JP2007294435A - Glass powder-containing paste composite for plasma display, and transfer film using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To produce a paste having excellent dispersion stability of glass powder with good productivity and good yield at low cost, and also produce a glass powder-containing paste composite in which resin is never left in sintering of glass powder, and a transfer film using it. <P>SOLUTION: The glass powder-containing paste composite contains an acrylic resin containing urea group and/or urethane group, glass powder, and a solvent. The transfer film includes a transfer layer formed by applying the glass powder-containing paste composite on a support film. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a glass powder-containing paste composition for plasma display and a transfer film using the same. In particular, the present invention relates to a dielectric paste and a dielectric transfer film that can be suitably used for forming a dielectric film on a front plate or a back plate.

  In recent years, a plasma display has attracted attention as a flat fluorescent display. FIG. 1 is an example of a schematic diagram showing a cross-sectional shape of an AC type plasma display panel. In the figure, reference numerals 1 and 8 denote glass substrates facing each other (usually, 1 is a front plate, 8 is called a back plate), 11 is a partition wall, and cells are partitioned by the front plate 1, the glass substrate 8 and the partition wall 11. Is done. 2 is a transparent electrode fixed to the front plate 1, 7 is a bus electrode formed on the transparent electrode for the purpose of lowering the resistance of the transparent electrode, and a black conductive layer film 3 which is black and main for low reflection It consists of an electrode 4. Reference numeral 5 denotes a dielectric film formed on the surface of the front plate 1 so as to cover the transparent electrode 2 and the bus electrode 7. Reference numeral 6 denotes a protective film made of, for example, magnesium oxide. Reference numeral 9 is an address electrode fixed to the back plate 8, 10 is a dielectric film formed on the surface of the glass substrate 8 so as to cover the address electrode 9, and 12 is a fluorescent material held in the cell.

As a method for forming the transparent electrode and the bus electrode, first, a transparent electrode having a predetermined pattern made of a film mainly composed of ITO or SnO ₂ is formed on a glass substrate by a CVD method, a sputtering method, or a vacuum evaporation method. In general, a bus electrode is formed on the transparent electrode to form a laminated structure. The bus electrode can be provided by laminating a metal such as chromium or copper by sputtering or vacuum deposition. In addition to this, studies are being made to form by a screen printing method using a low-cost thick film paste, a coating method, a dry film method, or the like.

  The dielectric film is formed of a glass sintered body, and the thickness thereof is, for example, 20 to 50 μm. As a method for forming the dielectric film, a paste-like composition (glass powder-containing paste composition) containing a low-melting-point glass powder, other inorganic powders, a resin and a solvent is prepared, and this glass powder-containing paste The mainstream method is to form a dielectric film by applying the composition to the surface of the front plate 1 and / or the back plate 8 by screen printing, drying and baking.

  However, this method has a problem that the variation in film thickness is large, the mesh mark remains, and the surface smoothness is inferior. Therefore, for example, a glass powder-containing paste composition is applied onto a support film substrate, the coating film is dried to form a transfer layer, transferred to the surface of the glass substrate on which the electrodes are fixed, and the transfer layer is baked. Thus, a transfer film method for forming a dielectric film on the surface of the glass substrate has been proposed (see Patent Document 1). In particular, the transfer film method can dramatically improve the manufacturing efficiency of each film forming process of the plasma display panel by a simple method including a film transferring process.

In addition, in order to improve the dispersibility of the low-melting glass, it has been proposed to use a resin having a hydrophilic functional group such as a hydroxyl group (see Patent Document 2).
JP-A-9-102273 Japanese Patent Laid-Open No. 10-324541

  However, a resin having a functional group as in Patent Document 2 is excellent in wettability (affinity) to glass, and the resin strongly adsorbs to the glass surface. In other words, the dielectric film becomes black and the transmittance decreases. In particular, when used in a dielectric transfer film method, the thermal decomposability is further deteriorated because it is necessary to increase the proportion of the resin as compared with conventional coating and printing methods. Furthermore, the baking time has been shortened in order to improve productivity, and it is necessary to further shorten the time for thermally decomposing the resin, and the reduction in transmittance is a further problem.

  The present invention has been made to solve the above problems. An object of the present invention is to provide a glass powder-containing paste composition for plasma display and a transfer film using the same, such that no resin remains during glass powder sintering. In particular, when glass for plasma display dielectric film production is used as the glass powder, no resin remains at the time of sintering, and the glass powder-containing paste for plasma display does not reduce the optical properties of the dielectric film. The object is to provide a composition and a transfer film using the composition.

  In order to solve the above problems, the glass powder-containing paste composition for plasma display of the present invention comprises the following composition. That is, the glass powder-containing paste composition for plasma display of the present invention is a glass powder-containing paste composition for plasma display containing an acrylic resin containing urea groups and / or urethane groups, glass powder, and a solvent. is there.

  The transfer film of the present invention is a transfer film in which a transfer layer is formed by coating the glass powder-containing paste composition for plasma display on a support film.

  The glass powder-containing paste composition for plasma display of the present invention (hereinafter simply referred to as a glass powder-containing paste composition) is excellent in the dispersibility of the glass powder, so that the dispersion time can be shortened. Paste can be produced efficiently in a short time. Moreover, since it is excellent in the dispersion stability of glass powder, it is excellent also in the long-term storage property of a paste, and can guarantee high quality over a long period of time. Furthermore, since the glass powder-containing paste composition of the present invention prevents aggregation of the glass powder, it is possible to produce a plasma display with few defects of the coating film and excellent quality. The transfer film in which the glass powder-containing paste composition of the present invention is coated on a support film to form a transfer layer is also excellent in quality with few defects because it prevents aggregation of the glass powder.

  In the glass powder-containing paste composition of the present invention, since an acrylic resin containing a urea group and / or a urethane group is excellent in thermal decomposability, the glass powder-containing paste composition is applied, dried, and then applied. Since the film is thermally decomposed in a relatively short time in the step of baking the film, a highly transparent dielectric film can be stably formed without a decrease in transmittance due to coloring due to defective baking. In particular, since the tact time is shortened to improve productivity, a high-quality dielectric film can be produced even in the case of production with a short firing time. As a result, advantages such as an improvement in the brightness of the panel, a reduction in power consumption, and an improvement in product yield can be obtained. The same applies to a transfer film in which this glass powder-containing paste composition is coated on a support film to form a transfer layer. Conventional transfer films add a lot of organic matter such as increasing the amount of resin and adding plasticizers in order to give the transfer layer tackiness and flexibility. However, since the transfer sheet of the present invention has good thermal decomposability, there is no firing failure and the productivity of plasma display can be improved. Furthermore, according to this transfer film, a thick dielectric film or the like can be formed while maintaining the uniformity and smoothness of the film thickness. Therefore, the transfer film is a dielectric film required for a large panel. Can also be formed efficiently. As a result, display defects such as luminance unevenness do not occur in the plasma display manufactured by this transfer film.

  Hereinafter, the glass powder-containing paste composition of the present invention will be described in detail. The glass powder-containing paste composition of the present invention is characterized by containing an acrylic resin containing a urea group, a glass powder, and a solvent.

<Acrylic resin>
The acrylic resin containing urea groups and / or urethane groups of the glass powder-containing paste composition of the present invention is capable of binding glass powder with appropriate tackiness, and firing the coating film. It is preferably selected from (co) polymers that are completely decomposed and removed by temperature (usually 400 ° C. to 600 ° C.). Specifically, in the acrylic monomer represented by the following structural formula 32, the monovalent organic group represented by R ₂ contains a urea group (—NCON—) and / or a urethane group (—NCO—). (A) a polymer of an acrylic monomer containing a urea group and / or a urethane group, (B) an acrylic monomer containing no urea group and a urethane group, and an acrylic containing a urea group and / or a urethane group A copolymer of monomers, a mixture of (C) a polymer of acrylic monomers containing urea groups and / or urethane groups and a polymer of acrylic monomers not containing urea groups and urethane groups, and these A mixture is included.

(Wherein R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents a monovalent organic group having a urea group and / or a urethane group).

The urea group can be synthesized, for example, by reacting an isocyanate group with an amino group. R ₂ may contain a polar group such as an alkyl group, an alkyloxy group, an alkylphenoxy group, an amide group, a sulfonamide group, an amino group, and a carbonyl group in addition to the urea group. Specific examples of the acrylic resin containing urea groups in the glass powder-containing paste of the present invention are shown below.

First, in the case where the acrylic resin containing a urea group is a (meth) acrylic acid ester polymer, an example of R _{2 in} Structural Formula 2 is shown in Structural Formula 3 below.

Such a (meth) acrylic acid ester polymer can be synthesized, for example, by reacting a (meth) acrylic acid monomer with a urea group-containing compound having a hydroxyl group and then polymerizing it.

Secondly, in the case where the acrylic resin containing a urea group is a (meth) acrylamide polymer, one example of R _{2 in} Structural Formula 2 is shown in Structural Formula 4 below.

Such a (meth) acrylamide polymer can be synthesized by, for example, reacting a (meth) acrylic acid monomer with a urea group-containing compound having an amine group, and then polymerizing it.

Thirdly, in the case where the acrylic resin containing a urea group is a polymer of a monomer in which a urea group is directly bonded to the acrylic group, an example of R _{2 in} Structural Formula 2 is shown in Structural Formula 5 below. Show.

  The (meth) acryl polymerization in which a urea group is directly bonded to such an acrylic group can be synthesized by, for example, reacting an isocyanate group-containing compound with a (meth) acrylamide monomer and then polymerizing it. .

  Moreover, as a urea group, what has ethylene urea group can be used preferably. What has an ethylene urea group shows that a urea group is the following structural formula 71.

Specific examples of the ethylene urea group-containing acrylic monomer represented by Structural Formula 1 include 2-methacryloyloxyethyl ethylene urea, 2-methacrylamidoethyl ethylene urea, and the like. This 2 example the chemical structure R ₂ in the structural formula 2, shown in structural formula 6.

  The urea group-containing acrylic monomer may be a single monomer, but a copolymer composed of acrylic monomers having two or more types of urea groups, a mixture of acrylic resins having two or more types of urea groups, and these It may be a mixture of

  Next, the urethane group can be synthesized, for example, by reacting an isocyanate group with a hydroxyl group. Specific examples of the acrylic resin containing a urethane group in the glass powder-containing paste of the present invention are shown below.

First, in the case where the acrylic resin containing a urethane group is a (meth) acrylic acid ester polymer, one example of R _{2 in} Structural Formula 32 is shown in Structural Formula 7 below.

  Such a (meth) acrylic acid ester polymer is polymerized after, for example, reacting an organic compound (alcohol) having a hydroxyl group with a (meth) acrylic acid ester monomer having an isocyanate group in the side chain. Can be synthesized. Moreover, it can also synthesize | combine by making it superpose | polymerize, after making the urethane group containing compound which has a hydroxyl group react with a (meth) acrylic acid monomer.

Secondly, in the case where the acrylic resin containing a urethane group is a (meth) acrylamide polymer, one example of R _{2 in} Structural Formula 32 is shown in Structural Formula 8 below.

  Such a (meth) acrylamide polymer can be synthesized by, for example, reacting a (meth) acrylic acid monomer with a urethane group-containing compound having an amine group, and then polymerizing.

  The urethane group-containing acrylic monomer may be used alone, but a copolymer comprising acrylic monomers having two or more types of urethane groups, a mixture of acrylic resins having two or more types of urethane groups, and these It may be a mixture of

  Further, the amount of the urea group and / or urethane group-containing acrylic monomer is preferably 0.1 to 30% by weight, more preferably 0. It is 2 to 20% by weight, particularly preferably 0.5 to 10% by weight. When the urea group and / or urethane group-containing acrylic monomer is 0.1% by weight or more, the dispersion of glass is good and the thermal decomposability of the acrylic resin is excellent, which is preferable. In addition, if it is 30% by weight or less, it is possible to stably produce an acrylic resin having an appropriate viscosity without causing gelation in the coating, and it is possible to reduce the number of expensive acrylic monomers containing urea groups or urethane groups. Therefore, the cost can be reduced, which is preferable. That is, a copolymer of an acrylic monomer containing a urea group and an acrylic monomer not containing a urea group is particularly preferable.

  Examples of acrylic monomers not containing urea groups and urethane groups include acrylic esters, methacrylic esters, alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, phenoxyalkyl (meth) acrylates, There are alkoxyalkyl (meth) acrylates, polyalkylene glycol (meth) acrylates, cycloalkyl (meth) acrylates, benzyl (meth) acrylates, tetrahydrofurfuryl (meth) acrylates, specifically ethyl (meth) acrylate, n -Propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate , Cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyl (meth) acrylate , Phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) Acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monophenyl (meth) acrylate, triethylene glycol monoethyl acetate (Meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, dicyclopentanyl (meta ) Acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, etc. Can do.

  Among these, particularly preferable (meth) acrylate compounds include methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and isodecyl (meth) acrylate. .

  In addition to this, acrylic monomers not containing urea groups and urethane groups include acrylic amides and methacrylic amides, specifically (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-cyclohexyl ( (Meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) ) Acrylamide, N, N-dimethyl (meth) acrylamide, N, - can be exemplified diethyl (meth) acrylamide, N- methyl -N-n-propyl (meth) acrylamide, N- methyl -N- isopropyl (meth) acrylamide, diacetone acrylamide and the like.

  Further, the other monomer that can be used for copolymerization with the urea group- and urethane group-containing acrylic monomer is not particularly limited as long as it is a compound copolymerizable with the acrylic monomer. For example, (meth) acrylic Unsaturated carboxylic acids such as acid, vinyl benzoic acid, vinyl maleic acid and vinyl phthalic acid; and vinyl group-containing radical polymerizable compounds such as vinyl benzyl methyl ether, vinyl glycidyl ether, styrene, α-methyl styrene, butadiene and isoprene Can do. The ratio of the acrylic resin component in the total resin is preferably 70% by weight or more, particularly preferably 90% by weight or more, and further preferably 100% by weight. By making it 70% by weight or more, the dispersibility of the glass powder is good and the thermal decomposability of the acrylic resin is excellent, which is preferable.

  As the molecular weight of the acrylic resin constituting the glass powder-containing paste composition of the present invention, the polystyrene-reduced weight average molecular weight (Mw) by gel permeation chromatography (GPC) is 2,000 to 400,000. More preferably, it is 10,000-300,000, More preferably, it is 50,000-250,000. By making these ranges, the viscosity of the glass powder-containing paste can be set to an appropriate range at the time of coating, and the mechanical strength of the transfer layer formed on the support film is improved. Can do.

  The acrylic resin preferably has adhesiveness, and preferably has a low glass transition temperature. The glass transition temperature is preferably 60 ° C. or lower, more preferably 20 ° C. or lower, and still more preferably 0 ° C. or lower. By making the glass transition temperature below these values, tackiness can be imparted.

  Moreover, it is also preferable to add a plasticizer, a tackifier, etc. to the glass particle containing paste composition of this invention. By adding these, tackiness can be imparted.

  Moreover, it is preferable that the thermal decomposition of the acrylic resin containing a urea group and / or a urethane group has a completion temperature of 400 ° C. or lower. More preferably, it is 380 degrees C or less, More preferably, it is 360 degrees C or less. If the temperature is lower than these thermal decomposition temperatures, the thermal decomposition of the resin proceeds quickly and does not remain in the fired film, so that there is no problem that the fired film is blackened or the transmittance is reduced. ,preferable. The thermal decomposition temperature is a temperature at which the thermal decomposition of the resin is completed by heating in air, and can be measured by measuring a weight change with a thermogravimetric measuring apparatus (TGA method). By including a predetermined amount of a monomer containing a urea group in the acrylic resin, the thermal decomposition can be easily completed at 400 ° C. or lower.

  As a content rate of an acrylic resin, it is preferable that it is 5-40 weight part with respect to 100 weight part of glass powder, More preferably, it is 10-30 weight part. By setting the amount to 5 parts by weight or more, it is preferable because the glass powder can be reliably bound and held and sufficient coating film strength can be obtained. Further, the content of 40 parts by weight or less is preferable because the firing process can be shortened and problems such as contamination of unfired components in the fired film do not occur.

<Glass powder>
In the glass powder-containing paste composition of the present invention, specific examples of suitable composition of the glass powder include (i) PbO—B ₂ O ₃ —SiO ₂ —CaO system, (ii) ZnO—B ₂ O ₃ -SiO _{2 system, (iii) PbO-B 2} O 3 -SiO 2 -Al 2 O 3 _{system, (iv) PbO-ZnO-} B 2 O 3 -SiO 2 _{system, (v) PbO-B 2} O 3 - Examples thereof include low melting glass such as SiO ₂ , (vi) Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ , and (vii) Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ . In addition, lithium oxide, silicon oxide, boron oxide, barium oxide, aluminum oxide, titanium oxide, calcium carbonate, RuO ₂ , Co—Cr—Fe, Co—Mn—Fe, Co—Mn—Fe—Al, Co— Inorganic powders such as Ni-Cr-Fe, Co-Ni-Mn-Cr-Fe, Co-Ni-Al-Cr-Fe, Co-Mn-Al-Cr-Fe-Si, Ag, Cr, Cu-Cr You may add metal powders, such as. The average particle size of the glass powder used in the present invention is preferably 0.1 to 5 μm. More preferably, it is 0.5-4 micrometers, More preferably, it is 1-3 micrometers. By setting the average particle size within this range, the bubble content in the fired film can be reduced, which is preferable.

  The softening point of the glass powder is preferably 400 ° C. or higher and lower than 600 ° C., more preferably 450 ° C. or higher and lower than 600 ° C. By setting the softening point within this range, it is possible to reduce thermal damage to the substrate during manufacturing of the plasma display, which is preferable. In order to adjust the softening point of the glass powder, generally, a method is used in which the composition ratio of each oxide component is varied at the time of weighing raw materials for glass production, and then the glass powder is vitrified. The “softening point” can be measured by a differential thermal analyzer.

<Solvent>
As a solvent of the glass powder-containing paste composition of the present invention, the affinity with the glass powder and the solubility of the binder resin are good, and an appropriate viscosity can be imparted to the glass powder-containing paste composition. At the same time, it is preferably one that can be easily removed by evaporation. Specific examples of such solvents include ketones such as methyl ethyl ketone, diethyl ketone, methyl butyl ketone, dipropyl ketone, and cyclohexanone; alcohols such as n-pentanol, 4-methyl-2-pentanol, cyclohexanol, and diacetone alcohol. Ether ether alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; saturated fats such as ethyl acetate, n-butyl acetate, and amyl acetate Group monocarboxylic acid alkyl esters; lactic acid esters such as ethyl lactate and lactic acid-n-butyl; methyl cellosolve acetate, ethyl cellosolve acetate, propylene Examples thereof include ether esters such as ethylene glycol monomethyl ether acetate and ethyl-3-ethoxypropionate, and aromatic hydrocarbons such as toluene and xylene. Among these, methyl butyl ketone, cyclohexanone, diester Acetone alcohol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, acetic acid-n-butyl, ethyl acetate ethyl lactate, ethyl-3-ethoxypropionate, toluene and the like are preferable.

  The content ratio of the solvent in the glass powder-containing paste composition of the present invention can be appropriately adjusted from the viewpoint of maintaining the viscosity of the composition in a suitable range. For example, the solvent is preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the glass powder and the resin combined.

<Glass powder-containing paste>
In addition to the above essential components, the glass powder-containing paste composition of the present invention includes various additives such as a dispersant, a tackifier, a plasticizer, a surface tension modifier, a stabilizer, an antifoaming agent, and a dispersant. An agent may be contained as an optional component.

  The glass powder-containing paste composition is prepared by kneading the glass powder, the binder resin and the solvent and optional components using a kneading / dispersing machine such as a roll kneader, a mixer, a homomixer, or a sand mill. Can do.

  The viscosity of the glass powder-containing paste composition of the present invention is preferably 0.1 to 100 Pa · s, more preferably 1 to 10 Pa · s. By setting the viscosity within these ranges, it is possible to improve the coatability and to prevent the glass powder from settling. In order to adjust the coating liquid viscosity within these ranges, the amount of solvent and the molecular weight of the acrylic resin are appropriately adjusted.

As the rheological characteristics of the paste containing glass powder, the absolute value of the yield value according to Casson's flow equation is preferably 1 Pa or less, more preferably 0.5 Pa or less, and still more preferably 0.1 Pa or less. When the pressure is 1 Pa or less, the fluidity of the glass powder-containing paste is improved, the dispersion stability of the glass powder powder is good, the glass powder is not aggregated, no aggregates are formed, and the life of the paste is increased. It is long and preferable. When S = shear stress (Pa), D = shear rate (s ⁻¹ ), τ ₀ = yield value (Pa), μ ₀ = Casson viscosity (Pa · s), the flow equation is expressed by the following equation: . Yield value ^is calculated by the square of the intercept of the ^{S 1/2} axis in the graph of ^{S 1/2} for ^{D 1/2.}
(S) ^1/2 = (τ ₀ ) ^1/2 + (μ ₀ ) ^1/2 × (D) ^1/2 .

  The glass powder-containing paste composition thus obtained is directly applied to the glass substrate for plasma display by a coating method such as screen printing, slit die coater, curtain flow coater, blade coater, wire bar coater, roll coater. In some cases, it is applied, and after the transfer film is manufactured, it is transferred onto a glass substrate for plasma display using a laminator.

<Transfer film>
Next, a glass powder-containing paste composition for forming a dielectric film for plasma display and a transfer film in which a transfer layer is formed by applying a glass powder-containing paste composition to a support film will be described as an example.

  An example of a preferred glass powder-containing paste composition is a glass powder having a softening point of 450 to 580 ° C. (lead oxide 30 to 80% by weight, silicon oxide 1 to 20% by weight, boron oxide 10 to 50% by weight and others. 100 parts by weight of component (0-30% by weight), acrylic resin (polybutyl methacrylate, 2-ethylhexyl methacrylate and a copolymer of urea group and / or urethane group-containing methacrylate, etc.), and plasticizer ( A composition containing 1 to 30 parts by weight of dibutyl phthalate and the like and 10 to 50 parts by weight of a solvent (toluene, butyl acetate, propylene glycol monomethyl ether and the like) can be given. If necessary, inorganic powders such as aluminum oxide, titanium oxide, lithium oxide, silicon oxide, boron oxide, and barium oxide may be added.

  The transfer film includes a support film substrate and a transfer layer (dielectric film) laminated on the support film substrate. The film substrate for the transfer film is preferably a resin film having heat resistance and solvent resistance and flexibility. Examples of the resin that forms the film substrate include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, polyfluoroethylene, and other fluorine-containing resins, nylon, and cellulose. As thickness of a film substrate, 10-100 micrometers is preferable, for example. By setting it within this range, the strength and softness as the support substrate can be exhibited with a good balance. Moreover, it is preferable that the surface of the film substrate on which the dielectric film is applied is subjected to a release treatment. Thereby, in the transfer process to the glass substrate, the peeling operation of the film substrate can be easily performed, and furthermore, the adhesion between the film substrate and the dielectric film can be changed by changing the type of the release agent. it can.

  The dielectric film constituting the transfer film can be formed by applying the glass powder-containing paste composition of the present invention on the film substrate, drying the coating film, and removing the solvent.

  As a method of applying the glass powder-containing paste composition on the film substrate, it is preferable that a thick film coating (for example, 20 μm or more) excellent in film thickness uniformity can be efficiently formed. Specifically, a coating method such as a slit die coater, a curtain flow coater, a blade coater, a wire bar coater, or a roll coater is preferable. Among these, a slit die coater and a curtain flow coater are particularly preferable because of a change in concentration due to evaporation of the solvent over time and little adhesion of dust.

In order to form a film on a film substrate, a glass powder-containing paste composition is applied and then dried in an oven. Thereafter, it is usually wound up while laminating a protective film on the membrane. Examples of such a protective film include a polyethylene terephthalate film, a polyethylene film, a polyvinyl alcohol film, and the like, and those having a release treatment applied to the surface of these films. The roll pressure is preferably 1 to 10 kg / cm ² , and the roller surface temperature is preferably 10 to 130 ° C, more preferably 20 to 80 ° C, and further preferably 25 to 60 ° C. The laminating speed is preferably 0.1 to 10 m / min.

<Preparation of front plate / back plate for plasma display>
Using the transfer film produced as described above, the film material on the transfer film is transferred to the surface of the glass substrate serving as the front plate and / or the back plate to which the electrodes are fixed. An example of the transfer process is as follows. The protective film of the transfer film is peeled off before transfer. Next, a transfer film is superimposed on the surface of the glass substrate (electrode fixing surface) so that the film surface comes into contact with the glass substrate, and this transfer film is thermocompression bonded with a heating roller or the like, and then the support film substrate is peeled off from the transfer film. Remove. As a result, the film is transferred and adhered to the surface of the glass substrate. As the transfer conditions, for example, the surface temperature of the heating roller is preferably 10 to 130 ° C., more preferably 20 to 80 ° C., further preferably 25 to 60 ° C., and the roll pressure by the heating roller is 1 to 10 kg / cm ² , The moving speed of the heating roller is 0.1 to 10.0 m / min. Further, the glass substrate may be preheated, and the preheat temperature can be set to 50 to 100 ° C., for example.

  Thereafter, the film transferred to the surface of the glass substrate is baked. Specifically, by placing the glass substrate on which the transfer film is formed in a high temperature atmosphere, organic substances (acrylic resin, residual solvent, various additives, etc.) contained in the transfer film are decomposed. The glass powder that is removed is melted and sintered. As a result, a dielectric film made of a glass sintered body is formed on the glass substrate. Here, the firing temperature is, for example, 500 to 600 ° C., although it varies depending on the constituent materials in the transfer film.

In addition to the dielectric film, when used as a partition film, it can be manufactured using a known partition wall material. For example, it can be manufactured by applying a paste containing glass powder such as lithium oxide, silicon oxide, boron oxide, barium oxide, aluminum oxide, or titanium oxide, an acrylic resin, an organic solvent, or the like. Moreover, when it uses as a black conductive layer film | membrane, it can produce using a well-known black conductive layer material. For _{example, RuO 2, Co-Cr-} Fe, Co-Mn-Fe, Co-Mn-Fe-Al, Co-Ni-Cr-Fe, Co-Ni-Mn-Cr-Fe, Co-Ni-Al-Cr It can be produced by applying a paste containing metal powder such as -Fe, Co-Mn-Al-Cr-Fe-Si, Cr, Cu-Cr, and an acrylic resin having a urea group, glass powder, an organic solvent, and the like. Also when used as the main electrode film, it can be produced using a known electrode material. For example, it can be produced by applying a paste containing a metal powder such as silver, Cr, or Cu—Cr and an acrylic resin having a urea group, glass particles, or an organic solvent. Besides this, it can also be used as a sealing agent for plasma displays.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

-Thermal decomposition completion temperature of acrylic resin The thermal decomposition completion temperature of acrylic resin was determined by drying the paste composition in an oven at 60 ° C for 10 minutes, removing the solvent, and then measuring the thermogravimetry (type TGA-50, Shimadzu). The product is heated from room temperature to 600 ° C. while heating at a heating rate of 10 ° C./min under an air stream of 20 ml / min. At this time, the acrylic resin decomposes from around 300 ° C., and the weight gradually decreases. However, thermal decomposition is completed at a temperature that changes by 0.1% of the weight when heated to 600 ° C. Let it be temperature.

-Softening point of glass powder The softening point of glass powder is measured according to the "glass softening point test method" of JIS R3103-1. In addition to this, as shown in Japanese Patent Laid-Open No. 2003-95697, a method of measuring with a thermomechanical analyzer (TMA), as shown in Japanese Patent Laid-Open No. 2002-308645, differential thermal analysis. There is a method of measuring by (DTA), which may be used as appropriate.

-Yield value of paste composition Using an E-type viscometer (manufactured by Toki Sangyo), the shear rate was changed at 25 ° C to measure the viscosity, and the yield value was obtained from the flow equation.

-Storage stability of paste composition The paste composition is stored at 5 ± 5 ° C for 1 month, and the sedimentation of the glass powder is confirmed. When the aggregated glass sediment did not occur, it was judged as good, and when it occurred, it was judged as poor.

-Light transmittance The light transmittance with visible light having a wavelength of 550 nm was measured using a spectrophotometer. The light transmittance was measured by setting the transmittance of the glass substrate to 100% and then measuring the transmittance of the portion where the dielectric film was laminated on the glass substrate.

Example 1
<Preparation of Glass Powder-Containing Paste Composition A1>
As a glass powder, PbO—B ₂ O ₃ —SiO ₂ —BaO-based glass (softening) having a composition of 40% by weight of lead oxide, 30% by weight of boron oxide, 10% by weight of silicon oxide, and 20% by weight of barium oxide as a main component. A polymer of Methyl methacrylate / 2-ethylhexyl methacrylate / 2-methacryloyloxyethylethylene urea = 11/85/4 (wt%) as an acrylic resin having a urea group (Mw: 250, point 580 ° C.) 000) 20 parts by weight, 7 parts by weight of dibutyl phthalate and 35 parts by weight of toluene (solvent) were kneaded to prepare a glass powder-containing paste composition A1. As a result of measuring the viscosity and the yield value with an E-type viscometer, the viscosity was 2 Pa · s, the yield value was as very small as 0.02 Pa, and the dispersibility was good. The storage stability of the paste composition was tested, but the storage stability was good without aggregation of glass powder.

<Preparation of Glass Powder-Containing Paste Composition A2>
Further, as a glass powder, PbO—B ₂ O ₃ —SiO ₂ —ZnO-based glass having a composition of 70% by weight of lead oxide, 15% by weight of boron oxide, 8% by weight of silicon oxide, and 3% by weight of zinc oxide as glass powders. (Softening point 470 ° C.) 100 parts by weight and a polymer of methyl methacrylate / 2-ethylhexyl methacrylate / 2-methacryloyloxyethylethylene urea = 11/85/4 (wt%) as an acrylic resin having a urea group (Mw: 250,000) 15 parts by weight, 7 parts of dibutyl phthalate and 35 parts by weight of toluene (solvent) were kneaded to prepare a glass powder-containing paste composition A2. As a result of measuring the viscosity and the yield value with an E-type viscometer, the viscosity was 3 Pa · s, the yield value was as very small as 0.04 Pa, and the dispersibility was good. The storage stability of the paste composition was tested, but the storage stability was good without aggregation of glass powder.

