 Toppan Printing Co Ltd Plasma display and its manufacture
JPH1192171A (en) * 1997-09-12 1999-04-06 Okuno Chem Ind Co Ltd Glass paste composition for formation of partition of plasma display panel
JP2000026558A (en) * 1998-07-07 2000-01-25 Mitsubishi Rayon Co Ltd Hardenable resin composition, and execution of waterproof agent and resin concrete using the same
JP2000319476A (en) * 1999-05-07 2000-11-21 Toray Ind Inc Photosensitive paste and production of member for plasma display
JP2002214781A (en) * 2001-11-21 2002-07-31 Nippon Synthetic Chem Ind Co Ltd:The Photosensitive resin composition
JP2002326839A (en) * 2001-02-28 2002-11-12 Nippon Electric Glass Co Ltd Material for forming plasma display panel barrier rib and glass compound
JP2003054992A (en) * 2001-08-09 2003-02-26 Nippon Electric Glass Co Ltd Paste for forming partition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10241580A (en) * 1997-02-27 1998-09-11 Toppan Printing Co Ltd Plasma display and its manufacture
JPH1192171A (en) * 1997-09-12 1999-04-06 Okuno Chem Ind Co Ltd Glass paste composition for formation of partition of plasma display panel
JP2000026558A (en) * 1998-07-07 2000-01-25 Mitsubishi Rayon Co Ltd Hardenable resin composition, and execution of waterproof agent and resin concrete using the same
JP2000319476A (en) * 1999-05-07 2000-11-21 Toray Ind Inc Photosensitive paste and production of member for plasma display
JP2002326839A (en) * 2001-02-28 2002-11-12 Nippon Electric Glass Co Ltd Material for forming plasma display panel barrier rib and glass compound
JP2003054992A (en) * 2001-08-09 2003-02-26 Nippon Electric Glass Co Ltd Paste for forming partition
JP2002214781A (en) * 2001-11-21 2002-07-31 Nippon Synthetic Chem Ind Co Ltd:The Photosensitive resin composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011213526A (en) * 2010-03-31 2011-10-27 Nihon Yamamura Glass Co Ltd Glass composition

Also Published As

Publication number Publication date
JPWO2005086199A1 (en) 2008-01-24
TW200531951A (en) 2005-10-01

Similar Documents

Publication Publication Date Title
KR20060048253A (en) Laminated sheet, method for manufacturing of rear substrate for plasma display panel, rear substrate for plasma display panel and plasma display panel
JP2004115783A (en) Paste for use in partition, and method for manufacturing plasma display panel
JP2007126350A (en) Barrier rib forming material for plasma display panel and glass composition for barrier rib forming material
WO2005086199A1 (en) Paste for diaphragm and process for producing plasma display panel
JP2008150272A (en) Partition wall-forming material for plasma display panel and glass composition for partition wall-forming material
JP2006032141A (en) Manufacturing method of paste for barrier rib and plasma display panel
JP2008156192A (en) Glass paste for dielectric
JP2000053443A (en) Lead-free glass composition and composition for forming plasma display panel partition
JP2006111658A (en) Paste for partition wall and method for producing glass substrate with partition wall
JP2004277212A (en) Glass composition for forming partition wall of plasma display panel
JPWO2008084656A1 (en) Glass paste
JP2003054992A (en) Paste for forming partition
WO2004023511A1 (en) Pastes for forming barrier ribs and process for production of plasma display panels
JP2005035850A (en) Paste for barrier, method for producing base plate having barrier, and plasma display panel
JP2010159198A (en) Dielectric material for plasma display panel
JP3722185B2 (en) Bulkhead forming material for plasma display panel
JP2009144078A (en) Sheet for forming dielectric layer, sheet for forming dielectric layer/glass rib, method of manufacturing plasma display panel, and plasma display panel
JP4958078B2 (en) A material for a plasma display panel, a method for producing a rear glass substrate for a plasma display panel, and a rear glass substrate for a plasma display panel produced by the method.
JP2009057272A (en) Glass paste for forming partitioning wall
JP2005216767A (en) Resin composition containing inorganic powder for plasma display panel, transfer film and method of manufacturing plasma display panel
JPH1125867A (en) Base plate for plasma display
JP2008201593A (en) Glass ceramic composition for plasma display panel backside dielectric
JP2007066692A (en) Member for display and display using the same
JP2005008514A (en) Inorganic material membrane, inorganic material membrane structure, its forming process, and transfer film
JP2006257230A (en) Glass powder-containing resin composition, transfer film and method for producing plasma display panel by using the same film

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2006510698

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase