JP2009249608A - Paste composition, fired product, and component for flat panel display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a paste composition which can ensure a good dispersion or dissolution state, is excellent in printability, and can further impart a good surface state to a fired product after firing; a fired product and a component for a flat panel display obtained by firing the paste composition. <P>SOLUTION: The paste composition is prepared by compounding a polyurethane resin obtained by a reaction of a polyoxyalkylene glycol, containing 1-85 mol% of a 2-3C alkylene group and 15-99 mol% of a 4-6C alkylene group, with a diisocyanate, a solvent and a powder. By firing the composition, components for a flat panel display such as a dielectric layer, a sealed body, a partition wall, a phosphor and an electron emitter are manufactured. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a paste composition, a fired body, and a flat panel display component, and more particularly, to a paste composition, a fired body obtained by firing the paste composition, and a flat panel display component.

Conventionally, a fired body obtained by firing a paste composition has been used as a part of a flat panel display (FPD) such as a plasma display panel (PDP) or a field emission display (FED).
As a paste composition for obtaining such a fired body, for example, a paste composition prepared from ethyl cellulose, a solvent, and a dielectric glass powder is known.

In addition, a phosphor paste prepared from polymethyl methacrylate, benzyl alcohol, and phosphor powder (BaMgAl ₁₀ O ₁₇ glass) has been proposed (see, for example, Patent Document 1).
Further, polyurethane resin obtained by reacting comb-shaped diol and polyethylene glycol (PEG) with hexamethylene diisocyanate, N-methylpyrrolidone, and dielectric glass powder (PbO—B ₂ O ₃ —SiO ₂ —CaO-based glass) ) And a dielectric paste composition prepared from (see, for example, Patent Document 2).
JP 2001-329256 A International publication pamphlet WO2005 / 040280

However, a paste composition containing ethyl cellulose generates cracks during firing. Therefore, the surface of the obtained fired body has many irregularities, and as a result, there is a problem that the transparency of the fired body is lowered. Moreover, there exists a malfunction that the residue resulting from ethyl cellulose remains in a baked body.
Further, the phosphor paste proposed in Patent Document 1 does not have high printing characteristics. For example, when the paste is applied to a glass substrate for PDP production by screen printing, stringing is performed between the screen and the printed surface of the substrate. There is a defect that occurs.

In addition, the dielectric paste composition proposed in Patent Document 2 is precipitated during preparation to become a cloudy slurry. For this reason, cracking may occur during paste firing.
An object of the present invention is to provide a paste composition that can ensure a good dispersed state or dissolved state, has excellent printing characteristics, and can give a good surface state to the fired body after firing, and its paste An object of the present invention is to provide a fired body and a flat panel display component obtained by firing the composition.

In order to achieve the above object, the paste composition of the present invention comprises 1 to 85 mol% of an alkylene group having 2 to 3 carbon atoms and 15 to 99 mol% of an alkylene group having 4 to 6 carbon atoms. It is characterized by containing a polyurethane resin obtained by reacting at least an alkylene glycol and a diisocyanate, a solvent, and a powder.
In the paste composition of the present invention, it is preferable that the polyoxyalkylene glycol has a number average molecular weight of 2000 or more.

  Further, in the paste composition of the present invention, the polyurethane resin comprises the polyoxyalkylene glycol, the diisocyanate, a comb diol represented by the following general formula (1) and / or a comb shape represented by the following general formula (2). It is preferable to obtain it by reacting at least with a diol.

(In the formula, R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms or a nitrogen-containing hydrocarbon group which may be substituted with a halogen atom. R ² and R ³ are the same or different from each other. And a hydrocarbon group having 4 to 21 carbon atoms which may be substituted with a halogen atom, and Y ¹ and Y ² are the same as or different from each other, and represent a hydrogen atom, a methyl group or CH _2. Represents a Cl group, Z ¹ and Z ² are the same or different from each other, and represent an oxygen atom, a sulfur atom or a CH ₂ group, and n ¹ and n ² are the same or different from each other. Differently, an integer of 0 to 15 is shown.)

(In the formula, R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom. R ⁵ and R ⁶ are the same or different from each other, R 4 represents an optionally substituted hydrocarbon group having 4 to 21 carbon atoms, R ⁷ represents an alkylene group having 2 to 4 carbon atoms, and Y ³ , Y ⁴ and Y ^5. Are the same or different from each other and represent a hydrogen atom, a methyl group or a CH ₂ Cl group, and Z ³ and Z ⁴ are the same or different from each other and represent an oxygen atom, a sulfur atom or a CH ₂ group. And k represents an integer of 0 to 15. n ³ and n ⁴ are the same or different from each other and represent an integer of 0 to 15.)
In the paste composition of the present invention, it is preferable that the powder contains a low-melting glass powder.

In the paste composition of the present invention, it is preferable that the powder further contains an inorganic filler.
In addition, the fired body of the present invention is obtained by firing the paste composition described above.
In the paste composition of the present invention, it is preferable that the low melting glass powder is a dielectric glass powder.

Moreover, in the paste composition of this invention, it is suitable that the said low melting glass powder is glass powder for sealing.
Moreover, in the paste composition of this invention, it is suitable that the said low melting glass powder is a partition material glass powder.
Moreover, in the paste composition of this invention, it is suitable that the said powder contains fluorescent substance powder.

In the paste composition of the present invention, it is preferable that the powder contains a carbon nanomaterial.
The dielectric layer of the present invention is characterized by being obtained by firing the above paste composition.
Moreover, the sealing body of this invention is obtained by baking the above-mentioned paste composition, It is characterized by the above-mentioned.

Moreover, the partition of this invention is obtained by baking the above-mentioned paste composition.
Moreover, the phosphor of the present invention is obtained by firing the paste composition described above.
The electron emitter of the present invention is obtained by firing the paste composition described above.

  The flat panel display component of the present invention is characterized by being obtained by firing the above paste composition.

Since the paste composition of the present invention contains a polyurethane resin obtained by the reaction of a specific polyoxyalkylene glycol and diisocyanate, a solvent, and a powder, it is possible to ensure a good dispersed state or dissolved state. And a good paste state can be secured.
When the paste composition is applied by, for example, screen printing, the paste composition is quickly extruded from the screen to the printing surface, and stringing is prevented from occurring between the screen and the printing surface. it can. As a result, the paste composition can be applied on a smooth surface.

And if a paste composition is baked, in the obtained baked body, generation | occurrence | production of a crack and a flaw can be prevented and a favorable surface state can be ensured. Moreover, generation | occurrence | production of the residue after baking can be prevented effectively.
And since the components for flat panel displays of this invention consist of an above-mentioned sintered body, a favorable surface state can be ensured.

In particular, in the dielectric layer of the present invention, the polyurethane resin is less likely to be carbonized during firing, and deterioration of the low-melting glass, which is a dielectric glass powder, is reduced, so that the occurrence of cracks can be more effectively prevented.
Moreover, since the polyurethane resin is less likely to be carbonized during firing and the deterioration of the sealing glass powder is reduced, the sealing body of the present invention can more effectively prevent the occurrence of cracks.

Further, since the partition wall of the present invention contains low melting point glass that is a partition wall material glass powder, the partition wall under the sand blast resist is polished (scraped) in the polishing step when the partition wall is formed by the sand blasting method. ) Oversand can be prevented.
In addition, the phosphor of the present invention can keep the luminance of the phosphor high because the polyurethane resin is hardly carbonized during firing.

  Further, the electron emitter of the present invention can stabilize the electron emission characteristics because the polyurethane resin is hardly carbonized during firing.

The paste composition of the present invention contains a polyurethane resin, a solvent, and a powder.
The polyurethane resin is obtained by reacting at least polyoxyalkylene glycol and diisocyanate.
In the present invention, the polyoxyalkylene glycol has an alkylene group having 2 to 3 carbon atoms and an alkylene group having 4 to 6 carbon atoms.

Examples of the alkylene group having 2 to 3 carbon atoms include an ethylene group, a propylene group (methylethylene group), and a trimethylene group. The alkylene group having 2 to 3 carbon atoms is contained in the polyoxyalkylene glycol in an amount of 1 to 85 mol%, preferably 5 to 80 mol%, more preferably 10 to 75 mol%. Yes.
Examples of the alkylene group having 4 to 6 carbon atoms include linear alkylene groups such as tetramethylene, pentamethylene, and hexamethylene, and examples include 2-methyl-trimethylene, 1,1-dimethylethylene, 1,2- Such as dimethylethylene, 2-methyl-tetramethylene, 1,1-dimethyltrimethylene, 2,2-dimethyltrimethylene, 2-methyl-pentamethylene, 1,1-dimethyltetramethylene, 2,2-dimethyltetramethylene, etc. Examples include branched alkylene groups. If the alkylene group having 4 to 6 carbon atoms is contained, the solubility of the polyurethane resin in a solvent having a low polarity is improved, so that the polyurethane resin can be used as a good paste material. The alkylene group having 4 to 6 carbon atoms is contained in polyoxyalkylene glycol in an amount of 15 to 99 mol%, preferably 20 to 95 mol%, more preferably 25 to 90 mol%. Yes.

In order to obtain the above polyoxyalkylene glycol, for example, the alkylene oxide having 2 to 3 carbon atoms and the alkylene oxide having 4 to 6 carbon atoms are mixed with the stoichiometric ratio (moles) of each alkylene group described above. The alkylene oxide is copolymerized at a ratio such that the ratio of
Examples of the alkylene oxide having 2 to 3 carbon atoms include ethylene oxide (also known as ethylene oxide), propylene oxide, and trimethylene oxide. These can be used alone or in combination of two or more. Of these, ethylene oxide (ethylene oxide) is preferable.

  Examples of the alkylene oxide having 4 to 6 carbon atoms include linear alkylene oxides such as tetramethylene oxide (also known as tetrahydrofuran), pentamethylene oxide, and hexamethylene oxide, and examples thereof include 2-methyl-trimethylene oxide, 1, 1-dimethylethylene oxide, 1,2-dimethylethylene oxide, 2-methyl-tetramethylene oxide, 1,1-dimethyltrimethylene oxide, 2,2-dimethyltrimethylene oxide, 2-methyl-pentamethylene oxide, 1, Examples include branched alkylene oxides such as 1-dimethyltetramethylene oxide and 2,2-dimethyltetramethylene oxide. These can be used alone or in combination of two or more. Of these, tetramethylene oxide (tetrahydrofuran) and 2-methyl-tetramethylene oxide are preferable.

The above-described polymerization of the alkylene oxide may be a known method (for example, living polymerization with an alkali metal or the like). The polymerization conditions are such that the polymerization temperature is, for example, 50 to 150 ° C., preferably 80 to 120. ° C. The polymerization time is, for example, 1 to 10 hours, preferably 2 to 7 hours.
Examples of the structure of the polyoxyalkylene glycol copolymer obtained as described above include a random structure and a block structure, and a random structure is preferable.

  Specific examples of the polyoxyalkylene glycol include linear copolymer such as ethylene oxide / tetramethylene oxide copolymer, ethylene oxide / pentamethylene oxide copolymer, ethylene oxide / hexamethylene oxide copolymer, etc. , Ethylene oxide / 2-methyl-trimethylene oxide copolymer, ethylene oxide / 1,1-dimethylethylene oxide copolymer, ethylene oxide / 1,2-dimethylethylene oxide copolymer, etc. Is mentioned. Among these, Preferably, a linear copolymer is mentioned, More preferably, an ethylene oxide tetramethylene oxide copolymer is mentioned.

  The number average molecular weight (Mn) of the polyoxyalkylene glycol is, for example, 400 or more, preferably 1000 or more, more preferably 1500 or more, and usually, for example, 100,000 or less, preferably 20000 or less, More preferably, it is 15000 or less. The number average molecular weight (Mn) of the polyoxyalkylene glycol is determined according to JIS K1557-1 (2007) “Plastic-Polyurethane Raw Material Polyol Test Method—Part 1: Determination of Hydroxyl Value”. And the number of functional groups of the initiator).

  When the polyoxyalkylene glycol has a number average molecular weight of 400 or more, a polyurethane resin having a length sufficient to obtain a uniform printed surface can be obtained. When the number average molecular weight of the polyoxyalkylene glycol is 100,000 or less, it is possible to obtain a polyurethane resin that can sufficiently accelerate the polymerization reaction and can substantially prevent the occurrence of stringing. In particular, if the number average molecular weight of the polyoxyalkylene glycol is 2000 or more, the blending ratio of diisocyanate can be reduced, and the amount of residual carbon when the resulting paste composition is fired at 400 ° C. or less is extremely reduced, A paste composition having higher thermal decomposability can be obtained.

These polyoxyalkylene glycols can be used alone or in combination of two or more.
In the present invention, examples of the diisocyanate include known diisocyanates usually used in the production of polyurethane resins.
Specific examples of the diisocyanate include aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate.

  Examples of the aliphatic diisocyanate include methylene diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, 1-methylethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 2-methylbutane-1,4-diisocyanate, hexamethylene diisocyanate (HMDI), hepta. Methylene diisocyanate, 2,2′-dimethylpentane-1,5-diisocyanate, lysine diisocyanatomethyl ester (LDI), octamethylene diisocyanate, 2,5-dimethylhexane-1,6-diisocyanate, 2,2,4- Trimethylpentane-1,5-diisocyanate, nonamethylene diisocyanate, 2,4,4-trimethylhexane-1,6-diisocyanate DOO, decamethylene diisocyanate, undecamethylene diisocyanate, dodecamethylene diisocyanate, tridecamethylene diisocyanate, tetradecamethylene diisocyanate, pentamethylene decamethylene diisocyanate, hexamethylene decamethylene diisocyanate, trimethylhexamethylene diisocyanate.

Examples of the alicyclic diisocyanate include cyclohexane-1,2-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1-methylcyclohexane-2,4-diisocyanate, and 1-methylcyclohexane-2. , 6-diisocyanate, 1-ethylcyclohexane-2,4-diisocyanate, 4,5-dimethylcyclohexane-1,3-diisocyanate, 1,2-dimethylcyclohexane-ω, ω'-diisocyanate, 1,4-dimethylcyclohexane- ω, ω′-diisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate, dicyclohexylmethylmethane-4,4′-diisocyanate, dicyclohexyldimethyl Rumethane-4,4′-diisocyanate, 2,2′-dimethyldicyclohexylmethane-4,4′-diisocyanate, 3,3′-dimethyldicyclohexylmethane-4,4′-diisocyanate, 4,4′-methylene-bis ( Isocyanatocyclohexane), isopropylidenebis (4-cyclohexylisocyanate) (IPCI), 1,3-bis (isocyanatomethyl) cyclohexane, hydrogenated tolylene diisocyanate (H-TDI), hydrogenated 4,4′-diphenylmethane diisocyanate (H ₁₂ MDI), hydrogenated xylylene diisocyanate (H ₆ XDI), norbornane diisocyanatomethyl (NBDI) and the like.

  Examples of the aromatic diisocyanate include 1,3- and 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate (2,4-TDI), 1-methyl-2,6-phenylene diisocyanate (2 , 6-TDI), 1-methyl-2,5-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1,3-dimethyl-2,4-phenylene diisocyanate, 1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, m-xylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene Diisocyanate, 1-methyl-3,5-diethylbenzene-2,4-diisocyanate, 3-methyl-1,5-diethylbenzene-2,4-diisocyanate, 1,3,5-triethylbenzene-2,4-diisocyanate, naphthalene -1,4-diisocyanate, naphthalene-1,5-diisocyanate, 1-methylnaphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, 1,1-dinaphthyl-2, 2'-diisocyanate, biphenyl-2,4'-diisocyanate, biphenyl-4,4'-diisocyanate, 1,3-bis (1-isocyanato-1-methylethyl) benzene, 3,3'-dimethylbiphenyl-4, 4'-diisocyanate, diphenylmethane , 4'-diisocyanate (MDI), diphenylmethane-2,2'-diisocyanate, diphenylmethane-2,4'-diisocyanate, and the like xylylene diisocyanate (XDI).

These diisocyanates can be used alone or in combination of two or more. Of these diisocyanates, HMDI and MDI are preferable.
In the present invention, in the polymerization of the polyurethane resin, a comb diol represented by the following general formula (1) and / or a comb diol represented by the following general formula (2) (hereinafter referred to as a comb diol unless otherwise specified) , Which is a generic name of comb-shaped diols represented by the general formulas (1) and (2)) can be reacted together with the above-described reaction components (polyoxyalkylene glycol and diisocyanate). That is, the polyurethane resin can be obtained by reacting polyoxyalkylene glycol and diisocyanate as essential reaction components with a comb-shaped diol as an optional reaction component.

(In the formula, R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms or a nitrogen-containing hydrocarbon group which may be substituted with a halogen atom. R ² and R ³ are the same or different from each other. And a hydrocarbon group having 4 to 21 carbon atoms which may be substituted with a halogen atom, and Y ¹ and Y ² are the same as or different from each other, and represent a hydrogen atom, a methyl group or CH _2. Represents a Cl group, Z ¹ and Z ² are the same or different from each other, and represent an oxygen atom, a sulfur atom or a CH ₂ group, and n ¹ and n ² are the same or different from each other. Differently, an integer of 0 to 15 is shown.)

(In the formula, R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom. R ⁵ and R ⁶ are the same or different from each other, R 4 represents an optionally substituted hydrocarbon group having 4 to 21 carbon atoms, R ⁷ represents an alkylene group having 2 to 4 carbon atoms, and Y ³ , Y ⁴ and Y ^5. Are the same or different from each other and represent a hydrogen atom, a methyl group or a CH ₂ Cl group, and Z ³ and Z ⁴ are the same or different from each other and represent an oxygen atom, a sulfur atom or a CH ₂ group. And k represents an integer of 0 to 15. n ³ and n ⁴ are the same or different from each other and represent an integer of 0 to 15.)
In the general formula (1), examples of the hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom represented by R ¹ include methyl, ethyl, propyl, iso-propyl, butyl, and iso-butyl. , Sec-butyl, tert-butyl, pentyl, iso-pentyl, sec-pentyl, hexyl, heptyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosanyl, etc. Alkyl groups such as cycloalkyl groups such as cyclopentyl and cyclohexyl groups, such as alkenyl groups such as vinyl, 2-propenyl (allyl) and 1-propenyl, such as aryl groups such as phenyl, tolyl and naphthyl, such as benzyl Aralkyl as such And the like. Also, some or all of the hydrogen atoms bonded to these carbon atoms are substituted with halogen atoms (fluorine, chlorine, bromine, iodine, etc.), for example, chloromethyl group, 3,3,3-trifluoropropyl Examples thereof include an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms selected from a group and the like.

In the general formula (1), examples of the nitrogen-containing hydrocarbon group include dialkylaminoalkyl groups such as N, N-dibutylaminohexyl.
In the general formula (1), examples of the hydrocarbon group having 4 to 21 carbon atoms which may be substituted with a halogen atom represented by R ² and R ³ include unsubstituted or substituted hydrocarbon represented by R ¹ . Among the hydrocarbon groups, those obtained by removing hydrocarbon groups having 1 to 3 carbon atoms can be mentioned.

In the general formula (1), n ¹ is preferably 0 when Z ¹ is a sulfur atom or a CH ₂ group. N ² is preferably 0 when Z ² is a sulfur atom or a CH ₂ group.
In the general formula (2), examples of the hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom represented by R ⁴ include an unsubstituted or substituted hydrocarbon group represented by R ¹ described above. The same thing is mentioned.

In the general formula (2), examples of the hydrocarbon group having 4 to 21 carbon atoms which may be substituted with a halogen atom represented by R ⁵ and R ⁶ include those represented by R ² and R ³ described above. The thing similar to an unsubstituted or substituted hydrocarbon group is mentioned.
In the general formula (2), examples of the alkylene group having 2 to 4 carbon atoms represented by R ⁷ include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, 2-methyl-trimethylene, 1,1- Examples thereof include dimethylethylene and 1,2-dimethylethylene.

In the general formula (2), n ³ is preferably 0 when Z ³ is a sulfur atom or a CH ₂ group. N ⁴ is preferably 0 when Z ⁴ is a sulfur atom or a CH ₂ group.
The above comb-shaped diol can be prepared in accordance with, for example, the method described in Examples of Japanese Patent Application Laid-Open No. 2000-297133.

The polyurethane resin is obtained by reacting the above-described polyoxyalkylene glycol, diisocyanate, and, if necessary, a comb-shaped diol.
In this reaction, the equivalent ratio of the isocyanate group of the diisocyanate (NCO group / OH group) to the hydroxyl group of the polyoxyalkylene glycol and, if necessary, the comb-shaped diol contained as a reaction component is, for example, 0.8 to 1.1, preferably 0.85 to 1.05.

The reaction conditions may be those usually used for the production of polyurethane resins. For example, in a nitrogen atmosphere, polyoxyalkylene glycol, diisocyanate, and, if necessary, comb-shaped diol, so as to have the above equivalent ratio. For example, it is polymerized at 50 to 120 ° C. for 3 to 15 hours.
Further, in this reaction, for example, a polymerization solvent such as toluene can be blended and solution polymerization can be performed, or the above components can be bulk polymerized as they are without blending the polymerization solvent. In addition, the mixing ratio of the polymerization solvent in the case of solution polymerization is, for example, 300 to 1000 parts by weight with respect to 100 parts by weight of the total amount of polyoxyalkylene glycol and diisocyanate (including a comb diol if necessary).

Furthermore, in this reaction, a catalyst (for example, a tin-based catalyst such as dibutyltin dilaurate (DBTDL) or an amine-based catalyst such as monoethanolamine) or an antioxidant (for example, di-tert- Additives such as butylhydroxytoluene (BHT) and the like can be added.
In addition, when a polymer is obtained by solution polymerization, the solvent can be distilled off by drying under reduced pressure or the like. When the polymer is obtained by bulk polymerization, the polymer is pulverized by, for example, a pulverizer such as a mill, and then the coarse pulverized product is removed by sieving to obtain an average particle size of, for example, 100 to It can also be adjusted to 800 μm.

Thereby, a polyurethane resin can be obtained.
The weight average molecular weight of the polyurethane resin thus obtained is, for example, 10,000 to 2,000,000, and preferably 100,000 to 1,000,000 from the viewpoint of printing characteristics. The weight average molecular weight of the polyurethane resin is a weight average molecular weight based on a calibration curve of polystyrene by gel permeation chromatography.

  If the polyurethane resin has a weight average molecular weight of 10,000 or more, a paste composition (in particular, a dielectric paste composition, a sealing paste composition, a partition material paste composition, a phosphor paste composition, and a carbon nanomaterial paste composition described later) The viscosity of the product can be increased. Further, if the weight average molecular weight is 2000000 or less, a paste composition (in particular, a dielectric paste composition, a sealing paste composition, a partition material paste composition, a phosphor paste composition, and a carbon nanomaterial paste composition) The occurrence of stringing between the screen and the printing surface during screen printing can be prevented. That is, in the above range, the printing characteristics of the paste composition can be improved.

The hydroxyl value of the polyurethane resin is, for example, 0 to 11.3, preferably 0 to 1.2.
Moreover, the isocyanate group content of a polyurethane resin is 0-0.55 weight%, for example, Preferably, it is 0-0.51 weight%.
In the present invention, the solvent is not particularly limited as long as it can dissolve the polyurethane resin and can disperse the powder. Examples of such a solvent include alcohols having 3 to 12 carbon atoms such as terpineol (α-, β-, γ-, I-, IV-terpineol, etc.), dodecanol, 2-phenoxyethanol, isopropanol, butanol, etc. Diols such as 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, ketones such as propylene carbonate, such as dimethyl phthalate, phthalic acid Esters having 3 to 12 carbon atoms such as diethyl, dipropyl phthalate, dioctyl phthalate, ethyl acetate, butyl acetate, butyl carbitol and butyl carbitol, for example, ethers such as tetrahydrofuran, for example, toluene, xylene, benzyl Aromatic compounds such as alcohol, - pyrrolidones such as methyl pyrrolidone (NMP), for example, dimethylformamide, an aprotic polar solvent such as dimethyl sulfoxide and the like.

In addition, the solvent is preferably less affected by the emulsion of screen-making at the time of screen printing, and includes a low-polarity one that can more uniformly disperse a low-polarity powder such as a carbon nanomaterial, More specifically, the solubility parameter (SP value) is, for example, 8 to 11 (cal / cm ³ ) ^1/2 .
Among the solvents described above, examples of the solvent within the range of the solubility parameter include alcohols having 4 to 12 carbon atoms such as terpineol, dodecanol, and butanol, butyl carbitol acetate, butyl carbitol, and diethyl phthalate. Examples thereof include esters having 4 to 12 carbon atoms and pyrrolidones such as NMP. Of these, terpineol, butyl carbitol acetate, and NMP are preferable.

In the present invention, the powder can be appropriately selected according to the use of the fired body described later, and examples thereof include a low-melting glass powder, a phosphor powder, and a carbon nanomaterial.
The low melting glass powder is a glass powder that can be heat-sealed at a temperature at which the plate glass (soda lime glass) is not thermally deformed (for example, 600 ° C. or less) or at a temperature lower than the heat resistance temperature of the plate glass (for example, 750 to 800 ° C.). For example, it is used as sealing glass, sealing glass, or solder glass. Such a low-melting glass powder usually has a glass transition point (Tg) of 250 ° C. or higher and 600 ° C. or lower.

Further, the low melting point glass powder has a maximum particle diameter D _max of, for example, 100 μm or less, preferably 1 to 50 μm. If the maximum particle diameter D _max is 100 μm or less, the paste composition can be reliably applied by screen printing.
Examples of the low melting glass powder include oxide glass powder, and more specifically, PbO—B ₂ O ₃ —SiO ₂ glass, PbO—B ₂ O ₃ —SiO ₂ —CaO glass, PbO—B. ₂ O ₃ —SiO ₂ —ZnO—CaO glass, PbO—B ₂ O ₃ —SiO ₂ —ZnO—BaO—CaO glass, PbO—B ₂ O ₃ —SiO ₂ —ZnO—BaO—CaO—Bi ₂ O ₃ based _{glass, ZnO-Bi 2 O 3 -B} 2 O 3 -SiO 2 -CaO-SrO-BaO -based glass, B ₂ O ₃ -PbO type glass, B ₂ O ₃ -PbO-ZnO-based glass, Cu ₂ O —P ₂ O ₅ glass, P ₂ O ₅ —SnO glass, P ₂ O ₅ —SnO—B ₂ O ₃ glass, BaO—ZnO—B ₂ O ₃ —SiO ₂ glass, ZnO—Bi ₂ O ₃ such as a powder of -B ₂ O ₃ -SiO ₂ based glass may be mentioned .

The low melting point glass powder is used as a dielectric glass powder, a sealing glass powder, and a partition wall glass powder, respectively, when the fired body is used as a dielectric layer, a sealing body, and a partition wall, which will be described later.
The dielectric glass powder is used, for example, in a plasma display panel (PDP), and more specifically, used to form a dielectric layer of the PDP.

  Such a dielectric glass powder has a voltage resistance without causing defects at a firing temperature (for example, 400 to 600 ° C., preferably 530 to 580 ° C.) at the firing of the paste composition containing the dielectric glass powder. A glass powder capable of forming a high dielectric layer, and the glass transition point (Tg) of the dielectric glass powder is, for example, 600 ° C. or lower and 300 ° C. or higher, and preferably 500 ° C. or lower and 390 ° C. or higher. is there.

Such dielectric glass powder, for _{example, PbO-B 2 O 3 -SiO} 2 based _{glass, PbO-B 2 O 3 -SiO} 2 -CaO -based _{glass, PbO-B 2 O 3 -SiO} 2 -ZnO- CaO glass, PbO—B ₂ O ₃ —SiO ₂ —ZnO—BaO—CaO glass, PbO—B ₂ O ₃ —SiO ₂ —ZnO—BaO—CaO—Bi ₂ O ₃ glass, ZnO—Bi ₂ O _{3 -B 2 O 3 -SiO 2 -CaO} -SrO-BaO -based powder of the glass and the like, preferably, powders of _{PbO-B 2 O 3 -SiO 2} -CaO -based glass.

  The sealing glass powder is, for example, a sealing glass powder used for sealing a flat panel display (FPD) or an IC package, and more specifically, a sealing glass powder, a sealing glass powder, or a frit. Also called glass powder or the like, it is glass powder for sealing (sealing) an opening (through hole) of an FPD such as a PDP or a field emission display (FED), or for sealing an IC package.

Such a glass powder for sealing is a glass powder that can be sealed at a sealing treatment temperature (for example, 410 to 480 ° C.) by baking a paste composition containing the glass powder. The transition point (Tg) is, for example, 400 ° C. or lower, preferably 350 ° C. or lower, and more preferably 330 ° C. or lower, 250 ° C. or higher.
Examples of such sealing glass powder include B ₂ O ₃ —PbO glass, PbO—B ₂ O ₃ —SiO ₂ glass, B ₂ O ₃ —PbO—ZnO glass, Cu ₂ O—P. ₂ O ₅ glass, P ₂ O ₅ —SnO glass, P ₂ O ₅ —SnO—B ₂ O ₃ glass powder, etc., preferably P ₂ O ₅ —SnO—B ₂ O ₃ Glass powder can be mentioned.

As the glass powder for sealing, a general commercial product is used, for example, frit glass (AFS1304M, ASF1200M, IWF2300M, ASF1307, manufactured by Asahi Glass Co., Ltd.) or the like.
The partition wall material glass powder is used in, for example, a PDP, and more specifically, is a glass powder that forms a glass component of a partition wall material glass paste for forming a partition wall that partitions a discharge space. The softening point of such partition wall glass powder is, for example, 450 ° C. or higher and 650 ° C. or lower. The thermal expansion coefficient is, for example, 60 × 10 ^{−7 to} 90 × 10 ⁻⁷ (1 / ° C.). Further, the average particle diameter D ₅₀ of the barrier rib material a glass powder, e.g., a 1 to 7 [mu] m, maximum particle diameter D _max is, for example, 5 to 30 [mu] m.

Examples of the partition wall material glass powder include PbO—B ₂ O ₃ —SiO ₂ glass, BaO—ZnO—B ₂ O ₃ —SiO ₂ glass, and ZnO—Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ glass. glass powder and the like, preferably, powders of PbO-B ₂ O ₃ -SiO ₂ based glass.
The phosphor powder is a powder used when the fired body is a phosphor to be described later, and is used for PDP and FED. Examples thereof include a blue phosphor powder, a red phosphor powder, and a green phosphor powder.

Examples of the blue phosphor powder include BaMgAl ₁₄ O ₂₄ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, and SrMg (SiO ₄ ) ₂ : Eu powder. Examples of the red phosphor powder include (Y, Gd) BO ₃ : Eu, Y ₂ O ₃ : Eu, Y (P, V) O ₄ : Eu, (Y, Gd) ₂ O ₃ : Eu powder, etc. Is mentioned. Examples of the green phosphor include Zn ₂ SiO ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, YBO ₃ : Tb powder, and the like.

The average particle diameter D ₅₀ of these phosphor powders is, for example, 0.01 to 20 μm, preferably 0.1 to 10 μm.
The carbon nanomaterial is a powder used when the fired body is an electron emitter described later, and is not particularly limited as long as it is a carbon nanomaterial used for FED.
The carbon nanomaterial is a carbon nanoparticle, and has a shape capable of emitting electrons in part. Examples of such a shape include a tube (tube) shape, a spherical shape, a linear shape, a disc shape, Examples include a plate (wall) shape.

Specific examples of the carbon nanomaterial include carbon nanotubes, fullerenes, carbon nanohorns, and carbon nanowalls.
The maximum length of these carbon nanomaterials is, for example, 1 to 200 nm, preferably 10 to 150 nm.
In the paste composition, when a low melting glass powder is used as the powder, the powder can further contain an inorganic filler.

The inorganic filler is optionally blended in the powder and blended to adjust the fluidity and thermal expansion coefficient of the paste composition.
Examples of the inorganic filler exclude the above-described low melting point glass powder, and examples thereof include alumina, α-quartz, titania, zirconia, cordierite, zircon, tin oxide, niobium oxide, zirconium phosphate, willemite, and mullite. .

The average particle diameter D50 of such an inorganic filler is, for example, 0.1 to 100 μm, preferably 1 to ₅₀ μm.
As the inorganic filler, when the dielectric glass powder and / or the partition wall glass powder is contained in the powder as the low melting point glass powder, preferably, alumina, α-quartz, titania, zirconia are used. The inorganic filler preferably includes cordierite, zircon, tin oxide, niobium oxide, zirconium phosphate, willemite, and mullite when the sealing glass powder is contained in the powder as a low melting glass powder.

Further, when a phosphor powder or a carbon nanomaterial is used as the powder, the powder can further contain an inorganic binder material (for example, a low-melting glass powder or a known conductive material).
Furthermore, additives such as a plasticizer, a dispersant, and an antifoaming agent can be added to the paste composition of the present invention at a ratio that does not inhibit the effects of the present invention.

And in order to prepare the paste composition of this invention, the binder resin solution (henceforth a binder resin solution) which consists of a polyurethane resin and a solvent is prepared, and this is mix | blended with the powder prepared separately. .
In order to prepare a binder resin solution, a polyurethane resin and a solvent are charged in a container such as a separable flask at a blending ratio described later, and for example, while heating at 40 to 80 ° C., for 30 to 120 minutes (specifically, , 60 minutes).

The binder resin solution thus obtained contains, for example, 1 to 30% by weight of a polyurethane resin and 70 to 99% by weight of a solvent, for example. The binder resin solution has a viscosity at 20 ° C. of, for example, 20 to 50 Pa · s.
Then, the paste composition of the present invention is obtained by kneading the binder resin solution prepared as described above and the separately prepared powder at a blending ratio described later using a kneader such as a three-roll mill. Can do.

The paste composition thus obtained contains, for example, 30 to 95% by weight of powder, and contains, for example, 5 to 70% by weight of the binder resin solution.
Moreover, when the powder contains at least one selected from dielectric glass powder, sealing glass powder and partition wall glass powder, the paste composition has a viscosity at 20 ° C. of, for example, 1 ˜1000 Pa · s, preferably 5 to 50 Pa · s. When the phosphor powder or the carbon nanomaterial is contained as the powder, the paste composition has a viscosity at 20 ° C. of, for example, 1 to 1000 Pa · s, preferably 10 to 150 Pa · s. . If the viscosity of the paste composition is within the above range, excellent printing characteristics in screen printing of the paste composition can be obtained.

Next, a method for producing the fired body of the present invention using the paste composition of the present invention will be described.
In this method, first, the paste composition is printed on a printing surface by, for example, a screen printer, an applicator, a bar coater, a roll coater, or the like, or a space between parts is filled by, for example, a screen printer, a dispenser, or the like. .

Thereafter, the paste composition is fired. The firing temperature is, for example, 300 to 650 ° C., preferably 350 to 600 ° C., and the firing time is, for example, 0.1 to 5 hours, preferably 0.3 to 4 hours. Thereby, the sintered body of the present invention can be obtained.
Specifically, the fired body is formed as an FPD part such as a PDP part or an FED part, and is preferably formed as a dielectric layer, a sealing body, a partition, a phosphor, or an electron emitter. Note that a fired body formed as a sealing body can also be used as a sealing body for an IC package.

Hereinafter, specific examples of the FPD component will be described in detail.
In the FPD, the dielectric layer is coated with a paste composition containing dielectric glass powder (hereinafter sometimes referred to as a dielectric paste composition) on a glass substrate provided with electrodes, for example, a back glass substrate. Is formed.
In order to form the dielectric layer, first, a dielectric paste composition is prepared.

In order to prepare the dielectric paste composition, glass powder and an inorganic filler to be blended if necessary and a binder resin solution are blended and mixed uniformly. The binder resin solution contains, for example, 1 to 30% by weight of polyurethane resin and 70 to 99% by weight of solvent, for example.
The dielectric paste composition thus obtained contains, for example, 40 to 80% by weight, preferably 55 to 65% by weight of dielectric glass powder, and preferably contains 10% by weight or less of inorganic filler, for example. Contains 5% by weight or less, and contains a binder resin solution, for example, 20 to 60% by weight, preferably 35 to 45% by weight. If the blending ratio of the dielectric glass powder is less than 40% by weight, a dielectric having sufficient insulation and transparency may not be obtained. On the other hand, when the blending ratio of the dielectric glass powder exceeds 80% by weight, the fluidity of the dielectric paste composition is lowered, and uniform coating may be difficult.

  Next, the obtained dielectric paste composition is applied onto a glass substrate using, for example, a screen printer, an applicator, a bar coater, a roll coater, etc., and then heated with a hot air dryer or the like, for example, 80 to Dry the solvent at 150 ° C. The thickness after drying (the thickness of the dried body) is, for example, 30 to 500 μm. Then, a dry body is baked at 500-600 degreeC, for example for 5 to 15 minutes, for example.

Thereby, a dielectric layer can be formed. In addition, the thickness of a dielectric material layer is 20-100 micrometers, for example.
The sealing body is filled with a paste composition containing a sealing glass powder (hereinafter sometimes referred to as a sealing paste composition) between the front glass substrate and the back glass substrate of the PDP. It is a filling body (filling layer) formed by.

And in order to form a sealing body, first, the sealing paste composition is prepared.
In order to prepare the paste composition for sealing, glass powder for sealing, an inorganic filler to be blended if necessary, and a binder resin solution are blended and mixed uniformly. The binder resin solution contains, for example, 1 to 30% by weight of polyurethane resin and 70 to 99% by weight of solvent, for example.

  The sealing paste composition thus obtained contains, for example, 30 to 95% by weight of a sealing glass powder, contains an inorganic filler, for example, 50% by weight or less, and contains a binder resin solution, for example. 5 to 30% by weight. If the blending ratio of the glass powder for sealing is less than 30% by weight, the sealing body may have many defects and sealing may be insufficient. On the other hand, if the blending ratio of the glass powder for sealing exceeds 95% by weight, the fluidity of the paste composition for sealing may be lowered and processing may be difficult.

  Next, the obtained paste composition for sealing is filled between the front glass substrate and the rear glass substrate of the PDP using, for example, a screen printer, a dispenser, or the like. Next, the solvent is dried at, for example, 80 to 150 ° C. with a hot air dryer or the like. Thereafter, the dried body is fired at, for example, 400 to 500 ° C., for example, for 5 to 15 minutes. In this firing, the space between the PDP substrates is sealed while the polyurethane resin in the sealing paste composition is decomposed.

Thereby, a sealing body can be formed. In addition, as an atmosphere (baking atmosphere) when baking a dry body, either an air atmosphere (oxygen atmosphere) or a nitrogen atmosphere may be sufficient.
Then, PDP can be manufactured by enclosing a low-pressure Xe-containing Ne gas or the like into a rare gas atmosphere.

In the FPD, the barrier ribs are formed on a glass substrate (for example, a rear glass substrate) provided with electrodes and a dielectric layer as rib-like patterns that are spaced apart from each other so as to partition the discharge space. The
In order to form the partition walls, first, a paste composition containing the partition wall material glass powder (hereinafter sometimes referred to as partition wall material paste composition) is prepared.

In order to prepare the partition wall material paste composition, first, the partition wall material glass powder and the inorganic filler to be blended if necessary and the binder resin solution are blended and mixed uniformly. The binder resin solution contains, for example, 1 to 30% by weight of polyurethane resin and 70 to 99% by weight of solvent, for example.
The partition wall material paste composition thus obtained contains, for example, 30 to 80% by weight of the partition wall glass powder, contains an inorganic filler, for example, 1 to 40% by weight as necessary, and contains a binder resin solution. For example, it contains 5 to 30% by weight.

Next, partition walls are formed by using the obtained partition material paste composition by, for example, a method mainly using a sand blasting method or a method mainly using screen printing. Preferably, the partition walls are formed by a method mainly using a sand blast method.
In order to form the partition by a method mainly using the sandblast method, first, the partition material paste composition is applied to the entire upper surface of the glass substrate by a known coating method such as screen printing. Next, the solvent is dried at, for example, 80 to 150 ° C. with a hot air dryer or the like to obtain a dried product. The thickness of the dried body is, for example, 50 to 200 μm. Next, a dry film resist is laminated on the dried body, exposed in a predetermined pattern, and developed to form a sandblast resist having a predetermined pattern. Thereafter, the dry body (unnecessary portion) exposed from the sandblast resist is removed by polishing by a sandblast method. Then, this is baked at 500-600 degreeC, for example. By this baking, the sandblast resist is decomposed and removed.

On the other hand, in order to form barrier ribs by a method mainly using screen printing, for example, a barrier rib glass paste composition is first formed directly on the substrate by a plurality of screen printings. Next, drying is performed in the same manner as described above to obtain a dried product. Then, after removing unnecessary portions of the dried body, such as a comb-shaped blade, firing is performed.
In this way, a partition wall can be formed.

In the PDP or FED, the phosphor is provided on a glass substrate (back glass substrate) and in a discharge space partitioned by a partition wall. The phosphor provided in the discharge space emits fluorescence by light rays (such as ultraviolet rays) generated from a rare gas such as a low-pressure Xe-containing Ne gas sealed in the discharge space.
In order to form the phosphor, first, a paste composition (phosphor paste composition) containing the phosphor powder is prepared.

  In order to prepare the phosphor paste composition, the phosphor and the binder resin solution are blended and mixed uniformly. The binder resin solution contains, for example, 2 to 20% by weight of a polyurethane resin, and contains 80 to 98% by weight of a solvent, for example. When the binder resin solution optionally contains a conductive material, the blending ratio is, for example, 50% by weight or less with respect to the binder resin solution.

The phosphor paste composition thus obtained contains, for example, 30 to 70% by weight of the phosphor powder, and contains, for example, 30 to 70% by weight of the binder resin solution.
Next, the phosphor paste composition is filled between the barrier ribs formed on the glass substrate of the PDP using, for example, a screen printer or a dispenser. Next, the solvent is dried at, for example, 80 to 150 ° C. with a hot air dryer or the like. Thereafter, the dried body is fired at, for example, 400 to 500 ° C., for example, for 5 to 15 minutes. In firing, the space between the partition walls is filled while the polyurethane resin in the paste composition is decomposed.

Thereby, a phosphor can be formed.
After that, the separately manufactured front glass substrate and the above-mentioned back plate member are sealed (sealed) with a known sealing material (for example, low melting point glass), and rare gas (low pressure Xe-containing Ne gas, etc.) is enclosed. Thus, the FDP can be manufactured.
The electron emitter is provided on the cathode glass substrate in the FED including the cathode glass substrate and the anode glass substrate. Specifically, the electron emitter is disposed on a cathode electrode formed on a cathode glass substrate.

In order to form an electron emitter, first, a paste composition containing a carbon nanomaterial (hereinafter sometimes referred to as a carbon nanomaterial paste composition) is prepared.
In order to prepare the carbon nanomaterial paste composition, the carbon nanomaterial and the binder resin solution are blended and mixed uniformly. In addition, the binder resin solution contains 2 to 20% by weight of polyurethane resin and 80 to 98% by weight of solvent, for example. Moreover, when a binder resin solution contains an inorganic binder material and an electroconductive material arbitrarily, the mixture ratio is 50 weight% or less with respect to a binder resin solution, for example.