<Preparation of transfer films A1 and A2>
First, the glass powder-containing paste composition A1 is applied onto a support film substrate (250 mm in width and 50 μm in thickness) made of a polyethylene terephthalate (PET) film that has been pre-released using a blade coater to form a coating film. did. The solvent was removed by drying the formed coating film at 110 ° C. for 5 minutes, thereby laminating a dielectric transfer film A1 having a thickness of 30 μm on the support film substrate. Thereafter, a release film (width 250 mm, thickness 38 μm) was wound as a protective film while laminating at room temperature at a roll pressure of 4 kg / cm ² . This is called a transfer film A1.

Similarly, a glass powder-containing paste composition A2 was applied onto a support film substrate, a dielectric transfer film A2 having a thickness of 30 μm was laminated on the support film substrate, and then wound up while laminating a protective film. . This is called transfer film A2.
As a result of TGA analysis of the dielectric transfer layers of the transfer films A1 and A2, the thermal decomposition temperature of the acrylic resin was both good at 370 ° C.

<Transfer Process of Dielectric Transfer Film A1>
An ITO transparent conductive film was formed in advance on a glass substrate for a 6-inch panel, and a silver paste was applied thereon by screen printing and baked to form a bus electrode having a thickness of 10 μm and a width of 100 μm. Next, the transfer film A1 is prepared, the cover film substrate is peeled off from the transfer film, the transfer film is overlaid on the substrate on which the bus electrodes are formed, so that the surface of the dielectric transfer film is brought into contact with the transfer film, and the transfer film is laminated on the laminator. And thermocompression bonded. Here, as pressure bonding conditions, the surface temperature of the heating roller was 60 ° C., the roll pressure was 4 kg / cm ² , and the moving speed of the heating roller was 1 m / min. After completion of the thermocompression treatment, the support film substrate was peeled off from the transfer film. As a result, the dielectric transfer film A1 was brought into close contact with the surface of the glass substrate.

<Baking Process of Dielectric Transfer Film A1>
The dielectric transfer film A1 transferred onto the glass substrate is heated from room temperature to 590 ° C. at a temperature rising rate of 10 ° C./min, and baked for 30 minutes in a temperature atmosphere of 590 ° C., whereby the surface of the glass substrate In addition, a dielectric film A1 made of a glass sintered body was formed.

<Transfer Process of Dielectric Transfer Film A2>
Next, the transfer film A2 is prepared, the cover film substrate is peeled off from the transfer film, the transfer film is overlaid on the dielectric film A1 so that the surface of the dielectric transfer film A2 comes into contact, and the transfer film is laminated to the laminator. And thermocompression bonded. Here, similarly, the surface temperature of the heating roller was 60 ° C., the roll pressure was 4 kg / cm ² , and the moving speed of the heating roller was 1 m / min. After completion of the thermocompression treatment, the support film substrate was peeled off from the transfer film. As a result, the dielectric transfer film A2 was brought into close contact with the surface of the glass substrate.

<Baking process of dielectric transfer film A2>
The dielectric transfer film A2 transferred onto the glass substrate is heated from room temperature to 570 ° C. at a temperature rising rate of 10 ° C./min, and baked for 30 minutes in a temperature atmosphere of 570 ° C. Then, a dielectric film A2 made of a glass sintered body was formed. When the thickness of the dielectric films A1 and A2 was measured by observing the cross section with a scanning electron microscope, it was in the range of 30 μm ± 1.0 μm, and the film thickness was excellent.

<Performance evaluation of dielectric film>
Thus, a panel material made of a glass substrate having a dielectric film was produced. When the cross section and the surface of the formed dielectric film were observed with a scanning electron microscope, no film defects such as pinholes and cracks were found in the dielectric films formed on all panel materials. Further, the low melting point glass did not soften and flow and eroded between the bus electrode and the transparent conductive film, and the bus electrode did not peel from the transparent conductive film. Also, in the visual appearance observation, the bus electrode was not colored. Furthermore, when the light transmittance (measurement wavelength 550 nm) of the formed dielectric film was measured with a spectrophotometer, it was found that the average value of the light transmittance was 88%, and it had good transparency. It was.

(Example 2)
<Preparation of Glass Powder-Containing Paste Composition B>
Further, as a glass powder, PbO—B ₂ O ₃ —SiO ₂ —ZnO-based glass having a composition of 70% by weight of lead oxide, 15% by weight of boron oxide, 8% by weight of silicon oxide, and 3% by weight of zinc oxide as glass powders. (Softening point 470 ° C.) 100 parts by weight and a polymer of n-butyl methacrylate / 2-ethylhexyl methacrylate / 2-methacryloyloxyethylethylene urea = 56/43/1 (% by weight) as an acrylic resin having a urea group Mw: 300,000) 15 parts by weight, 7 parts of dibutyl phthalate and 35 parts by weight of toluene (solvent) were kneaded to prepare a glass powder-containing paste composition B. As a result of measuring the viscosity and the yield value with an E-type viscometer, the viscosity was 3 Pa · s, the yield value was as very small as 0.06 Pa, and the dispersibility was good. The storage stability of the paste composition was tested, but the storage stability was good without aggregation of glass powder.

<Preparation of transfer film B>
In the same manner as in Example 1, the glass powder-containing paste composition B was coated on the support film substrate, the dielectric transfer film B having a thickness of 30 μm was laminated on the support film substrate, and then the protective film was laminated. I wound it up. This is referred to as transfer film B. As a result of TGA analysis of this dielectric transfer layer, the thermal decomposition temperature of the acrylic resin was as good as 380 ° C.

<Transfer Process of Dielectric Transfer Film A1>
In the same manner as in Example 1, a transfer film A1 was prepared, and the dielectric transfer film A1 was transferred onto a glass substrate for a 6-inch panel.

<Baking Process of Dielectric Transfer Film A1>
In the same manner as in Example 1, the dielectric transfer film A1 transferred onto the glass substrate was heated from room temperature to 590 ° C. at a heating rate of 10 ° C./min, and baked for 30 minutes in a temperature atmosphere of 590 ° C. As a result, a dielectric film A1 made of a glass sintered body was formed on the surface of the glass substrate.

<Transfer process of dielectric transfer film B>
Next, a transfer film B is prepared, and in the same manner as in Example 1, the transfer film is overlaid on the dielectric film A1 so that the surface of the dielectric transfer film B is in contact with the dielectric film A1, and the dielectric transfer film B is formed. Transcribed.

<Baking process of dielectric transfer film B>
In the same manner as in Example 1, the dielectric transfer film B transferred onto the glass substrate was heated from room temperature to 570 ° C. at a heating rate of 10 ° C./min, and baked for 30 minutes in a temperature atmosphere of 570 ° C. By processing, a dielectric film B made of a glass sintered body was formed on the surface of the glass substrate.
When the cross-section was observed with a scanning electron microscope and the film thickness of the dielectric films A1 and B was measured, the film thickness was in the range of 30 μm ± 1.0 μm, and the film thickness was excellent.

<Performance evaluation of dielectric film>
Thus, a panel material made of a glass substrate having a dielectric film was produced. When the cross section and the surface of the formed dielectric film were observed with a scanning electron microscope, no film defects such as pinholes and cracks were found in the dielectric films formed on all panel materials. Further, the low melting point glass did not soften and flow and eroded between the bus electrode and the transparent conductive film, and the bus electrode did not peel from the transparent conductive film. Also, in the visual appearance observation, the bus electrode was not colored. Furthermore, when the light transmittance (measurement wavelength 550 nm) of the formed dielectric film was measured with a spectrophotometer, it was found that the average value of the light transmittance was 88%, and it had good transparency. It was.

