TW200525556A - Composition for dielectric layer, green sheet, dielectric-layer-formed substrate, and its production method - Google Patents

Abstract

To provide a composition for a dielectric layer capable of yielding a PDP (plasma display panel) free from picture element defects; a green sheet formed thereof; a dielectric-layer-formed substrate having a dielectric layer formed of the green sheet; and a production method of the substrate. The composition for a dielectric layer contains a thermally decomposable binder, a glass component, and a dispersant. The thermally decomposable binder has a wt. average molecular wt. of 100,000-250,000 and is contained in a quantity of 15-50 pts.wt. based on 100 pts.wt. of the glass component (in a solid content ratio). The green sheet is produced by drying the composition and forming it into a film. The dielectric-layer-formed substrate has a dielectric layer formed from the composition. The production method of the dielectric-layer-formed substrate comprises the step of laminating the green sheet on a substrate and the step of baking the green sheet.

Description

200525556 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a composition for a dielectric layer suitable for the development of a dielectric > of a plasma display panel, and the composition is formed into a film. The finished green sheet, green sheet laminated substrate and manufacturing method thereof. [Prior art] The display device includes a liquid crystal display device, an electroluminescence display device, a plasma display panel, and the like. Among them, the plasma display panel (hereinafter referred to as "PDP") has attracted much attention as a new-generation multimedia display. However, PDP has a large number of layers due to the glass surface area of the substrate, and the manufacturing process is complicated. As a result, the yield has improved and the process has been simplified. Fig. 3 is a cross-sectional view of an example of a PDP. The pDp in FIG. 3 is composed of a glass substrate 1 for a front panel, a glass substrate 2 for a back panel, and a pair of glass substrates. A transparent electrode 3 and a data electrode 4 which are orthogonal to each other are formed on the inner surface of the glass substrate for front panel 丨 and the glass substrate 2 for back panel. The transparent electrode 3 and the data electrode 4 are each covered by a dielectric layer 5 (front panel dielectric layer) and 6 (back panel dielectric layer). Further, the glass substrates i and 2 separate the discharge space Γβ1 (pixel) through the protective film 7 at the partition wall, and a phosphor 9 is formed in each pixel. Conventionally, a method for forming a front-layer dielectric layer and a back-surface dielectric layer is a screen printing method. In this method, a dielectric agent containing a glassy earth powder component and a resin is repeatedly printed on a glass substrate to obtain a desired thick sound with a desired performance, and then 'calcined' to obtain a dielectric layer. However, in this method, it is necessary to repeat the application of the paste to volatilize the solvent, and the operation of applying the paste is then performed. Mind

2209-6564-PF 5 200525556 Residual solvents cause deterioration of dielectric layer performance. Therefore, there is a problem that the film thickness is not necessary, and the surface is not smooth. In order to solve such a problem, a method of transderm has been developed in recent years. For example, 'Patent Document 1 discloses that a dispersion containing a glass powder component or a vitrified substance is formed on a tape or a film to form a green powder component or a vitrified substance, and the green chip is pressed onto a glass. A manufacturing method of a glazed glass substrate (ceramic substrate) on a substrate or a ceramic substrate, which is melted and consolidated by heating to form a glass layer on a glass substrate (or ceramic substrate). However, the blank obtained by this method has a problem of weak adhesion to the glass substrate (ceramic substrate). In addition, Patent Documents 2 and 3 propose that a pressure-sensitive adhesive layer of powder flakes with an inorganic powder be added to the object to be coated with a glass powder component and a binder as the main component, followed by calcined coating. method. However, in this method, an additional pressure-sensitive adhesive layer is required, and the manufacturing process becomes complicated. When the pressure-sensitive adhesive component is thermally decomposed during the calcination process, the generated decomposition gas causes the glass layer to bulge, etc., and the quality of the dielectric product is degraded. 〇1: Patent Document 1 Japanese Patent Laid-Open No. 61-22682 Patent Document 2 Japanese Patent Laid-Open No. 63-197640 Patent Literature 3 Japanese Patent Laid-Open No. 64-73086 [Summary of the Invention] Problems to be Solved by the Invention

The present invention has been made in view of the problems of the conventional technology, and its subject is to provide a composition for a dielectric layer, a green sheet, which can obtain a PDP without pixel defects, 2209-6564-PF 6 200525556. The dielectric layer forming substrate of the formed dielectric layer and a manufacturing method thereof. Means for Solving the Problems In order to solve the above problems, the present inventors tried a method using a green sheet as described in Patent Documents 丨 and the like to form a pDp dielectric layer. In this method, a composition for a dielectric layer is formed on a thin film, a so-called blank is laminated on a substrate, and then a dielectric layer is obtained by calcining. However, when laminations are laminated on the glass substrate for front panel or glass substrate for back plate before the electrodes have been formed on the surface, fine voids are created between the electrodes and the blanks. The voids become bubbles during the firing process. 'Cause short circuit' has the problem of causing pixel defects in the PDP. Therefore, as a result of careful investigation, it was found that a composition for a dielectric layer containing a thermally decomposable adhesive having a specific weight average molecular weight was prepared, and a green sheet was obtained by using the composition for a dielectric layer. Then, by using this blank, the uneven shape of the front substrate (and / or the back substrate) on which the electrodes have been formed can be laminated uniformly without generating voids. It was also found that a calcined green sheet can obtain a dielectric layer without bubbles and a good film quality. Using a substrate formed with the dielectric layer, a plasma display panel without pixel defects and excellent withstand voltage characteristics can be obtained. And finally completed the present invention. Thus, the first aspect of the present invention provides a composition for a dielectric layer containing a thermally decomposable adhesive, a glass component, and a dispersant, characterized in that the weight-average molecular weight of the thermally decomposable adhesive is 100, 〇 The content of the thermally decomposable adhesive is from 15 to 50 parts by weight based on 100 parts by weight of the glass component based on the solid content ratio.

2209-6564-PF 7 200525556: The composition for the dielectric layer is preferably a dielectric layer for a plasma display panel. : A second aspect of the present invention is characterized in that: ... ... the embryonic sheet formed by drying the dielectric layer of the present invention with the composition a. The embryo piece of the present invention is LV ο. The storage elasticity of t A in May at 25 c is preferably from 1.0 × 108 Pa to 1.0 × 108 Pa. This specification provides that the pot 4 ± ^ / r /-JtK * θ. /, Is characterized by a dielectric layer formed with a dielectric layer formed from the composition for a dielectric layer of the present invention. Substrate. The fourth aspect of the present invention provides, 1 Nash ', /, characterized in that it includes a method for manufacturing a substrate including a dielectric sheet attached to a substrate of the present invention, and a method for forming a dielectric layer on the substrate during the firing process. . Effects of the Invention According to the present invention, it is possible to provide a composition for a dielectric layer and a green sheet without a pixel defect. According to the present invention, the green sheet ′ can be laminated uniformly along the unevenness of the surface of the substrate on which the electrode has been formed, without generating voids.

It is necessary to form a dielectric layer-forming substrate having a dielectric layer that does not contain air waves and has a good MV cell bubble quality.

According to this & manufacturing method, a substrate for forming a dielectric layer can be obtained simply and efficiently. Using the dielectric layer of the present invention to form a substrate, a plasma display panel without pixel defects and excellent withstand voltage characteristics can be obtained. [Embodiment]

Hereinafter, the composition of the present invention for a dielectric layer, 2) a green sheet, 2209-6564-PF 200525556, and 3) a dielectric layer forming substrate and a manufacturing method thereof will be described in detail one by one. 1) Composition for a dielectric layer The composition for a dielectric layer of the present invention contains a glass component, a dispersant and a thermally decomposable adhesive. (1) Glass component The glass component used in the composition for a dielectric layer of the present invention is, for example,

Pb0-B203 (lead oxide_boron oxide) series glass, Pb〇_B2〇3_Si〇2 (oxidized oxide-boron oxide-silicon oxide) series glass, PbHO3_Si〇2_A12〇3 (oxidized oxide-boron oxide-oxidation; ε evening · oxidation) series glass, Zn〇-B2〇3-Si〇2 (oxidation _ oxide side · silica) series glass, Pb0_ Zn〇_B2〇3 _si〇2 (lead oxide-zinc oxide · oxidation Boron · Silicon Oxide) based glass, Na20-B203-Si02 (Sodium Oxide-Boron Oxide-Silicon Oxide) based glass, Ba〇-Ca〇-SiO2 (Barium Oxide-Calcium Oxide. Silicon Oxide) based glass, etc. Among them, PbHOrSiOrAUO3 glass is preferred. In the present invention, these glasses are used in a powder form. The uniform particle position of the glass powder is from 0.1 to 5 microns, and the maximum particle size of the glass powder is from 20 microns to 佺. By setting the particle size of the glass powder in this manner, a dielectric layer having excellent withstand voltage characteristics can be formed. When the composition for a dielectric layer of the present invention is used as a dielectric layer for a back plate, and the mouthpiece is a white dielectric layer, the glass component preferably contains a filler component. The shapeable filler components include Ti02 (titanium oxide), Al203 (oxygen), Si02 (silicon oxide), Zr02 (thorium oxide), and the like. Among them, Ti02 and AI2O3 are particularly preferred. In glass components, the mixing ratio of glass powder and filler components is usually

2209-6564-PF 200525556 50: 50 to 100: 〇, when used as a composition for the back surface dielectric layer, 50: 50 to 95 · 5 is used as the front panel dielectric layer When using the composition, it is preferably 10: 0. In the present invention, a glass component can also be used as a glass frit. The glass frit is obtained by mixing a glass-breaking powder and a desired filler component in a specific ratio, melting the resulting mixture, and then cooling the mixture. The obtained glass frit was pulverized into a powder and used. The amount of the glass component to be added is usually 40 to 80% by weight based on the composition for the dielectric layer. (2) Dispersant The dispersant used in the composition for a dielectric layer of the present invention is not particularly limited as long as it can uniformly disperse glass components. There are, for example, surfactants and silane coupling agents. Surfactants include alkylbenzenesulfonate, alkylnaphthalenesulfonate, sodium alkylsulfonate succinate, sodium alkyldiphenyl ether disulfonate, sodium formalin condensate, and aromatic sulfonic acid. Anionic surfactants such as formalin condensate sodium salts; cationic surfactants such as alkylamine salts, quaternary ammonium salts; polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene Non-ionic surfactants such as glycol distearate, polyethylene glycol monooleate laurate diethanolamine, decyl bran fur, lauryl glycoside; α-olefin / maleic acid copolymer Partially brewed, aliphatic polyacrylic acid salt, aliphatic polycarboxylic acid, special polyazo, and other polycarboxylic acid type surfactants; obtained from polyether polyacetic acid, polyether polyalcoholic acid, etc. S purpose acids and polymer amines and other organic amine-based polymer dispersants (specifically, DISPERONDA_234 (trade name, manufactured by Kusumoto Chemical Co., Ltd.), etc.) polyether polyester amine salt and the like. 2209-6564-PF 10 200525556 Silane coupling agents are vinyltrimethoxysilane, vinyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, Ν_β_ (Ν_ ethylene Benzylaminoethyl) -γ-aminopropyltrioxocyanate • hydrochloride, N_ (p_aminoethyl) -γ-aminopropylfluorenyldimethoxysilane, γ-glycidoxy Propyltrimethoxysilane, β-glycidoxypropylmethyldimethoxysilane, γ-methylpropoxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxy Silane, y_mercaptopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ_ (2_aminoethyl) aminopropylmethyldimethoxysilane, aminosilane, ethylene Triethoxysilane, γ-anilinepropyltrimethoxysilane, octadecyldimethyl (3- (dimethoxysilyl) propyl) ammonium, [ureapropyltriethoxysilane, etc. Among them, for reasons of excellent dispersibility, polycarboxylic acid type polymer surfactants and polyetherester acid amine salts are preferred. The addition amount of the dispersant is usually 0.01 to 10% by weight, preferably 0.05 to 5% by weight, and 0 to 3% by weight relative to the composition for the dielectric layer.

% Is better. The amount of dispersant added is less than G. Q1% by weight, the dispersion state is not uniform. There may be a composition for the dielectric layer where the glass components are liable to settle. Even at 10% by weight, the dispersant remains in the calcination process In the dielectric layer, the withstand voltage and transparency or reflectance are reduced. , S (3) Thermally decomposable adhesive The dielectric layer of the present invention is used as a ^ Λ Α ^ agent. It is used for the thermal decomposition of the present invention; "Thermo-decomposable viscous calcining and decomposition is easy to go / 'If it has #binding agent's function because it has excellent adhesion. The cutting effect is not limited. Among them, the agent is $, # 5 & Have pressure contact with glass substrate

2209-6564-PF 200525556 Acrylic resins include, for example, monopolymers of (meth) acrylate compounds, copolymers of two or more types of (meth) acrylate compounds, (meth) acrylate compounds and other copolymers Copolymers of sexual monomers. Specific examples of the (meth) acrylate compound include (meth) acrylic acid, methyl (meth) acrylate, ethyl (fluorenyl) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate S purpose, butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, amyl (meth) acrylate, amyl (fluorenyl) acrylate, ( Isoamyl methacrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, twelve (meth) acrylate Esters, (meth) acrylic acid lauryl esters, (meth) acrylic acid stearyl (meth) acrylic acid stearyl esters, etc. (meth) acrylic acid alkyl esters; (2-hydroxyethyl methacrylate), ( 2-hydroxypropyl methacrylate, 4-hydroxybutyl (meth) acrylate, (meth) 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and other hydroxyalkyl (meth) acrylates; phenoxyethyl (meth) acrylate, 2-hydroxy-3-benzyloxypropyl (meth) acrylate, and phenoxyalkyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate Alkoxyalkyl (meth) acrylates, such as 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, and 2-oxobutyl (meth) acrylate; polyethylene Diol mono (fluorenyl) acrylate, ethoxy diethylene glycol (fluorenyl) acrylate, phenoxy polyethylene glycol (fluorenyl) acrylate, phenylphenoxy polyethylene glycol (methyl 2209-6564- PF 12 200525556 based) acrylate, polypropylene glycol mono (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate, phenylphenoxy polypropylene glycol (formaldehyde) Poly) alkylene glycol (meth) acrylates such as acrylate; cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate Dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadiene (meth) acrylate, fluorenyl (meth) acrylate, isofluorenyl (meth) acrylate, (meth) ) Cycloalkyl (meth) acrylates such as tricyclodecyl acrylate; (fluorenyl) benzyl acrylate, methyl) acrylic acid tetrahydrouranyl and the like. Of these, alkyl (fluorenyl) acrylate or hydroxy alkyl (fluorenyl) acrylate is preferred. Examples of the (meth) acrylic acid esters include butyl (meth) acrylate, hexyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, and 2-methacrylate Ethylhexyl ester and the like, for example, hydroxyalkyl (meth) acrylate include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and the like. The other copolymerizable monomer is not particularly limited as long as it is a compound that can be copolymerized with the above (meth) acrylate compound. For example, (meth) acrylic acid, vinyl benzoic acid, maleic acid, and vinyl fumaric acid can be used. And other unsaturated carboxylic acids; vinyl benzyl methyl ether, vinyl glycidyl ether, styrene, cardiac styrene, butadiene, isopropyl vinyl-containing radical polymerizable compounds, and the like. Acrylic resin can be obtained by (co) polymerizing these (meth) acrylate compounds and desired other copolymerizable monomers. The polymerization method is not particularly limited, and conventional polymerization methods can be used. For example, there is a radical polymerization method using a radical polymerization initiator such as azobisisobutyronitrile (αιβν). In the present invention, a thermally decomposable adhesive is used, and the weight average molecular weight is 100.