The carbon nanomaterial paste composition contains, for example, 10 to 50% by weight of the carbon nanomaterial and 30 to 70% by weight of the binder resin solution.
Next, the obtained carbon nanomaterial paste composition is screen-printed in a predetermined pattern using, for example, a screen printer on a cathode glass substrate. Next, the solvent is dried at, for example, 80 to 150 ° C. with a hot air dryer or the like. Thereafter, the dried body is baked, for example, at 350 to 400 ° C., for example, for 5 to 15 minutes.

In this firing, the electron emitter is formed while the polyurethane resin in the paste composition is decomposed.
Thereby, an electron emitter can be formed.
After that, the cathode glass electrode on which the electron emitter is formed and the separately manufactured anode glass substrate are opposed to each other and sealed with a sealing material (for example, low melting point glass powder), and then vacuum-desorbed. The FED can be manufactured by taking care.

And since the paste composition of this invention contains the polyurethane resin obtained by reaction of specific polyoxyalkylene glycol and diisocyanate, a solvent, and a powder, it ensures a favorable dispersion state or melt | dissolution state. And a good paste state can be secured.
In addition, since the paste composition is excellent in printing characteristics, for example, when the paste composition is applied by screen printing, the paste composition is quickly extruded from the screen to the printing surface, and the screen and the printing surface. It is possible to prevent stringing from occurring between the two. As a result, the paste composition can be applied on a smooth surface.

And if a paste composition is baked, in the obtained baked body, generation | occurrence | production of a crack and a flaw can be prevented and a favorable surface state can be ensured. Moreover, generation | occurrence | production of the residue after baking can be prevented effectively.
And since the components for flat panel displays of this invention consist of an above-mentioned sintered body, a favorable surface state can be ensured.

In particular, in the dielectric layer of the present invention, the polyurethane resin is less likely to be carbonized during firing, and deterioration of the low-melting glass, which is a dielectric glass powder, is reduced, so that the occurrence of cracks can be more effectively prevented.
Moreover, since the polyurethane resin is less likely to be carbonized during firing and the deterioration of the sealing glass powder is reduced, the sealing body of the present invention can more effectively prevent the occurrence of cracks.

Since the partition wall of the present invention contains low melting point glass which is a partition wall material glass powder, the partition wall under the sand blast resist is polished (scraped) in the polishing step when the partition wall is formed by the sand blasting method. Sand can be prevented.
In addition, since the phosphor of the present invention is hard to carbonize the polyurethane resin during firing, the luminance of the fluorescence can be kept high.

  Further, the electron emitter of the present invention can stabilize the electron emission characteristics because the polyurethane resin is hardly carbonized during firing.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples and comparative examples.
The measurement is based on the following example.
Average particle size D ₅₀ ... Laser diffraction scattering particle size distribution measurement method Weight average molecular weight ... Gel permeation chromatography
(Based on polystyrene calibration curve)
・ Mobile phase Tetrahydrofuran (THF)
・ Use column Plgel GUARD (nothing)
5 μmMixed-C (3)
・ System used: Alliance (Waters)
.. 2410 differential refraction detector (manufactured by Waters)
..996 type multi-wavelength detector (manufactured by Waters)
..Millennium data processor (Waters)
Thread length ......... Thread length measured by NEVA METER IMI0501 manufactured by Ishikawa Iron Works Dielectric Layer Example 1
(Polyurethane resin A)
In a 1000 ml SUS separable flask, ethylene oxide (EO), tetrahydrofuran (THF) random copolymer (trade name “Polyserine DC3000E” manufactured by NOF Corporation, molar ratio (EO / THF) = 50/50, number average molecular weight 3057, hereinafter referred to as DC3000) was charged and melted at 150 ° C. in a nitrogen atmosphere. This was dried for 3 hours under reduced pressure (400 Pa) while stirring. Residual moisture was 200 ppm.

  Subsequently, the temperature was lowered to 70 ° C., and the flask was filled with 1 atm of nitrogen. An antioxidant (BHT: di-tert-butylhydroxytoluene) was added at 500 ppm based on DC3000. Next, while stirring the inside of the flask, 1.6506 g of hexamethylene diisocyanate (HMDI: manufactured by Mitsui Chemicals Polyurethane Co., Ltd., the same applies hereinafter) was charged (NCO / OH = 1.00 mol / mol).

Next, 120 g of toluene was charged, 0.009 g of a catalyst (DBTDL: dibutyltin dilaurate) was further added, and the mixture was reacted at 70 ° C. for 7 hours. Thereby, a toluene solution of polyurethane resin A was obtained. The weight average molecular weight of the reaction product was 260000.
(Preparation of binder resin solution A)
To the resulting toluene solution of polyurethane resin A, 270 g of terpineol (manufactured by Nippon Terpene Chemical Co., Ltd.) was charged to uniformly dissolve the polyurethane resin, and the remaining toluene was removed under reduced pressure (400 Pa) while stirring these.

Then, the binder resin solution was taken out from the flask and obtained. The string length of this binder resin solution A was measured by a string measuring device (NEVA METER manufactured by Ishikawa Iron Works) and found to be 10.2 mm.
(Preparation of dielectric paste composition A)
In a mixing container, 35 g of binder resin solution A and dielectric glass powder (PbO—B ₂ O ₃ —SiO ₂ —CaO glass, glass transition point Tg: 400 ° C., average particle diameter D ₅₀ : 2 μm, maximum particle diameter D _max : 5 μm) 65 g was added and mixed, and then these were kneaded by a three-roll mill to prepare a dielectric paste composition A.

(Formation of dielectric layer)
Dielectric paste composition A was applied to the entire upper surface of the soda glass plate using a bar coater. The terpineol was dried at 120 ° C. with a hot air dryer and then baked at 550 ° C. for 10 minutes to form a dielectric layer having a thickness of 50 μm.
(Evaluation of dielectric layer)
The formed dielectric layer was measured for surface roughness Ra (based on JIS R1636, the same applies hereinafter) using a stylus type surface roughness meter, and found to be 0.15 μm. Further, when the surface was observed (hereinafter the same) with a scanning electron microscope (SEM) (manufactured by Hitachi, Ltd.), it was confirmed that the surface of the dielectric manipulation was flat.
Example 2
(Preparation of binder resin solution B)
A 200 ml glass separable flask was charged with 50 g of the toluene solution of the polyurethane resin A obtained in Example 1, and the remaining toluene was removed under reduced pressure (400 Pa) while stirring them. Thereafter, 90 g of N-methylpyrrolidone (NMP, manufactured by Kanto Chemical Co., Ltd., the same shall apply hereinafter) was charged and stirred for 1 hour while heating at 60 ° C. to dissolve the polyurethane resin A, thereby obtaining a binder resin solution B.

(Preparation of dielectric paste composition B)
45 g of binder resin solution B, 50 g of dielectric glass powder (PbO—B ₂ O ₃ —SiO ₂ —CaO glass) and 5 g of α-quartz powder (average particle diameter D ₅₀ : 5 μm, the same applies hereinafter) are added to the mixing container. After mixing, a dielectric paste composition B was obtained by kneading with a three-roll mill.

(Formation of dielectric layer)
Dielectric paste composition B was applied to the entire upper surface of the soda glass plate using a bar coater. The NMP was dried at 120 ° C. with a hot air dryer and then baked at 550 ° C. for 10 minutes to form a dielectric layer having a thickness of 30 μm.
(Evaluation of dielectric layer)
When the surface roughness Ra of the formed dielectric layer was measured using a stylus type surface roughness meter, it was 0.20 μm. Further, when the surface was observed, it was confirmed that the surface of the dielectric layer was flat.
Comparative Example 1
(Preparation of binder resin solution C)
A binder resin solution C was prepared by charging 10 g of ethyl cellulose and 90 g of terpineol in a 200 ml glass separable flask and stirring for 1 hour while heating to 60 ° C. to dissolve the ethyl cellulose.

(Preparation of dielectric paste composition C)
Dielectric paste composition is obtained by adding 40 g of binder resin solution C and 60 g of dielectric glass powder (PbO—B ₂ O ₃ —SiO ₂ —CaO glass) to a mixing container and mixing them, and then kneading them with a three-roll mill. Product C was obtained.
(Formation of dielectric layer)
Dielectric paste composition C was applied to the entire upper surface of the soda glass plate using a bar coater. The terpineol was dried at 120 ° C. with a hot air dryer and then baked at 550 ° C. for 10 minutes to form a dielectric layer having a thickness of 50 μm.

(Evaluation of dielectric layer)
With respect to the formed dielectric layer, the surface roughness Ra was measured using a stylus type surface roughness meter and found to be 1.0 μm. Further, when the surface was observed, it was confirmed that the surface of the dielectric layer was a surface with many irregularities. And transparency was impaired due to the unevenness. Furthermore, there were cracks on the surface. Moreover, the foreign material considered to be the residue in baking of ethyl cellulose was confirmed.
Comparative Example 2
(Synthesis of polyurethane resin D)
A 1000 ml SUS separable flask was charged with 200 g of polyoxyethylene glycol (“PEG # 6000” trade name, number average molecular weight 8630, manufactured by Sanyo Chemical Co., Ltd., hereinafter referred to as PEG6000) at 150 ° C. in a nitrogen atmosphere. Melted. This was dried for 3 hours under reduced pressure (400 Pa) while stirring. The water remaining in PEG 6000 was 200 ppm. Subsequently, it cooled to 70 degreeC and filled the inside of a flask with 1 atmosphere of nitrogen.

  Subsequently, 300 ppm of antioxidant (BHT) was added to PEG6000. Next, while stirring in the flask, a comb-shaped diol produced in accordance with the description in Example 1 of JP-A-11-343328 (2-ethylhexyl glycidyl ether at a ratio of 2 mol to 1 mol of 2-ethylhexylamine). 1.90 g of added comb-shaped hydrophobic diol (average molecular weight based on OH number 490) and 4.41 g of HMDI were charged (NCO / OH = 0.98 mol / mol).

Next, when 0.05 g of a catalyst (DBTDL) was added, the viscosity rapidly increased after 10 minutes. The stirring was immediately stopped and the reaction was carried out at 70 ° C. for 2 hours. Then, it was heated to 120 ° C. and kept at a constant temperature for 30 minutes, and then the reaction product was taken out from the flask. The weight average molecular weight of the reaction product was 470000.
The removed polymer was cut into small pieces and allowed to cool. This was cooled with liquid nitrogen and pulverized with a small impact electric mill. The pulverized product was sieved to obtain a polyurethane resin D which is a powder having a particle diameter of 600 μm or less. The average particle size of this polyurethane resin D was 400 μm.

(Preparation of binder resin solution D)
A 200 ml glass separable flask was charged with 6 g of polyurethane resin D and 94 g of terpineol and stirred for 30 minutes while heating at 60 ° C. to dissolve the polyurethane resin D, thereby preparing a binder resin solution D. However, when the binder resin solution D was cooled to room temperature, the polyurethane resin D was precipitated from terpineol, and the binder resin solution D became a white turbid slurry.