(Example 3)
In the same manner as in Example 1, glass powder-containing paste compositions A1 and A2 were prepared. The dispersibility and storage stability of the glass were good.

<Production process of dielectric coating film A1>
As in Example 1, an ITO transparent conductive film is formed in advance on a glass substrate for a 6-inch panel, and a silver paste is applied onto the glass substrate by screen printing and then fired to form a bus electrode having a thickness of 10 μm and a width of 100 μm. Formed. Next, the glass powder-containing paste composition A1 is applied to the substrate on which the bus electrode is formed with a single-wafer coater, and the formed coating film is dried at 110 ° C. for 5 minutes to remove the solvent. A dielectric coating film A1 having a thickness of 30 μm was formed on the surface of the glass substrate.

<Baking process of dielectric coating film A1>
The dielectric coating film A1 formed on the glass substrate is heated from room temperature to 590 ° C. at a temperature rising rate of 10 ° C./min, and is baked in a temperature atmosphere of 590 ° C. for 30 minutes, whereby the surface of the glass substrate In addition, a dielectric film A1 made of a glass sintered body was formed.

<Production process of dielectric coating film A2>
Further, the glass powder-containing paste composition A2 was applied on the substrate with a single-wafer coater, and the solvent was removed by drying the formed coating film at 110 ° C. for 5 minutes, whereby a dielectric having a thickness of 30 μm was obtained. The coating film A2 was formed on the surface of the glass substrate.

<Baking process of dielectric coating film A2>
The dielectric coating film A2 is heated from room temperature to 570 ° C. at a heating rate of 10 ° C./min, and is baked for 30 minutes in a temperature atmosphere of 570 ° C., so that the surface of the glass substrate A dielectric film A2 was formed.
When the cross-section was observed with a scanning electron microscope and the thickness of the dielectric films A1 and A2 was measured, the film thickness was in the range of 30 μm ± 1.5 μm, and the film thickness was excellent.

<Performance evaluation of dielectric film>
Thus, a panel material made of a glass substrate having a dielectric film was produced. When the cross section and the surface of the formed dielectric film were observed with a scanning electron microscope, no film defects such as pinholes and cracks were found in the dielectric films formed on all panel materials. Further, the low melting point glass did not soften and flow and eroded between the bus electrode and the transparent conductive film, and the bus electrode did not peel from the transparent conductive film. Also, in the visual appearance observation, the bus electrode was not colored. Furthermore, when the light transmittance (measurement wavelength 550 nm) of the formed dielectric film was measured with a spectrophotometer, it was found that the average value of the light transmittance was 88%, and it had good transparency. It was.

Example 4
<Preparation of glass powder-containing paste composition E>
As a glass powder, PbO—B ₂ O ₃ —SiO ₂ —ZnO-based glass (softening) whose main components are 70% by weight of lead oxide, 15% by weight of boron oxide, 8% by weight of silicon oxide, and 3% by weight of zinc oxide. A polymer of Methyl methacrylate / 2-ethylhexyl methacrylate / 2-methacrylamide ethylethylene urea = 9/58/30/3 (% by weight) as an acrylic resin having a urea group (Mw: 205) , 000) 15 parts by weight, 7 parts of dibutyl phthalate and 35 parts by weight of toluene (solvent) were kneaded to prepare a glass powder-containing paste composition A2. As a result of measuring the viscosity and the yield value with an E-type viscometer, the viscosity was 2 Pa · s, the yield value was as very small as 0.04 Pa, and the dispersibility was good. The storage stability of the paste composition was tested, but the storage stability was good without aggregation of glass powder.

<Preparation of transfer film E>
In the same manner as in Example 1, the glass powder-containing paste composition E was coated on the support film substrate, the dielectric transfer film E having a thickness of 30 μm was laminated on the support film substrate, and then the protective film was laminated. I wound it up. This is called a transfer film E. As a result of TGA analysis of this dielectric transfer layer, the thermal decomposition temperature of the acrylic resin was as good as 380 ° C.

<Transfer Process of Dielectric Transfer Film A1>
In the same manner as in Example 1, a transfer film A1 was prepared, and the dielectric transfer film A1 was transferred onto a glass substrate for a 6-inch panel.

<Baking Process of Dielectric Transfer Film A1>
In the same manner as in Example 1, the dielectric transfer film A1 transferred onto the glass substrate was heated from room temperature to 590 ° C. at a heating rate of 10 ° C./min, and baked for 30 minutes in a temperature atmosphere of 590 ° C. As a result, a dielectric film A1 made of a glass sintered body was formed on the surface of the glass substrate.

<Transfer process of dielectric transfer film E>
Next, a transfer film E is prepared, and in the same manner as in Example 1, the transfer film is overlaid on the dielectric film A1 so that the surface of the dielectric transfer film E is in contact with the dielectric film A1, and the dielectric transfer film E is formed. Transcribed.

<Baking process of dielectric transfer film E>
In the same manner as in Example 1, the dielectric transfer film E transferred onto the glass substrate was heated from room temperature to 570 ° C. at a heating rate of 10 ° C./min, and baked for 30 minutes in a temperature atmosphere of 570 ° C. By processing, a dielectric film E made of a glass sintered body was formed on the surface of the glass substrate.
When the laminated film thickness of the dielectric films A1 and E was measured by observing the cross section with a scanning electron microscope, it was in the range of 30 μm ± 1.0 μm, and the film thickness was excellent.

<Performance evaluation of dielectric film>
Thus, a panel material made of a glass substrate having a dielectric film was produced. When the cross section and the surface of the formed dielectric film were observed with a scanning electron microscope, no film defects such as pinholes and cracks were found in the dielectric films formed on all panel materials. Further, the low melting point glass did not soften and flow and eroded between the bus electrode and the transparent conductive film, and the bus electrode did not peel from the transparent conductive film. Also, in the visual appearance observation, the bus electrode was not colored. Furthermore, when the light transmittance (measurement wavelength 550 nm) of the formed dielectric film was measured with a spectrophotometer, it was found that the average value of the light transmittance was 87%, and the film had good transparency. It was.

(Example 5)
<Preparation of Glass Powder-Containing Paste Composition F1>
As a glass powder, PbO—B ₂ O ₃ —SiO ₂ —BaO-based glass (softening) having a composition of 40% by weight of lead oxide, 30% by weight of boron oxide, 10% by weight of silicon oxide, and 20% by weight of barium oxide as a main component. A polymer of Methyl methacrylate / 2-ethylhexyl methacrylate / 2-methacryloyloxyethylbutoxyurethane = 11/85/4 (wt%) as an acrylic resin having a urethane group (Mw: 285). 000) 20 parts by weight, 7 parts by weight of dibutyl phthalate and 35 parts by weight of toluene (solvent) were kneaded to prepare a glass powder-containing paste composition F1. As a result of measuring the viscosity and yield value with an E-type viscometer, the viscosity was 4 Pa · s, the yield value was relatively small at 0.1 Pa, and the dispersibility was good. The storage stability of the paste composition was tested, but the storage stability was good without aggregation of glass powder.

<Preparation of Glass Powder-Containing Paste Composition F2>
Further, as a glass powder, PbO—B ₂ O ₃ —SiO ₂ —ZnO-based glass having a composition of 70% by weight of lead oxide, 15% by weight of boron oxide, 8% by weight of silicon oxide, and 3% by weight of zinc oxide as glass powders. (Softening point 470 ° C.) 100 parts by weight and a polymer of methyl methacrylate / 2-ethylhexyl methacrylate / 2-methacryloyloxyethylbutoxyurethane = 11/85/4 (wt%) as an acrylic resin having a urethane group (Mw: 285,000) 15 parts by weight, 7 parts of dibutyl phthalate and 35 parts by weight of toluene (solvent) were kneaded to prepare a glass powder-containing paste composition F2. As a result of measuring the viscosity and the yield value with an E-type viscometer, the viscosity was 5 Pa · s, the yield value was relatively small at 0.1 Pa, and the dispersibility was good. The storage stability of the paste composition was tested, but the storage stability was good without aggregation of glass powder.