2209-6564-PF 13 200525556 ′ 〇 0 0. Also, the "content of the thermally decomposable binder in the composition for the dielectric layer" is a solid content ratio of 15 to 50 parts by weight based on 100 parts by weight of the glass component. Based on the thermal decomposition f of the weight average molecular weight system of 100,000 to 250,000, it is used for the formation of the dielectric layer. The proportion of the solid content is 1 to 50% by weight for the dielectric layer. The composition has excellent shape retention, and can be laminated uniformly on the front substrate (or back substrate) with the electrodes along the uneven shape without voids. The laminated swatches can be calcined to form a bubble-free voltage resistance. Excellent dielectric layer. (4) Other ingredients The composition for electric layer [1] of this hair month may also contain a solvent as other ingredients. The solvent is used to impart appropriate fluidity or plasticity to the composition for a dielectric layer, and good film-forming properties. The solvents used are, for example, diethyl ether, diisocyanate, dibutyl M, I, one or two *, dimethyethane, tetrahydrofuran, 1,4-dioxane; methylacetic acid 3r. Text B, propyl acetate, butyl acetate, milk

Acrylates and other esters; acetone, methyl ethyl ketone, methyl isobutyl ketone 'diethyl ketone, ketones and other classes; N, N, dimethylformamide, N, N, dimethylacetamidine Ammonium hexamethylphosphorylamide, N-methylpyrrolidone, and other amines; ^ Caprolactams such as endoamines; γ • Endolactine, § _ Endoline, and other vinegars; trimethylamine Master = Asian maple and other Asian maple H, Yung, Geng, Suan, Ren, ^ Hydrocarbons; ring money, cyclohex, and cycloaliphatic alicyclic smoke benzene, benzene, xylene and other aromas Family hydrocarbons; dichloromethanes, chloroform, and four: halogenated hydrocarbons such as monochloroethane, chlorobenzyl; and these 2 3

2209-6564-PF 14 200525556 A mixed solvent composed of the above. Among them, it is preferable to use vinegars, maggots, aromatic tobaccos, or a mixed solvent composed of two or more of these, and it is more preferable to use maggots and vinegars. The amount of the solvent used is usually 0 to 55% by weight based on the composition for the dielectric layer. Benmemine's composition for electric layers may contain a plasticizer, if necessary, a (meth) acetic acid pure polymer having a molecular weight of 5, 0 () () or less, a preservation tincture, 4 > Additives such as encapsulants, thermal decomposition accelerators, antioxidants. The composition for a dielectric layer of the present invention can be prepared by pre-mixing the aforementioned glass components, a dispersant, a thermally decomposable binder, and a solvent with a disperser as a mechanical dispersion. The dispersing machine used for the dispersing is not particularly limited, and there are known dispersing machines such as a ball mill, a bead mill, a three-roll mill, a kneader, and the like. The dielectric layer of the composition for a dielectric layer of the present invention obtained from the above is excellent in its voltage characteristics because it has no bubbles, and is suitable as a material for forming a dielectric layer of pDp. Also, as described later, the green sheet of the present invention can be produced by using the composition for a dielectric layer of the present invention. 2) Green sheet The dielectric sheet of the present invention 胚 The green sheet of the present invention is characterized in that the composition is dried and formed into a film. 2. The green sheet of the present invention can be produced by applying the composition for a dielectric layer of the present invention to a carrier film, followed by drying and forming the film. • The first diagram shows an example of the production of the embryo piece of the present invention. In Fig. I, 13 is a carrier film, 14 is a coating device for coating the composition for a dielectric layer of the present invention, and 18 is a drying device for drying (removing a solvent) a coating film for a composition for a dielectric layer.