(Preparation of dielectric paste composition D)
Dielectric paste composition D was obtained by kneading 40 g of this slurry-like binder resin solution D and 60 g of dielectric glass powder (PbO—B ₂ O ₃ —SiO ₂ —CaO glass) with a three-roll mill.
(Formation of dielectric layer)
Dielectric paste composition D was applied to the entire upper surface of the soda glass plate using a bar coater. The terpineol was dried at 120 ° C. with a hot air dryer and then baked at 550 ° C. for 10 minutes to form a dielectric layer having a thickness of 50 μm.

(Evaluation of dielectric layer)
When the surface roughness Ra of the formed dielectric layer was measured using a stylus type surface roughness meter, it was 2.0 μm. Further, when the surface was observed, it was confirmed that the surface of the dielectric layer was a surface with many irregularities. And transparency was impaired due to the unevenness. Moreover, there were cracks on the surface.

(Discussion)
In the dielectric paste composition A of Example 1 containing the polyurethane resin A within the scope of the present invention and the dielectric paste composition B of Example 2, the deterioration of the dielectric glass powder is reduced even without a plasticizer. It is thought that a flat surface was obtained.
On the other hand, in the dielectric paste composition C of Comparative Example 1 containing ethylcellulose, a flat surface cannot be obtained, and in order to obtain a flat surface, it is necessary to add a plasticizer to the dielectric paste composition C. It is thought that there is.

Furthermore, since the paste composition D contains a polyurethane resin D that does not uniformly dissolve in terpineol, the fired body of the dielectric paste composition D is considered to have a surface with many irregularities.
Moreover, in the dielectric layer of the comparative example 2, since the crack was cracked, a decrease in pressure resistance when used as a PDP dielectric layer was expected.
2. Encapsulant Example 3
(Polyurethane resin E)
In a 1000 ml SUS separable flask, ethylene oxide (EO), tetrahydrofuran (THF) random copolymer (trade name “Polyserine DC1800E” manufactured by NOF Corporation, molar ratio (EO / THF) = 50/50, number average molecular weight 2040 or less, hereinafter referred to as DC1800) was charged and melted at 150 ° C. in a nitrogen atmosphere. This was dried for 3 hours under reduced pressure (400 Pa) while stirring. Residual moisture was 200 ppm.

Subsequently, the temperature was lowered to 70 ° C., and the flask was filled with 1 atm of nitrogen. Antioxidant BHT was added at 500 ppm with respect to DC1800. Next, while stirring the flask, 2.4735 g of HMDI was charged (NCO / OH = 1.00 mol / mol).
Next, 120 g of toluene was charged, 0.009 g of catalyst DBTDL was further added, and the mixture was reacted at 70 ° C. for 7 hours. Thereby, a toluene solution of polyurethane resin A was obtained. The weight average molecular weight of the reaction product was 215000.

(Preparation of binder resin solution E)
To the obtained toluene solution of polyurethane resin E, 270 g of terpineol was charged to uniformly dissolve the polyurethane resin, and the remaining toluene was removed under reduced pressure (400 Pa) while stirring them. Then, the binder resin solution was taken out from the flask and obtained. It was 9.7 mm when the string length of this binder resin solution A was measured with the stringiness measuring apparatus.

(Preparation of sealing paste composition E)
10 g of binder resin solution E, 70 g of glass powder for sealing (P ₂ O ₅ —SnO—B ₂ O ₃ glass, glass transition point Tg: 450 ° C., maximum particle diameter D _max 10 μm, the same shall apply hereinafter) and inorganic filler (oxidation) Tin powder, average particle diameter D ₅₀ : 5 μm, the same applies hereinafter.) After adding 20 g and mixing, a paste composition E for sealing was prepared by kneading with a three-roll mill.

(Screen printing of sealing paste composition E)
The sealing paste composition E was screen-printed in a predetermined pattern on the upper surface of the soda glass plate using a screen (opening diameter: 80 μm, the same applies hereinafter). The thickness of the printed paste composition E for sealing was 100 μm. Moreover, in screen printing, the paste composition did not cause stringing, and the filling property and the screen separation were good. Moreover, when the surface of the printed sealing paste composition E was observed, it was confirmed that the surface was flat.

(Formation of sealing body)
The screen-printed sealing paste composition E was dried in air at 150 ° C. for 10 minutes and then baked in air at 450 ° C. for 10 minutes to form a sealing body having a thickness of 100 μm.
(Evaluation of sealed body)
When the gloss of the surface of the formed sealing body was visually observed, it was confirmed that the surface was glossy and the deterioration of the sealing glass powder was prevented.
Example 4
(Formation of sealing body)
In the formation of the sealing body in Example 3, a sealing body was formed in the same manner as in Example 3 except that the firing temperature was changed to 480 ° C.

(Evaluation of sealed body)
When the gloss of the surface of the formed sealing body was visually observed, it was confirmed that the surface was glossy and the deterioration of the sealing glass powder was prevented.
Example 5
(Preparation of glass paste composition F for sealing)
In a mixing container, 20 g of binder resin solution E prepared in Example 3, 40 g of glass powder for sealing (P ₂ O ₅ —SnO—B ₂ O ₃ glass) and inorganic filler (tin oxide powder, average particle diameter D ₅₀₎ : (5 μm) After adding 40 g and mixing them, a glass paste composition F for sealing was prepared by kneading them with a three-roll mill.

(Screen printing of glass paste composition F for sealing)
The glass paste composition F for sealing was screen-printed with a predetermined pattern on the upper surface of the soda glass plate. The thickness of the printed glass paste composition F for sealing was 80 μm. Moreover, in screen printing, the paste composition did not cause stringing, and the filling property and the screen separation were good. Moreover, when the surface of the printed sealing paste composition E was observed, it was confirmed that the surface was flat.

(Formation of sealing body)
The screen-printed sealing paste composition F was dried in air at 150 ° C. for 10 minutes and then baked in air at 450 ° C. for 10 minutes to form a sealing body having a thickness of 80 μm.
(Evaluation of sealed body)
When the gloss of the surface of the formed sealing body was visually observed, it was confirmed that the surface was glossy and the deterioration of the sealing glass powder was prevented.
Example 6
(Formation of sealing body)
In Example 4, a sealing body was formed in the same manner as in Example 4 except that the firing atmosphere was changed from air to nitrogen.

(Evaluation of sealed body)
When the gloss of the surface of the formed sealing body was visually observed, it was confirmed that the surface was glossy and the deterioration of the sealing glass powder was prevented.
Example 7
(Formation of sealing body)
In Example 5, a sealed body was formed in the same manner as in Example 5 except that the firing atmosphere was changed from air to nitrogen.

(Evaluation of sealed body)
When the gloss of the surface of the formed sealing body was visually observed, it was confirmed that the surface was glossy and the deterioration of the sealing glass powder was prevented.
Comparative Example 3
(Preparation of binder resin solution G)
A binder resin solution G was prepared by charging 5 g of ethyl cellulose and 95 g of terpineol in a 200 ml glass separable flask and stirring for 1 hour while heating at 60 ° C. to dissolve the ethyl cellulose.

(Preparation of glass paste composition G for sealing)
To the mixing container, 10 g of binder resin solution G, 70 g of glass powder for sealing (P ₂ O ₅ —SnO—B ₂ O ₃ glass) and 20 g of inorganic filler (tin oxide powder) were added and mixed. A glass paste composition G for sealing was prepared by kneading with a roll mill.

(Screen printing of glass paste composition G for sealing)
The glass paste composition G for sealing was screen-printed with a predetermined pattern on the upper surface of the soda glass plate. The thickness of the printed glass paste composition G for sealing was 75 μm. In screen printing, stringing did not occur. Moreover, when the surface of the printed glass paste composition G for sealing was observed, it was confirmed that the surface was flat.

(Formation of sealing body)
The screen-printed sealing paste composition G was dried in air at 150 ° C. for 10 minutes and then baked in air at 480 ° C. for 10 minutes to form a sealing body having a thickness of 90 μm.
(Evaluation of sealed body)
When the gloss of the surface of the formed sealing body was visually observed, the surface was not glossy, and the deterioration of the sealing glass powder was confirmed.
Comparative Example 4
(Preparation of binder resin solution H)
A 200 ml glass separable flask was charged with 5 g of acrylic resin (poly (butyl methacrylate)) and 95 g of terpineol and stirred for 1 hour while heating to 60 ° C. to dissolve the acrylic, thereby preparing a binder resin solution H. .

(Preparation of sealing pattern space composition H)
In a mixing container, 10 g of binder resin solution H, 70 g of dielectric glass powder (PbO—B ₂ O ₃ —SiO ₂ —CaO glass) and 20 g of inorganic filler (tin oxide powder) were added and mixed. The glass paste composition H for sealing was prepared by kneading.

(Screen printing of sealing paste composition H)
When the sealing paste composition H was screen-printed in a predetermined pattern on the upper surface of the soda glass plate, stringing occurred, and the screen was not released properly. Further, when the surface of the printed sealing paste composition H was observed, irregularities were confirmed on the surface. The thickness of the printed sealing paste composition H was 100 μm.

(Formation of sealing body)
The screen-printed sealing paste composition H was dried in air at 150 ° C. for 10 minutes and then baked in air at 480 ° C. for 10 minutes to form a sealing body having a thickness of 105 μm.
(Evaluation of sealed body)
When the gloss of the surface of the formed sealing body was visually observed, it was confirmed that the surface was glossy and the deterioration of the sealing glass powder was prevented. On the other hand, irregularities on the surface remained after firing.

(Discussion)
In Examples 6 and 7 in which the sealing paste compositions E and F of Examples 4 and 5 within the scope of the present invention were fired in nitrogen, respectively, deterioration of the sealing glass powder was not confirmed. Therefore, in general, in the glass paste composition for sealing of Examples 6 and 7 within the scope of the present invention, the glass powder for sealing is not easily decomposed by baking at a low temperature or baking in nitrogen. It was confirmed that it was difficult to deteriorate.
3. Partition Example 8
(Synthesis of polyurethane resin I)
In a 1000 ml SUS separable flask, ethylene oxide (EO), tetrahydrofuran (THF) random copolymer (trade name “Polyserine DC6000E” manufactured by NOF Corporation, molar ratio (EO / THF) = 50/50, number average molecular weight 6230 or less, DC6000) was charged and melted at 150 ° C. in a nitrogen atmosphere. This was dried for 3 hours under reduced pressure (400 Pa) while stirring. Residual moisture was 200 ppm.

Subsequently, the temperature was lowered to 70 ° C., and the flask was filled with 1 atm of nitrogen. Antioxidant (BHT) was added at 500 ppm with respect to DC6000. Next, 0.8095 g of HMDI was charged while stirring the flask (NCO / OH = 1.00 mol / mol).
Next, 120 g of toluene was charged, and further 0.009 g of a catalyst (stannic octylate: product name Stanocto, manufactured by API, hereinafter referred to as Stanocto) was added and reacted at 70 ° C. for 7 hours. Thereby, a toluene solution of polyurethane resin A was obtained. The weight average molecular weight of the reaction product was 315000.