<Preparation of transfer films F1 and F2>
In the same manner as in Example 1, the glass powder-containing paste composition F1 was applied on the support film substrate, the dielectric transfer film F1 having a thickness of 30 μm was laminated on the support film substrate, and then a protective film was laminated. I wound it up. This is called a transfer film F1.
Further, in the same manner as in Example 1, the glass powder-containing paste composition F2 was applied on the support film substrate, and the dielectric transfer film F2 having a thickness of 30 μm was laminated on the support film substrate, and then the protective film was applied. Rolled up while laminating. This is called a transfer film F2.
As a result of TGA analysis of the dielectric transfer layers F1 and F2, the thermal decomposition temperature of the acrylic resin was as good as 375 ° C.

<Transfer Process of Dielectric Transfer Film F1>
In the same manner as in Example 1, a transfer film F1 was prepared, and the dielectric transfer film F1 was transferred onto a glass substrate for a 6-inch panel.

<Baking process of dielectric transfer film F1>
In the same manner as in Example 1, the dielectric transfer film F1 transferred onto the glass substrate was heated from room temperature to 590 ° C. at a heating rate of 10 ° C./min, and baked for 30 minutes in a temperature atmosphere of 590 ° C. As a result, a dielectric film F1 made of a glass sintered body was formed on the surface of the glass substrate.

<Transfer process of dielectric transfer film F2>
Next, a transfer film F2 is prepared. In the same manner as in Example 1, the transfer film is overlaid on the dielectric film F1 so that the surface of the dielectric transfer film F2 comes into contact with the dielectric film F2. Transcribed.

<Baking process of dielectric transfer film F2>
In the same manner as in Example 1, the dielectric transfer film F2 transferred onto the glass substrate was heated from room temperature to 570 ° C. at a temperature rising rate of 10 ° C./min and baked in a temperature atmosphere of 570 ° C. for 30 minutes. By processing, a dielectric film F2 made of a glass sintered body was formed on the surface of the glass substrate.
When the cross-sectional surface was observed with a scanning electron microscope and the film thickness of the dielectric films F1 and F2 was measured, it was in the range of 30 μm ± 1.0 μm, and the film thickness was excellent.

<Performance evaluation of dielectric film>
Thus, a panel material made of a glass substrate having a dielectric film was produced. When the cross section and the surface of the formed dielectric film were observed with a scanning electron microscope, no film defects such as pinholes and cracks were found in the dielectric films formed on all panel materials. Further, the low melting point glass did not soften and flow and eroded between the bus electrode and the transparent conductive film, and the bus electrode did not peel from the transparent conductive film. Also, in the visual appearance observation, the bus electrode was not colored. Furthermore, a panel material made of a glass substrate having a dielectric film was produced in this way, and the light transmittance (measurement wavelength 550 nm) of the formed dielectric film was measured with a spectrophotometer. The average value was 89%, and it was confirmed to have good transparency.

(Comparative Example 1)
<Preparation of Glass Powder-Containing Paste Composition C1>
As a glass powder, PbO—B ₂ O ₃ —SiO ₂ —BaO-based glass (softening) having a composition of 40% by weight of lead oxide, 30% by weight of boron oxide, 10% by weight of silicon oxide, and 20% by weight of barium oxide as a main component. (Point 580 ° C.) 100 parts by weight and a polymer (Mw: 240,000) of n-butyl methacrylate / 2-ethylhexyl methacrylate / hydroxylethyl methacrylate = 27/70/3 (wt%) as an acrylic resin having a hydroxyl group Parts, 7 parts of dibutyl phthalate, and 35 parts by weight of toluene (solvent) were kneaded to prepare a glass powder-containing paste composition C1. As a result of measuring the viscosity and the yield value with an E-type viscometer, the viscosity was 2 Pa · s, the yield value was as small as 0.01 Pa, and the dispersibility was good. The storage stability of the paste composition was tested, but the storage stability was good without aggregation of glass powder.

<Preparation of Glass Powder-Containing Paste Composition C2>
Further, as a glass powder, PbO—B ₂ O ₃ —SiO ₂ —ZnO-based glass having a composition of 70% by weight of lead oxide, 15% by weight of boron oxide, 8% by weight of silicon oxide, and 3% by weight of zinc oxide as glass powders. (Softening point 470 ° C.) 100 parts by weight and a polymer of n-butyl methacrylate / 2-ethylhexyl methacrylate / hydroxylethyl methacrylate = 27/70/3 (wt%) as an acrylic resin having a hydroxyl group (Mw: 240,000) A glass powder-containing paste composition C2 was prepared by kneading 15 parts by weight, 7 parts by weight of dibutyl phthalate and 30 parts by weight of toluene (solvent). As a result of measuring the viscosity and the yield value with an E-type viscometer, the viscosity was as small as 1 Pa · s, the yield value was as small as 0.01 Pa, and the dispersibility was good. The storage stability of the paste composition was tested, but the storage stability was good without aggregation of glass powder.

<Preparation of transfer films C1 and C2>
In the same manner as in Example 1, the glass powder-containing paste composition C1 was applied onto the support film substrate, the dielectric transfer film C1 having a thickness of 30 μm was laminated on the support film substrate, and then a protective film was laminated. I wound it up. This is called a transfer film C1.
Further, in the same manner as in Example 1, the glass powder-containing paste composition C2 was applied on the support film substrate, and the dielectric transfer film C2 having a film thickness of 30 μm was laminated on the support film substrate. Rolled up while laminating. This is called a transfer film C2.
As a result of TGA analysis of the dielectric transfer layers C1 and C2, the thermal decomposition temperature of the acrylic resin was 405 ° C.

<Transfer Process of Dielectric Transfer Film C1>
In the same manner as in Example 1, a transfer film C1 was prepared, and the dielectric transfer film C1 was transferred onto a glass substrate for a 6-inch panel.

<Baking process of dielectric transfer film C1>
In the same manner as in Example 1, the dielectric transfer film C1 transferred onto the glass substrate was heated from room temperature to 590 ° C. at a heating rate of 10 ° C./min, and baked for 30 minutes in a temperature atmosphere of 590 ° C. As a result, a dielectric film C1 made of a glass sintered body was formed on the surface of the glass substrate.

<Transfer process of dielectric transfer film C2>
Next, a transfer film C2 is prepared. In the same manner as in Example 1, the transfer film is overlaid on the dielectric film C1 so that the surface of the dielectric transfer film C2 comes into contact with the dielectric film C2. Transcribed.

<Baking process of dielectric transfer film C2>
In the same manner as in Example 1, the dielectric transfer film C2 transferred onto the glass substrate was heated from room temperature to 570 ° C. at a heating rate of 10 ° C./min, and baked for 30 minutes in a temperature atmosphere of 570 ° C. By processing, a dielectric film C2 made of a glass sintered body was formed on the surface of the glass substrate.

  When the laminated film thickness of the dielectric films C1 and C2 was measured by observing the cross section with a scanning electron microscope, it was in the range of 30 μm ± 1.0 μm, and the film thickness was excellent. However, the dielectric film is colored black, and it is assumed that the undecomposed product of the acrylic resin remains in the film.

