KR20110083627A - Metal oxide microparticle dispersed slurry - Google Patents

Abstract

The present invention provides a metal oxide fine particle dispersion slurry that has achieved excellent screen printability by improving the dispersibility of metal oxide fine particles. Moreover, this invention is a manufacturing method of the metal oxide thin film dispersion paste containing this metal oxide fine particle dispersion slurry, this metal oxide fine particle dispersion slurry, or this metal oxide fine particle dispersion paste, and the manufacturing method of this metal oxide thin film. The metal oxide thin film obtained by this is provided. The present invention is a metal oxide fine particle dispersion slurry containing metal oxide fine particles and an organic solvent, the metal oxide fine particles having an average particle diameter of 10 to 100 nm, the organic solvent has two or more hydroxyl groups in one molecule, It is a metal oxide fine particle dispersion slurry containing the polyol whose ratio of carbon atom number to hydroxyl number in is less than 5, and the viscosity in normal temperature is 100 mPa * s or more.

Description

Metal Oxide Fine Particle Dispersion Slurry {METAL OXIDE MICROPARTICLE DISPERSED SLURRY}

The present invention relates to a metal oxide fine particle dispersion slurry that has achieved excellent screen printability by improving the dispersibility of metal oxide fine particles. In addition, the present invention provides a method for producing a metal oxide thin film dispersion paste containing the metal oxide fine particle dispersion slurry, the metal oxide fine particle dispersion slurry or the metal oxide fine particle dispersion paste, and the production of the metal oxide thin film. It relates to a metal oxide thin film obtained by the method.

In recent years, with the advance of the technology of refine | miniaturizing a metal oxide, many metal oxides are manufactured and used for various uses, such as a transparent electrode and an antistatic agent. For example, ITO doped with tin oxide has attracted attention as a transparent electrode material for producing a plasma display panel, a liquid crystal display panel, and the like. In addition, magnesium oxide is widely used as a dielectric protective layer of a front plate for plasma displays in terms of its impact resistance and electron emission characteristics.

Conventionally, for example, vacuum deposition has been used as a method of forming a metal oxide thin film using such a metal oxide. More specifically, for example, when forming a transparent electrode, the method of forming an electrode pattern by attaching a metal oxide to the surface of a base material by vacuum evaporation, developing or masking using a photoreactive material, It was used. However, since a physical method such as vacuum evaporation takes time necessary for evacuation, and it is necessary to strictly control the device, an alternative method having good mass productivity and good production efficiency has been desired.

Therefore, as an alternative method excellent in mass productivity, Patent Document 1, for example, applies a paste containing acetylacetone indium, acetylacetone tin or the like on a substrate, and after drying, ITO transparent by sol-gel reaction when firing A method of producing a conductive film is disclosed.

This method can easily produce an ITO transparent conductive film at low cost, but the ITO transparent conductive film formed by the sol-gel reaction is very unstable, making it difficult to stably obtain an ITO transparent conductive film having a desired performance and having low boiling point acetylacetone Was used as a solvent, and there existed a problem that a solvent was easy to volatilize and inferior to a handleability.

Therefore, as another alternative method excellent in mass productivity, the method of coating the dispersion paste containing the fine particle of a metal oxide by screen printing is used. In the method using screen printing, for example, a paste obtained by dispersing metal oxide fine particles in a binder resin such as ethyl cellulose is coated on a substrate by screen printing, and then sintered to form a layer made of metal oxide fine particles. .

However, the method using such screen printing is poor in thermal decomposition of ethyl cellulose, which is generally used as a binder resin, abundant residual carbon after sintering, deterioration of metal oxide by heating at high temperature during sintering, and metal oxide. In order to sufficiently exhibit the properties of the fine particles, it is necessary to disperse the fine particles well, but there are many problems such as agglomeration due to strong interaction between the particles and gelation of the dispersion paste.

Therefore, there has been a demand for a simple method for obtaining a metal oxide thin film having a performance equivalent to that by vacuum deposition.