(Preparation of binder resin solution I)
To the resulting toluene solution of polyurethane resin I, 270 g of terpineol was charged to uniformly dissolve the polyurethane resin, and the remaining toluene was removed under reduced pressure (400 Pa) while stirring them. Then, the binder resin solution was taken out from the flask and obtained. The string length of this binder resin solution A was measured by a string measurement device and found to be 11.0 mm.

(Preparation of partition wall paste composition I)
In a mixing container, binder resin solution I20 g, partition wall glass powder (PbO—B ₂ O ₃ —SiO ₂ glass powder, softening point 450 ° C., thermal expansion coefficient 80 × 10 ⁻⁷ (1 / ° C.), average particle diameter D ₅₀ g: 1 μm, maximum particle size D _max : 5 μm) 60 g and alumina (average particle size D ₅₀ : 5 μm, the same applies hereinafter) 20 g were added and mixed, and then kneaded in a three-roll mill to form a partition wall material paste composition Product I was prepared.

(Formation of partition walls)
The partition material paste composition I was applied to the entire upper surface of the soda glass plate using an applicator. The terpineol was dried with a hot air drier to form a dry body having a thickness of 180 μm.
Next, a dry film resist is laminated on the entire upper surface of the dried body, and further a light-shielding film is placed thereon, exposed and developed, unexposed portions are removed using a 1% aqueous sodium hydroxide solution, and sandblasting is performed in a predetermined pattern. A resist was formed. Then, the calcium carbonate powder was used for sand blasting by a sand blasting apparatus for 90 seconds to polish the dried body exposed from the sand blast resist. Thereafter, the sandblasted dried body was fired at 550 ° C. for 10 minutes to form a partition wall having a thickness of 180 μm.

(Evaluation of partition walls)
When the polishing depth by sandblasting in the partition wall was measured, it was 110 μm, which was an appropriate depth. Further, when the cross-sectional shape of the partition wall was observed by SEM (hereinafter the same), the wall surface of the partition wall was almost flat, and oversand due to sandblasting was not confirmed.
Comparative Example 5
(Preparation of binder resin solution J)
A 200 ml glass separable flask was charged with 20 g of ethyl cellulose and 80 g of terpineol, and stirred for 1 hour while heating at 60 ° C. to dissolve the ethyl cellulose, thereby preparing a binder resin solution J.

(Preparation of partition wall paste composition J)
A mixing vessel was mixed with 20 g of binder resin solution J, 60 g of partition wall glass powder (PbO—B ₂ O ₃ —SiO ₂ glass powder) and 20 g of alumina, and these were kneaded with a three-roll mill, thereby separating the partition wall material. Paste composition J was prepared.
(Formation of partition walls)
A partition wall was formed in the same manner as in Example 7 except that the partition material paste composition I was changed to the partition material paste composition J.

(Evaluation of partition walls)
When the polishing depth by sandblasting in the partition wall was measured, it was 100 μm, which was an appropriate depth. On the other hand, when the cross-sectional shape of the partition wall was observed, the central portion of the wall surface of the partition wall was excessively polished (oversanded), resulting in a depression.
4). Phosphor Example 9
(Synthesis of polyurethane resin K)
In a 1000 ml SUS separable flask, 30 g of DC3000 and 1 mol of comb-shaped diol (3-[(2-ethylhexyl) oxy] -1-propylamine prepared according to Example 1 of JP 2000-297133 A 0.30 g of a comb-shaped hydrophobic diol (average molecular weight 560 based on OH number) to which 2-ethylhexyl glycidyl ether was added at a ratio of 2 moles was charged and melted at 150 ° C. in a nitrogen atmosphere. This was dried for 3 hours under reduced pressure (400 Pa) while stirring. Residual moisture was 200 ppm.

Subsequently, the temperature was lowered to 70 ° C., and the flask was filled with 1 atm of nitrogen. Antioxidant BHT was added at 500 ppm with respect to DC3000. Next, 0.8884 g of HMDI was charged while stirring the inside of the flask (NCO / OH = 1.00 mol / mol).
Next, 120 g of toluene was added, and further a catalyst (0.009 g of stanoct was added and reacted for 7 hours at 70 ° C. This gave a toluene solution of polyurethane resin K. The weight average molecular weight of the reaction product was 285000.

(Preparation of binder resin solution K)
To the resulting toluene solution of polyurethane resin K, 270 g of terpineol was charged to uniformly dissolve the polyurethane resin, and the remaining toluene was removed under reduced pressure (400 Pa) while stirring them. Then, the binder resin solution was taken out from the flask and obtained. It was 9.9 mm when the string length of this binder resin solution A was measured with the stringiness measuring apparatus.

(Preparation of phosphor paste composition K)
In a mixing container, ₅₀ g of binder resin solution K and phosphor powder (blue phosphor powder, BaMgAl ₁₀ O ₁₇ : Eu, average particle diameter D ₅₀ : 5 μm) were added and mixed, and then kneaded in a three-roll mill. A phosphor paste composition K for blue was obtained.
(Screen printing of phosphor paste composition K)
The phosphor paste composition K was screen-printed in a predetermined pattern on the upper surface of the soda glass plate. The thickness of the printed phosphor paste composition K was 30 μm. Moreover, in screen printing, the paste composition did not cause stringing, and the filling property and the screen separation were good. Moreover, when the surface of the printed phosphor paste composition K was observed, it was confirmed that the surface was flat.

(Formation of phosphor)
The screen-printed phosphor paste composition K was dried at 150 ° C. for 10 minutes and then baked at 450 ° C. for 10 minutes to form a phosphor having a thickness of 80 μm.
(Evaluation of phosphor)
The formed phosphor was peeled from the soda glass plate, and the phosphor powder was recovered. The phosphor powder was irradiated with ultraviolet light (146 nm), and the emission intensity from the phosphor powder was measured. The emission intensity from the phosphor powder after firing was 96% with respect to the emission intensity from the unfired phosphor powder.
Example 10
(Synthesis of polyurethane resin L)
In a 1000 ml SUS separable flask, ethylene oxide (EO), tetrahydrofuran (THF) random copolymer (trade name “Polyserine 60DC-3000” manufactured by NOF Corporation, molar ratio (EO / THF) = 70/30, number 30 g of an average molecular weight of 3057 or less and 60DC-3000) and a comb-shaped diol (3-[(2-ethylhexyl) oxy] -1-) produced according to the description in Example 1 of JP-A-2000-297133. Charged 0.30 g of a comb-shaped hydrophobic diol (average molecular weight based on OH value 560) added with a ratio of 2 mol of 2-ethylhexyl glycidyl ether to 1 mol of propylamine, and melted at 150 ° C. in a nitrogen atmosphere. It was. This was dried for 3 hours under reduced pressure (400 Pa) while stirring. Residual moisture was 200 ppm.

Subsequently, the temperature was lowered to 70 ° C., and the flask was filled with 1 atm of nitrogen. Antioxidant BHT was added at 500 ppm with respect to 60DC-3000. Subsequently, 1.7294 g of HMDI was charged while stirring the inside of the flask (NCO / OH = 1.00 mol / mol).
Next, 120 g of toluene was added, and further a catalyst (0.009 g of stanoct was added and reacted for 7 hours at 70 ° C. This gave a toluene solution of polyurethane resin L. The weight average molecular weight of the reaction product was 270000.

(Preparation of binder resin solution L)
In a toluene solution of the obtained polyurethane resin L, 270 g of butyl carbitol was charged to dissolve the polyurethane resin uniformly, and the remaining toluene was removed under reduced pressure (400 Pa) while stirring them. Then, the binder resin solution was taken out from the flask and obtained. It was 8.9 mm when the string length of this binder resin solution L was measured with the stringiness measuring apparatus.

(Preparation of phosphor paste composition L)
After mixing and mixing 50 g of binder resin solution L and 50 g of phosphor powder (blue phosphor powder, BaMgAl ₁₀ O ₁₇ : Eu) in a mixing container, these are kneaded by a three-roll mill, whereby a phosphor paste composition for blue Product L was obtained.
(Screen printing of phosphor paste composition L)
The phosphor paste composition L was screen-printed in a predetermined pattern on the upper surface of the soda glass plate. The thickness of the printed phosphor paste composition L was 30 μm. Moreover, in screen printing, the paste composition did not cause stringing, and the filling property and the screen separation were good. Moreover, when the surface of the printed phosphor paste composition L was observed, it was confirmed that the surface was flat.

(Formation of phosphor)
The screen-printed phosphor paste composition L was dried at 150 ° C. for 10 minutes and then baked at 450 ° C. for 10 minutes to form a phosphor having a thickness of 80 μm.
(Evaluation of phosphor)
The formed phosphor was peeled from the soda glass plate, and the phosphor powder was recovered. The phosphor powder was irradiated with ultraviolet light (146 nm), and the emission intensity from the phosphor powder was measured. The light emission intensity from the phosphor powder after firing was 90% with respect to the light emission intensity from the unfired phosphor powder.
Comparative Example 6
(Preparation of binder resin solution M)
A 200 ml glass separable flask was charged with 5 g of ethyl cellulose and 95 g of butyl carbitol acetate, and stirred for 30 minutes while heating to 60 ° C. to dissolve the ethyl cellulose, thereby preparing a binder resin solution M.

(Preparation of phosphor paste composition M)
A phosphor paste composition M for blue was obtained by kneading 50 g of binder resin solution M and 50 g of phosphor powder (blue phosphor powder, BaMgAl ₁₀ O ₁₇ : Eu) with a three-roll mill.
(Screen printing of phosphor paste composition M)
The phosphor paste composition M was screen-printed in a predetermined pattern on the upper surface of the soda glass plate. The thickness of the printed phosphor paste composition M was 30 μm. In screen printing, stringing did not occur, and the surface of the printed phosphor paste composition M was flat.

(Formation of phosphor)
The screen-printed phosphor paste composition L was dried at 150 ° C. for 10 minutes and then baked at 500 ° C. for 10 minutes to form a phosphor having a thickness of 75 μm.
(Evaluation of phosphor)
The formed phosphor was peeled from the soda glass plate, and the phosphor powder was recovered. The phosphor powder was irradiated with ultraviolet light (146 nm), and the emission intensity from the phosphor powder was measured. The light emission intensity from the phosphor powder after firing was 80% with respect to the light emission intensity from the unfired phosphor powder.

(Discussion)
The phosphor paste composition K of Example 9 and the phosphor paste composition L of Example 10 within the scope of the present invention were the emission intensity of the phosphor obtained by firing at 450 ° C. (relative to the unfired emission intensity). (Emission intensity) was 90% or more.
On the other hand, in the phosphor paste composition M of Comparative Example 6 containing ethyl cellulose, the phosphor obtained by firing at 500 ° C. had a light emission intensity (relative light emission intensity with respect to the unfired light emission intensity) of 80%.