2209-6564-PF 15 200525556 2 > 0a and 20b are protective layers that are laminated on the green sheet. Hereinafter, a method for manufacturing a green sheet of the present invention will be described with reference to FIG. First, the carrier film 13 rolled into a roll shape is sent to a coating device 14. The carrier film 13 is not particularly limited as long as it is excellent in the peelability of the coating of the dielectric layer I composition. For example, polyethylene terephthalate film, polyethylene acetate film, poly = ene film, polymer Plastic film such as acrylic film. It is also preferable to use a single-coating release agent such as a polylithic resin, an alkyd resin, a fluorine-containing resin, or a long-chain resin based on the above-mentioned plastic film. (It can also be used, with peeling on the plastic film mentioned above.) · The raw tree month says, for example, there is a polysmoth tree on the polyethylene terephthalate film. The composition for a dielectric layer is coated on a single film 13. The coating device 14 is a dielectric #layer member of the present invention, which is composed of a storage section 15 and a coating section 16 and is stored in the storage section 15. The composition for the dielectric layer of the heart is successively fed to the coating section 16 by a certain amount. . The composition for a dielectric layer of the present specification is excellent in dispersibility and storage stability, and is uniformly dispersed in the core 15 without sedimentation of glass components and the like. Also, coating name

^ No special restrictions. For example, a knife coater or a die coater can be used. Zeng Hou: The coating amount of the composition for the dielectric layer of Γ may be used for the formed dielectric layer, and the thickness of the composite coating film 17a is appropriately set. The composition for a dielectric layer of the present invention can form a coating film 17a for a composition of an η electric shell layer having a uniform film thickness due to its excellent dispersibility and storage. ㈣Second time: A coating film of the composition for a dielectric layer has been formed on the surface, and the drying device 18 is used. The dielectric in the drying device 18

2209-6564-PF 16 200525556 Composition coating film for mass layer 17 yttrium exhibition (that is, removing solvent and other volatilized fresh :: dry coating film of composition for shell layer ', that is, there are embryos 17 laminated on The laminate on the film u. The method for drying the coating film 17a of the composition for the dielectric layer is not particularly limited, for example, the method of heating the carrier film on which the coating film has been formed to a specific temperature, and blowing it with "air or hot air" The method of coating the surface of the film, combining the above methods, etc. If the temperature during drying is the temperature at which the carrier film does not undergo thermal deformation: there is no special limitation below, usually from room temperature to 150., 60 to i3 (rC is more than The drying time is 丨 to 丨 0 minutes. The thickness of the coating film i7a after drying is usually 10 to 200 microns, and preferably 20 to 120 microns. Secondly, the protective film 19 is laminated on the embryo piece 17. In the first figure, The protective film 19 is a long film rolled into a roll shape. The protective film used may be a plastic film such as polyethylene terephthalate, polyethylene naphthalate film, polyethylene film, etc. x, a plastic film can be used One side is coated with a release agent such as polysilicon resin. In order to laminate a protective film 19 on the green sheet 17, The sheet 17 and the protective film 19 are bonded (laminated) between the two laminating rolls 20a and 20b in the first figure. At this time, either of the laminating rolls 20a and 20b or the two First, for example, the roller 20b of the protective film surface side is heated. As described above, the carrier film 13-blank sheet 17-protective film 19 three-layer laminated film 21 can be obtained. The obtained laminated film 21 can be rolled into a roll shape and recovered for storage. The storage elasticity of the slab 17 thus obtained at 25 ° C is not particularly limited, 2209-6564-PF 17 200525556 is more preferably 1 plus 105 pa to 10 × 5. The pride of the slab is Well, 5.0 · 10 × 10 Pa to 5.0 × 107 Pa is in the shape of 'I'm afraid it can't be laminated on ... 10 Pa 0', the stent is difficult to keep the storage elasticity of the slab on the glass substrate. On the other hand, the sintering process on the slab is at 80xlos. At the time of Pa, the embedding of the electrode is poor, which causes bubbles to be generated in the dielectric layer f after the R is strong. The storage of the blanks is placed in accordance with Jis K72 "4 using conventional dynamic viscoelasticity measurement equipment according to JIS Measured by the method of K7244. 3) Dielectric layer forming substrate and manufacturing method thereof The dielectric layer forming substrate of the present invention is characterized in that: The dielectric layer formed by the composition for the dielectric layer of the present invention. The 'I dielectric layer of the present invention forms a substrate, and the protective film can be peeled off from the blank obtained above, and then laminated on the substrate for the front panel or the substrate for the back panel * Conversely, secondly, after the carrier film is peeled off, it is obtained by calcining the blank. The substrates used here are glass substrates, ceramic substrates, etc., and glass substrates are preferred. If the glass substrates have electrodes formed on the surface, There is no particular limitation, and conventional materials can be used. For example, a glass substrate for a back plate having a data electrode formed on the surface. There is no particular limitation on the thickness of the substrate, and it is usually about 1 to 8 mm. The second example shows an example of manufacturing the dielectric layer forming substrate of the present invention. A method for forming a dielectric layer forming substrate according to the present invention will be described below with reference to FIG. 2. Fig. 2 is an example in which a transparent dielectric layer 5 is formed on a glass substrate for a front panel in Fig. 3. First, as shown in Fig. 2 (a), peel off and remove the protective film 19 on one side of the laminated film 21. 〇 2209-6564-PF 18 200525556 Second, as shown in Fig. 2 (b), heat-press the blank piece 17 onto the Before the transparent electrode 3 is formed, the glass substrate 1 for a panel (the side on which the transparent electrode 3 is formed) is formed. Since the thermally decomposable adhesive in the composition for a dielectric layer of the present invention is an adhesive and a pressure-sensitive adhesive, the green sheet 17 can be uniformly adhered to the glass substrate i by a simple operation. Next, as shown in FIG. 2 (c), the carrier film 13 is peeled off from the green sheet 17, and the glass substrate 1 on which the green sheet 17 is laminated is fired. In this process, the thermally decomposable adhesive in the composition for the dielectric layer is thermally decomposed, and the organic components are completely removed.