Japanese Laid-Open Patent Publication No. 2006-49019

An object of the present invention is to provide a metal oxide fine particle dispersion slurry that has achieved excellent screen printability by improving the dispersibility of metal oxide fine particles. Moreover, this invention is a manufacturing method of the metal oxide thin film dispersion paste containing this metal oxide fine particle dispersion slurry, this metal oxide fine particle dispersion slurry, or this metal oxide fine particle dispersion paste, and the manufacturing method of this metal oxide thin film. It is an object to provide a metal oxide thin film obtained by.

The present invention is a metal oxide fine particle dispersion slurry containing metal oxide fine particles and an organic solvent, the metal oxide fine particles having an average particle diameter of 10 to 100 nm, the organic solvent has two or more hydroxyl groups in one molecule, It is a metal oxide fine particle dispersion slurry containing the polyol whose ratio of carbon atom number to hydroxyl number in is less than 5, and the viscosity in normal temperature is 100 mPa * s or more.

The present invention is described in detail below.

In recent years, a binder resin is not contained in place of a method of forming a layer made of metal oxide fine particles by vacuum evaporation, a method of forming a layer made of metal oxide fine particles by coating the metal oxide fine particle dispersion paste by screen printing, or the like. After coating metal oxide fine particle dispersion slurry by screen printing, the method of solvent drying or sintering is examined. However, when the binder resin is not used, the dispersed state of the metal oxide fine particles deteriorates, and it is very difficult to obtain a metal oxide thin film equivalent to the case by vacuum deposition.

Therefore, the inventors of the present invention improve the screen printability by maintaining the high dispersibility of metal oxide fine particles in the metal oxide fine particle dispersion slurry in which metal oxide fine particles having an average particle diameter of 10 to 100 nm are dispersed in an organic solvent having a predetermined structure. It was found out that a metal oxide thin film having transparency, smoothness, denseness, and the like equivalent to that by vapor deposition could be easily produced, and thus, the present invention was completed.

The metal oxide fine particle dispersion slurry of this invention contains metal oxide fine particles.

The metal oxide fine particles have an average particle diameter of 10 to 100 nm. If the average particle diameter is less than 10 nm, the exact particle diameter cannot be grasped. When the average particle diameter exceeds 100 nm, it is difficult to produce a metal oxide thin film having desired transparency, conductivity, or the like even by screen printing using the resulting metal oxide fine particle dispersion slurry. The said metal oxide fine particle has a preferable minimum of 12 nm of preferable average particle diameters, a preferable upper limit of 70 nm, a more preferable minimum of 15 nm, and a more preferable upper limit of 50 nm.

In addition, the average particle diameter of metal oxide fine particles can be calculated | required by measuring the particle diameters of 50 metal oxide fine particles selected at random using an optical microscope or an electron microscope, and arithmetically averaging the measured particle diameter.

The metal oxide fine particles are not particularly limited, but for example, in the group consisting of zinc oxide, antimony oxide, silicon oxide, tin oxide, indium oxide, titanium oxide, iron oxide, magnesium oxide and metal oxides doped with other metals thereof. It is preferable to contain at least 1 sort (s) selected. Examples of the metal oxide doped with the other metal include ITO doped with indium in tin oxide, GZO doped with gallium in zinc oxide, and the like.

In the metal oxide fine particle dispersion slurry of this invention, the minimum with preferable content of the said metal oxide fine particle is 2 weight%, and a preferable upper limit is 70 weight%. If content of the said metal oxide fine particle is less than 2 weight%, even if it screen-prints using the obtained metal oxide fine particle dispersion slurry, a uniform metal oxide thin film may not be manufactured. When content of the said metal oxide fine particle exceeds 70 weight%, dispersion stability of the said metal oxide fine particle may not fully be obtained in the obtained metal oxide fine particle dispersion slurry.

The metal oxide fine particle dispersion slurry of this invention contains the organic solvent. In addition, the said organic solvent has 2 or more hydroxyl groups in 1 molecule, the ratio of the number of carbon atoms with respect to the number of hydroxyl groups in a molecule is less than 5, and the polyol whose viscosity at normal temperature is 100 mPa * s or more (Hereinafter, a polyol is simply It is also called).