From this, it was confirmed that the phosphor paste compositions K and L of Examples 9 and 10 within the scope of the present invention are less likely to be carbonized even at low temperature firing and can prevent a decrease in the emission intensity (luminance) of the phosphor. .
5. Electron Emitter Example 11
(Synthesis of polyurethane resin N)
In a 1000 ml SUS separable flask, ethylene oxide (EO), tetrahydrofuran (THF) random copolymer (trade name “Polyserine 30DC-3000” manufactured by NOF Corporation, molar ratio (EO / THF) = 30/70, number 30 g of an average molecular weight of 3057 or less and 30DC-3000) and a comb-shaped diol (3-[(2-ethylhexyl) oxy] -1- produced according to Example 1 of JP-A-2000-297133 Charged 0.30 g of a comb-shaped hydrophobic diol (average molecular weight based on OH value 560) added with a ratio of 2 mol of 2-ethylhexyl glycidyl ether to 1 mol of propylamine, and melted at 150 ° C. in a nitrogen atmosphere. It was. This was dried for 3 hours under reduced pressure (400 Pa) while stirring. Residual moisture was 200 ppm.

Subsequently, the temperature was lowered to 70 ° C., and the flask was filled with 1 atm of nitrogen. Antioxidant BHT was added at 500 ppm with respect to 30DC-3000. Subsequently, 1.7294 g of HMDI was charged while stirring the inside of the flask (NCO / OH = 1.00 mol / mol).
Next, 120 g of toluene was charged, and further a catalyst (0.009 g of stannoct was added and reacted for 7 hours at 70 ° C. This gave a toluene solution of polyurethane resin N. The weight average molecular weight of the reaction product was 265,000.

(Preparation of binder resin solution N)
To the resulting toluene solution of polyurethane resin N, 270 g of terpineol was charged to uniformly dissolve the polyurethane resin, and the remaining toluene was removed under reduced pressure (400 Pa) while stirring these. Then, the binder resin solution was taken out from the flask and obtained. It was 7.9 mm when the string length of this binder resin solution L was measured with the stringiness measuring apparatus.

(Preparation of carbon nanomaterial paste composition N)
In a mixing container, 60 g of binder resin solution N, 15 g of carbon nanotubes and 15 g of low melting glass powder (P2O5-SnO—B2O3 glass, average particle diameter D ₅₀ : 5 μm) are added and mixed, and then these are kneaded by a three roll mill. Thus, a carbon nanomaterial paste composition N was obtained.

(Formation of electron emitter)
The carbon nanomaterial paste composition N was screen-printed in a predetermined pattern on the upper surface of the soda glass plate. The thickness of the screen-printed carbon nanomaterial paste composition N was 5 μm. In screen printing, stringing did not occur. Moreover, when the surface of the printed carbon nanomaterial paste composition N was observed, it was confirmed that the surface was flat. Further, when the surface roughness Ra of the printed carbon nanomaterial paste composition N was measured using a stylus type surface roughness meter, the surface was as flat as 10 nm.

Next, the screen-printed carbon nanomaterial paste composition N was dried at 150 ° C. for 10 minutes and then baked at 400 ° C. for 10 minutes to form an electron emitter having a thickness of 5 μm.
(Evaluation of electron emitter)
The amount of degassing of the formed electron emitter was measured by heating to 800 ° C. by pyrolysis gas chromatography. As a result, the degassing amount derived from carbon was almost 0 (zero).
Comparative Example 7
(Preparation of carbon nanomaterial paste composition O)
After mixing and mixing the binder resin solution G60 g prepared in Comparative Example 3, 15 g of carbon nanotubes, and 15 g of low-melting glass powder in a mixing container, these are kneaded by a three-roll mill to obtain a carbon nanomaterial paste composition O. It was.

(Formation of electron emitter)
The carbon nanomaterial paste composition O was screen-printed in a predetermined pattern on the upper surface of the soda glass plate. The thickness of the screen-printed carbon nanomaterial paste composition O was 5 μm. Further, stringing did not occur in screen printing. Moreover, when the surface of the printed carbon nanomaterial paste composition O was observed, it was confirmed that the surface was flat. Further, the surface roughness Ra of the printed carbon nanomaterial paste composition O measured with a stylus type surface roughness meter was 5 nm.

Next, the printed carbon nanomaterial paste composition O was dried at 150 ° C. for 10 minutes and then baked at 400 ° C. for 10 minutes to form an electron emitter having a thickness of 5 μm.
(Evaluation of electron emitter)
The amount of degassing of the formed electron emitter was measured by heating to 800 ° C. by pyrolysis gax chromatography. As a result, degassing derived from carbon was confirmed.
Comparative Example 8
(Synthesis of polyurethane resin P)
In a 1000 ml glass separable flask, 30 g of PTMEG8000 (PTG8000 manufactured by Hodogaya Chemical Co., Ltd.) was charged and melted at 150 ° C. in a nitrogen atmosphere. This was dried for 3 hours under reduced pressure (400 Pa) while stirring. Residual moisture was 200 ppm.

Subsequently, the temperature was lowered to 70 ° C., and the flask was filled with 1 atm of nitrogen. Antioxidant (BHT) was added at 500 ppm with respect to PTMEG8000. Next, 2.3371 g of HMDI was charged while stirring the flask (NCO / OH = 0.95 mol / mol).
Next, 120 g of toluene was charged, 0.009 g of catalyst (DBTDL) was further added, and the mixture was reacted at 70 ° C. for 7 hours. Thereby, a toluene solution of the polyurethane resin P was obtained. The weight average molecular weight of the reaction product was 560000.

(Preparation of binder resin solution P)
In a toluene solution of the obtained polyurethane resin P, 303 g of terpineol was charged to uniformly dissolve the polyurethane resin P, and the remaining toluene was removed under reduced pressure (400 Pa) while stirring them. Then, the binder resin solution P was taken out from the flask and obtained. The string length of this resin solution was measured with a stringiness measuring device and found to be 48.5 mm.

(Preparation of carbon nanomaterial paste composition P)
After mixing and mixing the binder resin solution P60g prepared in Comparative Example 1, 15g of carbon nanotubes, and 15g of low-melting glass powder in a mixing container, these are kneaded by a three-roll mill to obtain a carbon nanomaterial paste composition P. It was.
(Formation of electron emitter)
The carbon nanomaterial paste composition P was screen-printed in a predetermined pattern on the upper surface of the soda glass plate. The thickness of the screen-printed carbon nanomaterial paste composition P was 5 μm. Further, stringing was slightly caused in screen printing, and the separation of the plate was bad. Moreover, when the surface of the printed carbon nanomaterial paste composition P was observed, it was confirmed that a part of the surface was not flat. Moreover, it was 15 nm when surface roughness Ra was measured about the printed carbon nanomaterial paste composition P using the stylus type surface roughness meter.

Next, the printed carbon nanomaterial paste composition P was dried at 150 ° C. for 10 minutes and then baked at 400 ° C. for 10 minutes to form an electron emitter having a thickness of 8 μm.
(Evaluation of electron emitter)
The amount of degassing of the formed electron emitter was measured by heating to 800 ° C. by pyrolysis gax chromatography. As a result, the degassing derived from carbon was zero.

(Discussion)
The carbon nanomaterial paste composition N of Example 11 within the scope of the present invention does not carbonize even when fired at a low temperature. Therefore, it was confirmed that the electron emitter formed by firing the carbon nanomaterial paste composition N of Example 11 can prevent deterioration of its electron emission characteristics.

On the other hand, the carbon nanomaterial paste composition O of Comparative Example 7 containing ethyl cellulose has insufficient thermal decomposition. Therefore, it was confirmed that the electron emitter formed by firing the carbon nanomaterial paste composition O of Comparative Example 7 affects the electron emission characteristics.
Moreover, the carbon nanomaterial paste composition P of Comparative Example 8 using a polyalkylene glycol having only 4 carbon atoms tends to cause stringing and has poor printability, and it is difficult to obtain a flat surface. Therefore, it was confirmed that the electron emitter formed by firing the carbon nanomaterial paste composition P of Comparative Example 8 has a slight effect on the electron emission characteristics.

  The paste composition of the present invention can obtain a fired body by firing. This fired body is suitably used, for example, as an FPD component, more specifically as a dielectric layer, a sealing body, a partition, a phosphor, and an electron emitter.

Claims (17)

A polyurethane resin obtained by reacting at least a polyoxyalkylene glycol containing 1 to 85 mol% of an alkylene group having 2 to 3 carbon atoms and 15 to 99 mol% of an alkylene group having 4 to 6 carbon atoms with a diisocyanate. When,
Solvent,
A paste composition comprising: a powder.   The paste composition according to claim 1, wherein the number average molecular weight of the polyoxyalkylene glycol is 2000 or more. The polyurethane resin is obtained by reacting at least the polyoxyalkylene glycol, the diisocyanate, a comb diol represented by the following general formula (1) and / or a comb diol represented by the following general formula (2). The paste composition according to claim 1 or 2, wherein

(In the formula, R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms or a nitrogen-containing hydrocarbon group which may be substituted with a halogen atom. R ² and R ³ are the same or different from each other. And a hydrocarbon group having 4 to 21 carbon atoms which may be substituted with a halogen atom, and Y ¹ and Y ² are the same as or different from each other, and represent a hydrogen atom, a methyl group or CH _2. Represents a Cl group, Z ¹ and Z ² are the same or different from each other, and represent an oxygen atom, a sulfur atom or a CH ₂ group, and n ¹ and n ² are the same or different from each other. Differently, an integer of 0 to 15 is shown.)

(In the formula, R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom. R ⁵ and R ⁶ are the same or different from each other, R 4 represents an optionally substituted hydrocarbon group having 4 to 21 carbon atoms, R ⁷ represents an alkylene group having 2 to 4 carbon atoms, and Y ³ , Y ⁴ and Y ^5. Are the same or different from each other and represent a hydrogen atom, a methyl group or a CH ₂ Cl group, and Z ³ and Z ⁴ are the same or different from each other and represent an oxygen atom, a sulfur atom or a CH ₂ group. And k represents an integer of 0 to 15. n ³ and n ⁴ are the same or different from each other and represent an integer of 0 to 15.)   The paste composition according to any one of claims 1 to 3, wherein the powder contains a low-melting glass powder.   The paste composition according to claim 4, wherein the powder further contains an inorganic filler.   A fired body obtained by firing the paste composition according to any one of claims 1 to 5.   The paste composition according to claim 4 or 5, wherein the low-melting glass powder is a dielectric glass powder.   The paste composition according to claim 4 or 5, wherein the low-melting glass powder is a glass powder for sealing.   The paste composition according to claim 4 or 5, wherein the low melting glass powder is a partition wall glass powder.   The paste composition according to claim 1, wherein the powder contains phosphor powder.   The paste composition according to claim 1, wherein the powder contains a carbon nanomaterial.   A dielectric layer obtained by firing the paste composition according to claim 7.   It obtains by baking the paste composition of Claim 8, The sealing body characterized by the above-mentioned.   A partition wall obtained by firing the paste composition according to claim 9.   A phosphor obtained by firing the paste composition according to claim 10.   An electron emitter obtained by firing the paste composition according to claim 11.   It is obtained by baking the paste composition in any one of Claims 7-11, The components for flat panel displays characterized by the above-mentioned.