<Performance evaluation of dielectric film>
Thus, a panel material made of a glass substrate having a dielectric film was produced. When the cross section and the surface of the formed dielectric film were observed with a scanning electron microscope, no film defects such as pinholes and cracks were found in the dielectric films formed on all panel materials. Further, the low melting point glass did not soften and flow and eroded between the bus electrode and the transparent conductive film, and the bus electrode did not peel from the transparent conductive film. Also, in the visual appearance observation, the bus electrode was not colored. Furthermore, a panel material made of a glass substrate having a dielectric film was produced in this way, and the light transmittance (measurement wavelength 550 nm) of the formed dielectric film was measured with a spectrophotometer. The average value was 75%, and the transparency was insufficient and failed.

(Comparative Example 2)
<Preparation of Glass Powder-Containing Paste Composition D1>
As a glass powder, PbO—B ₂ O ₃ —SiO ₂ —BaO-based glass (softening) whose main components are 40% by weight of lead oxide, 30% by weight of boron oxide, 10% by weight of silicon oxide, and 20% by weight of barium oxide. Point 580 ° C.) 100 parts by weight, polymer (Mw: 260,000) of n-butyl methacrylate / 2-ethylhexyl methacrylate = 30/70 (% by weight) as an acrylic resin, 7 parts of dibutyl phthalate, A glass powder-containing paste composition D1 was prepared by kneading 35 parts by weight of toluene (solvent). As a result of measuring the viscosity and the yield value with an E-type viscometer, the viscosity was 7 Pa · s, the yield value was 4 Pa, and the dispersibility was poor. The storage stability of the paste composition was tested, but agglomeration of the glass powder occurred, and the storage stability was poor and could not be reused.

<Preparation of Glass Powder-Containing Paste Composition D2>
Further, as a glass powder, PbO—B ₂ O ₃ —SiO ₂ —ZnO-based glass having a composition of 70% by weight of lead oxide, 15% by weight of boron oxide, 8% by weight of silicon oxide, and 3% by weight of zinc oxide as glass powders. (Softening point 470 ° C.) 100 parts by weight, 15 parts by weight of a polymer (Mw: 260,000) of n-butyl methacrylate / 2-ethylhexyl methacrylate = 30/70 (wt%) as an acrylic resin, and dibutyl phthalate 7 A glass powder-containing paste composition D2 was prepared by kneading parts and 35 parts by weight of toluene (solvent). As a result of measuring the viscosity and the yield value with an E-type viscometer, the viscosity was as large as 5 Pa · s, the yield value was as large as 3 Pa, and the dispersibility was poor. The storage stability of the paste composition was tested, but agglomeration of the glass powder occurred, the storage stability was poor and could not be reused.

<Preparation of transfer films D1 and D2>
In the same manner as in Example 1, the glass powder-containing paste composition D1 was applied onto the support film substrate, the dielectric transfer film D1 having a thickness of 30 μm was laminated on the support film substrate, and then a protective film was laminated. I wound it up. This is called a transfer film D1.
Further, in the same manner as in Example 1, the glass powder-containing paste composition D2 was applied on the support film substrate, the dielectric transfer film D2 having a thickness of 30 μm was laminated on the support film substrate, and then the protective film was applied. Rolled up while laminating. This is called a transfer film D2.
As a result of TGA analysis of the dielectric transfer layers D1 and D2, the thermal decomposition temperature of the acrylic resin was 410 ° C.

<Transfer Process of Dielectric Transfer Film D1>
In the same manner as in Example 1, a transfer film D1 was prepared, and the dielectric transfer film D1 was transferred onto a glass substrate for 6-inch panel.

<Baking Process of Dielectric Transfer Film D1>
In the same manner as in Example 1, the dielectric transfer film D1 transferred onto the glass substrate was heated from room temperature to 590 ° C. at a heating rate of 10 ° C./min, and baked for 30 minutes in a temperature atmosphere of 590 ° C. As a result, a dielectric film D1 made of a glass sintered body was formed on the surface of the glass substrate.

<Transfer Process of Dielectric Transfer Film D2>
Next, a transfer film D2 is prepared. In the same manner as in Example 1, the transfer film is overlaid on the dielectric film D1 so that the surface of the dielectric transfer film D2 comes into contact with the dielectric film D2. Transcribed.

<Baking process of dielectric transfer film D2>
In the same manner as in Example 1, the dielectric transfer film D2 transferred onto the glass substrate was heated from room temperature to 570 ° C. at a heating rate of 10 ° C./min, and baked for 30 minutes in a temperature atmosphere of 570 ° C. By processing, a dielectric film D2 made of a glass sintered body was formed on the surface of the glass substrate.

  When the cross-section was observed with a scanning electron microscope and the laminated film thickness of the dielectric films D1 and D2 was measured, it was in the range of 30 μm ± 2.5 μm, and the film thickness was inferior. The surface of the dielectric film was rough, and the undispersed glass powder was condensed.

<Performance evaluation of dielectric film>
Thus, a panel material made of a glass substrate having a dielectric film was produced. When the cross section and the surface of the formed dielectric film were observed with a scanning electron microscope, aggregates were observed in the dielectric films formed on all panel materials. Further, the low melting point glass did not soften and flow and eroded between the bus electrode and the transparent conductive film, and the bus electrode did not peel from the transparent conductive film. Also, in the visual appearance observation, the bus electrode was not colored. Furthermore, a panel material made of a glass substrate having a dielectric film was produced in this way, and the light transmittance (measurement wavelength 550 nm) of the formed dielectric film was measured with a spectrophotometer. The average value was 50%, and the transparency was insufficient and failed. Moreover, the display nonuniformity considered to be attributed to the aggregates was seen, and it was rejected.

  The glass powder-containing paste composition for plasma display according to the present invention can firstly produce various high-quality paste compositions efficiently, and secondly, the glass powder-containing paste composition of the present invention can be used. The transfer film had excellent film thickness uniformity, no defects, excellent surface smoothness, and could form a high quality transfer film for plasma display. Third, when used for plasma display applications, It is possible to produce a high-quality plasma display at a low cost and is very useful.

It is a schematic diagram which shows the cross-sectional shape of an alternating current type plasma display panel. It is an example of the cross-sectional schematic diagram of the transfer film for plasma displays of this invention.

Explanation of symbols

1 Glass substrate (front plate)
2 Transparent electrode 3 Black conductive layer 4 Main electrode 5 Dielectric film 6 Protective layer 7 Bus electrode 8 Glass substrate (back plate)
9 Address electrode 10 Dielectric film 11 Partition 12 Fluorescent material 20 Support film substrate 21 Transfer layer 22 Cover film substrate

Claims (8)

  A glass powder-containing paste composition for plasma display containing an acrylic resin containing urea groups and / or urethane groups, glass powder, and a solvent. The glass powder-containing paste composition for plasma display according to claim 1, wherein the urea group is an ethylene urea group represented by Structural Formula 1.

  The acrylic resin containing said urea group and / or urethane group contains 0.1-30 weight part of urea groups and / or urethane group containing acrylic monomers with respect to the whole acrylic resin. 2. A glass powder-containing paste composition for plasma display.   The glass powder for plasma display according to any one of claims 1 to 3, wherein the acrylic resin containing the urea group and / or the urethane group is 5 to 40 parts by weight with respect to 100 parts by weight of the glass powder. Paste composition.   The glass powder-containing paste composition for plasma display according to any one of claims 1 to 5, wherein the glass powder is a glass having a softening point of 400 ° C or higher and lower than 600 ° C.   The glass powder-containing paste composition for plasma display according to any one of claims 1 to 5, wherein the absolute value of the yield value of the glass powder-containing paste composition for plasma display is 1 Pa or less.   A transfer film in which the glass powder-containing paste composition for plasma display according to claim 1 is applied on a support film to form a transfer layer.   A transfer film using the transfer film according to claim 7 as a transfer film for forming a dielectric film on a front plate and / or a back plate of a plasma display.

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