The method of calcining the glass substrate of the hot-pressed green sheet 17 includes, for example, a method of feeding the glass substrate of the hot-pressed green sheet 17 into a heating furnace and heating the entire body. If the heating temperature and heating time are not due to thermal deformation of the glass substrate, the thermally decomposable adhesive can be thermally decomposed, the organic components are completely removed, and the inorganic components (glass components, etc.) become a uniform molten state, and the glass components are melted and homogenized. There are no special restrictions on time. The heating temperature is usually 500 to 700t :, and the heating time is usually several minutes to several hours. In the present invention, the calcining system is divided into a temperature of 300 to 4500 t and a temperature of 10

The pre-calcination process of heating to 60 minutes, and then more than 500 to 70 (TC to 20 degrees! Formal calcination process of 20 minutes, because more uniform film quality and thickness can be obtained. A dielectric layer with excellent reflectivity or reflectivity and surface smoothness is preferred.… Can be obtained after cooling, as shown in Figure 2 below, and the laminated layer has a transparent dielectric with a thickness of 5 to 50 μm and a thickness of 7 to 90 μm. The glass substrate of the dielectric layer 5 is preferably more than 70% of the total light transmittance of the transparent dielectric layer 5. The surface unevenness is preferably 0.4 micrometers or less.

2209-6564-PF 19 200525556 is better. In this embodiment, the formation of the transparent dielectric layer 5 used in the glass substrate i for the front panel of the PDP is described, and the white dielectric shell 6 corresponding to the glass-filled substrate 2 for the back panel is formed on the ceramic substrate. A dielectric layer and the like can also be formed in the same manner. The obtained white dielectric layer 6 preferably has a reflectance of ^ to 100% and a surface roughness of 0.05 to b. Using the dielectric layer of this embodiment to form a substrate, it is possible to manufacture a plasma display device that is resistant to plasma discharge when it is lit. High-quality PDP with low voltage and pixel defects. ... Examples The examples will be described below in more detail with reference to examples and comparative examples. However, the present invention is not limited to the following examples. (Example 1) A glass frit, a thermally decomposable binder, a dispersant, a plasticizer, and a solvent were dispersed with a bead mill-type disperser to prepare a composition slurry for a dielectric layer of Example 1. The glass frit, thermally decomposable adhesive, dispersant, plasticizer, and solvent used are as follows. (1) Glass frit uses 100% by weight [pb〇 (60% by weight) _B203 (10% by reset) -S102 (25% by weight) -Al2O3 (5% by weight) , Average particle size of 2 · 8 microns] 100 parts by weight of broken concrete. (2) Thermally decomposable adhesive Use 25 parts by weight of 2-ethylhexyl methacrylate and methacrylic acid

2209-6564-PF 20 200525556 Resin A obtained by copolymerizing 2-hydroxyethyl ester with a molar ratio of 95: 5 and a weight average molecular weight of 150,000. (3) Dispersing agent: 1% sodium glutamate molecular surfactant (FLOWLEN G-700, manufactured by Kyoeisha Chemical Co., Ltd.) was used in an amount of 0.5 parts by weight. (4) Plasticizer 2 parts by weight of di (2-ethylhexyl) adipate was used. (5) Solvent 40 parts by weight of a mixed solvent of ethyl acetate and methyl isobutyl ketone 1: 1 was used. As a carrier film, a long polyethylene terephthalate (pET) film with a thickness of 38 micrometers was prepared using a silicone resin with a thickness of 0.1 micrometers as a release film on one side. On the release-treated surface of the film, the slurry obtained above was applied with a knife coater for release treatment. Next, the slab b with a thickness of micron was dried at 10 ° C for 2 minutes. Secondly, on the slab 1 obtained as above, a strip of PET film as described above was used. 1 micron thickness for protection from mold release