Usually, it is difficult to disperse very fine metal oxide fine particles having an average particle diameter of 10 to 100 nm using a solvent other than a high polar solvent such as water, methanol, ethanol, isopropanol, and the like. Moreover, since the metal oxide fine particle dispersion slurry which disperse | distributed the said metal oxide microparticles | fine-particles in such a high polar solvent is very low in viscosity, it can adapt only to the process of solvent casting, inkjet, spray, etc. as it is, and it is a uniform metal about 1 micrometer in thickness. It is difficult to produce an oxide thin film.

The metal oxide fine particle dispersion slurry of this invention has a polyol which has two or more hydroxyl groups in 1 molecule, the ratio of the number of carbon atoms to the number of hydroxyl groups in a molecule is less than 5, and the viscosity in normal temperature is 100 mPa * s or more, If necessary, a good dispersion state of the metal oxide fine particles can be obtained by containing a polymeric anionic dispersant. Moreover, since the viscosity of the whole slurry becomes high, it becomes possible to perform a direct disintegration process using simple disintegration apparatuses, such as a three roll mill, and can obtain the metal oxide fine particle dispersion slurry which further improved the dispersion state of the said metal oxide fine particles. have. In addition, the metal oxide fine particle dispersion slurry thus obtained can be adapted to various printing processes such as screen printing, gravure offset printing, roll coater, blade coater and the like, thereby producing a uniform metal oxide thin film.

The polyol has two or more hydroxyl groups in one molecule. If the number of hydroxyl groups in one molecule is less than two, the hydrophilicity of the polyol is lowered and it is difficult to disperse the metal oxide fine particles well.

In addition, the polyol has a ratio of the number of carbon atoms to the number of hydroxyl groups in the molecule is less than five. If the ratio of the number of carbon atoms to the number of hydroxyl groups in a molecule | numerator is 5 or more, the hydrophilicity of a polyol will fall and it is difficult to disperse | distribute the said metal oxide fine particle favorable. It is preferable that the ratio of the number of carbon atoms with respect to the number of hydroxyl groups in a molecule | numerator of the said polyol is 1 or more. In addition, in this specification, "the ratio of the number of carbon atoms to the number of hydroxyl groups" means the value {(carbon number of atoms) / (number of hydroxyl groups)} which divided the number of carbon atoms by the number of hydroxyl groups.

The polyol has a viscosity at room temperature of 100 mPa · s or more. If the viscosity at room temperature is less than 100 mPa · s, the viscosity of the resulting metal oxide fine particle dispersion slurry is lowered, and the dispersibility of the metal oxide fine particles cannot be improved by performing a disintegration treatment using three roll mills or the like, or screen printing can be performed. Can or should not. From the viewpoint that the metal oxide fine particles can be more preferably disintegrated, the polyol preferably has a viscosity at room temperature of 1000 mPa · s or more. Moreover, it is preferable that the said polyol is 50000 mPa * s or less in viscosity at normal temperature.

As a polyol which has 2 or more hydroxyl groups in the said 1 molecule, the ratio of the number of carbon atoms to the number of hydroxyl groups in a molecule is less than 5, and the viscosity in normal temperature is 100 mPa * s or more, For example, 3-methyl-1 , 5-pentanediol, glycerin, glycerin monoacetate, 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, triethylene glycol, propanediol, butanediol, Ethanediol, pentanediol, hexanediol, 1,6-hexanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, 2-ethyl-2- (hydroxymethyl) -1 , 3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol and the like Can be. Among them, butanediol, pentanediol, hexanediol, 1,6-hexanediol, and 2-ethyl are relatively high in terms of viscosity and the disintegration of the metal oxide fine particles to facilitate the disintegration treatment using three roll mills and the like. Preference is given to -1,3-hexanediol, 3-methyl-1,5-pentanediol, glycerin, 2,4-diethyl-1,5-pentanediol. These polyols may be used independently and may use 2 or more types together.

In the metal oxide fine particle dispersion slurry of this invention, the polyol which has two or more hydroxyl groups in the said one molecule, the ratio of carbon atom number to the number of hydroxyl groups in a molecule is less than 5, and the viscosity in normal temperature is 100 mPa * s or more. The minimum with preferable content is 25 weight%, and a preferable upper limit is 85 weight%. When content of the said polyol is less than 25 weight%, it may become difficult to disperse | distribute the said metal oxide fine particle. When content of the said polyol exceeds 85 weight%, the viscosity of the metal oxide fine particle dispersion slurry obtained will become low, and handleability may fall when screen printing etc. are performed.