A PET film 'was used to press the release-treated surface through the rolls to obtain a laminated film formed by laminating a PET film-blade_PET film. It is a person, peeling and removing the protective PET film on the green sheet 1 obtained as described above, so that the green sheet of the laminated film is superposed on the glass substrate with a thickness of 3 mm (50 acres of wood on the mountain) On the surface, heat pressing (° C, 2 kg / cm2) with a heating roller). Then, the carrier film (PET film) is peeled off and sent to a heating furnace for

2209-6564-PF 21 200525556 > The temperature was raised to 10 ° C / min to 42 ° C and heated at 420 ° C for 10 minutes. The resin in the blank 1 was thermally decomposed. The temperature was further raised to 590 ° C, and firing was performed at this temperature for 60 minutes' to obtain a dielectric layer forming a dielectric layer 40 having a thickness of 40 µm. (Example 2) 30 parts by weight of butyl methacrylate and acrylic acid were copolymerized at a molar ratio of 99 ·· 1, except that the resin b having a weight average molecular weight of 20,000 was obtained as in Example 1. The green sheet 2 and the dielectric layer form a glass substrate 2. (Comparative Example 1) A resin obtained by copolymerizing 8 parts by weight of ethylhexyl methacrylate and 2-methylpropionate at a molar ratio of 95: 5 was used. The resin had a weight average molecular weight of 20,000. Except for C, a green sheet 3 and a dielectric layer were obtained in the same manner as in Example 1 to form a glass substrate 3. (Comparative Example 2) A resin having a weight average molecular weight of 120,000 was obtained by using 60 parts by weight of 2-ethylhexyl methacrylate and methacrylic acid 2-copolymerized with a molar ratio of 95.5 g. Except for D, a green sheet 4 and a dielectric layer were obtained as in Example 1 to form a glass substrate 4. (Comparative Example 3) 25 parts by weight of 2-ethylhexyl methacrylate and 2-methacrylic acid were obtained by copolymerizing ethyl methacrylate at a molar ratio of 95: 5. Except for resin E having a weight average molecular weight of 0.00, the same as Example 1 obtains a green sheet 5 and a dielectric layer to form a glass substrate 5. (Comparative Example 4) 2209-6564-PF 22 200525556 Using 25 parts by weight, copolymerized 2-ethylhexyl methacrylate and 2-hydroxyethyl methacrylate at a molar ratio of 95: 5, and obtained a weight average molecular weight of 50. Except for the resin F, the green sheet 6 and the dielectric layer were formed in the same manner as in Example 丨 to form a glass substrate 6. The types of thermally decomposable adhesives used in Example 2 and Comparative Examples 丨 to 4, the amount of thermally decomposable adhesives used relative to the weight of the glass frit, and the reset average molecular weight of the thermally decomposable adhesives are aggregated at Table 1. Table 1 Glass frit (parts by weight) Resin (parts by weight) Weight average molecular weight (Mw) Example 1 (100) Resin A (25) 150,000 Example 2 (100) Resin B (30) 200,000 Comparative Example 1 (100) Resin C (8) 200,000 Comparative Example 2 (100) Resin D (60) 120,000 Comparative Example 3 (100) Resin E (25) 350,000 Comparative Example 4 (100) Resin F (25) 50,000 (Measurement of slab thickness) Measurement implementation The thickness of the embryo pieces 1 to 6 in Example 2 and Comparative Examples 1 to 4. The measurement was performed using a constant-pressure thickness measuring device (manufactured by TECLOCK CORPORATION). The measurement results are shown in Table 2. (Measurement of storage elastic modulus of green sheets 1 to 6) The storage elastic modulus of green sheets 1 to 6 formed in Examples 1, 2 and Comparative Examples 1 to 4 was measured in accordance with JIS K7244.

The measurement was performed using a storage elastic modulus measuring device (DYNAMIC ANALYSER RDA II, manufactured by Rheometrics) under the conditions of 1 Hz, 25 ° C 2209-6564-PF 23 200525556. The test results are shown in Table 2. (Embryo shape conformability evaluation test) The shape-retaining embryo piece of the embryo piece 1 to 6 of Examples 1, 2 and Comparative Examples 1 to 4 was heat-bonded to a glass substrate, and then The exudation from the end of the embryo piece was evaluated. No exudation was 0, and exudation was X. The evaluation results are shown in Table 2.

(Evaluation test of the transferability of the green sheet to the broken glass substrate) The transferability when the green sheets i to 6 of the conventional examples 1, 2 and comparative examples J to 4 were laminated on the glass substrate with electrodes was evaluated. . After transferring the green sheet to the glass substrate, the evaluation is based on whether the carrier film is easy to peel off. The "easy peeling" is Q, and the peeling of the green sheet from the glass substrate is X when peeling. The evaluation results are shown in Table 2.矣 9

It is known from Table 2 that the germ pieces of Examples 1 and 2 and Comparative Examples 2 and 3 are worse than the germ pieces of Example 1. Also, I ca n’t keep it when I turn to the substrate

Comparative Example 2 Comparative Example 3 Comparative Example 4 The properties were excellent. However, the shape of the embryo piece was worse than that of Example 4 in the shape of 2209-6564-PF 24 200525556. Exudation was confirmed from the end of the embryo piece. (Determination of the thickness of the dielectric layer) The thickness of the dielectric layer of the dielectric layer-forming substrate 丨 to 6 was measured. The measurement was performed using a contact-type surface roughness measuring device (SV3000, manufactured by MITSUTOYO). The measurement results are shown in Table 3. (Dielectric layer transparency evaluation test) Example 2 and Comparative Example! [Dielectric layer formation substrate obtained from 4]] Total transmittance of the dielectric layer obtained from 6 to 6, measured by HAZEMeter

(HAZE Meter type NDH 2000, Nippon Denshoku Industries Co., Ltd.'s rules. As for transparency, the one with the transparency you want is 〇, and X cannot be evaluated. F ” (Evaluation test for presence or absence of bubbles in the dielectric layer) The dielectric layers and electrode bubbles of the dielectric layer-forming substrate of Example 2 and Comparative Examples i to 4 were observed and evaluated with an optical microscope. Table: No bubbles are 0, Bubbles are X. Evaluation results are listed in Table ° 3

The dielectric layer of Example 2 is excellent in transparency, no

2209-6564-PF 25 200525556 (Special rhenium electrodes are adjacent to the bubbles at the two ends. Comparative Example 2 II. In the dielectric layer of Comparative Example 1, many layers were observed to have poor transparency, and the second dielectric layer was observed to have poor transparency. Many bubbles were observed in the dielectric. From Table 1 to Table 3, from 100,000 to 250,000 °, the weight average molecular weight of the thermally decomposable adhesive ^ ^ hh ^ / 〇 'and the content of the thermally decomposable adhesive The solid piece of germ 糸 relative to the slope glass please 15 parts by weight and the storage elasticity of the piece of shim 2. 2 × 10 Pa to 1.0 × 108 Pa (Example) The shape retention and transfer of air bubbles Dielectric layer. The green sheet and the transparency are excellent. Therefore, the embodiment has excellent transparency and no bubbles. It is known that it is suitable for PDP and glass substrate.

And the dielectric layer of 2 forms a glass substrate because it has a dielectric layer (that is, excellent withstand voltage characteristics), especially for the front panel of a PDP with a dielectric layer. [Schematic description] = 1 The outline of the invention's embryo chip manufacturing process. Fig. 2 is a cross-sectional view showing a process of forming a substrate with a dielectric layer according to the present invention. Forming method Fig. 3 is a structural cross-sectional view of an example of a plasma display panel. [Description of main component symbols]

2 · 4 · month, glass substrate for J panel glass substrate for back panel transparent electrode material electrode dielectric layer (front panel dielectric layer)

2209-6564-PF 26 200525556 6 ··· Dielectric layer (dielectric layer on the back panel) 7 · •• Protective film 8 · • · Rib 9 · •• Fluorescent 13 · •• Load Film 14 • • Coating device 15 • • • Storage section 16 • • • Coating section 17 • • • Green sheet 17a · · · Composition coating film for dielectric layer 1 8 · · · Drying device 19 · · · Protection Films 20a, 20b · · • Laminated Roller 21 · · · Laminated Film 27

2209-6564-PF

Claims (1)

200525556 10. Scope of patent application: 1. A composition for a dielectric layer, a composition for a dielectric layer containing a thermally decomposable binder, a glass-breaking component, and a dispersant, which is characterized by: The weight average molecular weight of the binder is 100,000 to 250,000. The content of the thermally decomposable binder is based on the solid content ratio, and is 15 to 50 parts by weight based on 100 parts by weight of the glass component. 2. The composition for a dielectric layer according to item 1 of the scope of patent application, wherein the composition is used for a plasma display panel. 3. Seed seed pieces, characterized in that the composition for a dielectric layer as described in item No. 1 or 2 of the scope of patent application is dried and formed into a film. 4. The swatch according to item 3 of the scope of patent application, wherein the storage elasticity measured at 25 ° C is 1.0xlO5 Pa to 1.0xlO8 Pa. 5. A substrate for forming a dielectric layer, characterized in that it has a dielectric layer formed of a composition for a dielectric layer as described in item 1 or 2 of the patent application. 6. A method for manufacturing a substrate with a dielectric layer, comprising: a process of attaching a green sheet as described in item 3 or 4 of the patent application scope to a substrate, and a process of calcining the green sheet. 2209-6564-PF 28