The metal oxide fine particle dispersion slurry of the present invention has two or more hydroxyl groups in the above one molecule, has a ratio of the number of carbon atoms to the number of hydroxyl groups in the molecule is less than 5, and in addition to the polyol having a viscosity at room temperature of 100 mPa · s or more. It is preferable that boiling point contains the other organic solvent of 140 degreeC or more. When screen boiling is less than 140 degreeC using the obtained metal oxide fine particle dispersion slurry, the organic solvent may volatilize during printing, and printing may become difficult.

As another organic solvent whose said boiling point is 140 degreeC or more, For example, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisobutyl ether, trimethyl Pentanediol monoisobutylate, diethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol Monobutyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dihydroterpineol acetate, terpineol acetate, 2-butoxyethyl acetate, 2-ethoxyethyl acetate, 2-methoxy Ethyl acetate, propylene carbonate, Lupineol, dihydroterpineol, methyl salicylate, ethyl lactate, dipropylene glycol monomethyl ether, 2-ethylhexanoic acid, trimethylhexanoic acid, tetrahydrofurfuryl alcohol, furfuryl alcohol, 2- (benzyloxy) ethanol , 2-phenoxyethanol, 2- (methoxymethoxy) ethanol, triethylene glycol monomethyl ether, triethylene glycol, diethylene glycol monobutyl acetate, diethylene glycol monobutyl ether acetate, phenoxy acetate, phenoxyethyl Acetate, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monobenzyl ether, propylene glycol monophenyl ether, benzyl glycol, methyl phenyl acetate, ethyl phenyl acetate, ethyl benzoate, methyl benzoate , γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, N-methylacetamide, acetamide, N, N- Methyl-formamide, N- methyl formamide, dimethylformamide, Tech sanol, isophorone, butyl lactate, dioctyl phthalate, dioctyl adipate, benzyl alcohol, there may be mentioned Cresol.

In the metal oxide fine particle dispersion slurry of the present invention, the upper limit of the organic solvent having a boiling point of 140 ° C or higher is preferably 60% by weight. When content of the other organic solvent whose said boiling point is 140 degreeC or more exceeds 60 weight%, the dispersion stability of the said metal oxide fine particle may fall.

It is preferable that the metal oxide fine particle dispersion slurry of this invention contains a polymeric anionic dispersing agent. Although the said polymeric anionic dispersing agent is not specifically limited, For example, it is preferable that it is a polymeric polycarboxylic-acid dispersing agent. More specifically, examples of the polymer anionic dispersant include DEMO EP, Poise 520, Poise 521, Poise 532A, Homogenol L-18, Homogenol 1820, Homogenol L-95, Homogenol L-100, etc. DISTYBY-102, DISPERBYK-106, DISPERBYK-108, DISPERBYK-110, manufactured by BIC Chemistry, Inc., Polyti N-100K, Polyti A-530, Polyti A-540, Polyti A-550, etc. HIPLAAD ED-110, HIPLAAD ED-111, HIPLAAD ED-118, HIPLAAD ED-216, HIPLAAD ED-350, etc., manufactured by Kusumoto Chemical Co., Ltd., such as DISPERBYK-111, BYK-P105, etc. RS-610, RS manufactured by Toho Chemical Co., Ltd., KD-4, KD-8, KD-9, KD-15 manufactured by Kuroda Co., Ltd. -710, SM-210, etc. are mentioned. By containing such a polymeric anionic dispersant, the metal oxide fine particle dispersion slurry of this invention can inhibit aggregation of the said metal oxide fine particles, and can improve dispersibility.

In the metal oxide fine particle dispersion slurry of this invention, the minimum with preferable content of the said polymeric anionic dispersing agent is 0.1 weight%, and a preferable upper limit is 10 weight%. When content of the said polymeric anionic dispersing agent is out of the said range, the said metal oxide fine particle may not be disperse | distributed favorably. The minimum with more preferable content of the said polymeric anionic dispersing agent is 0.3 weight%, and a more preferable upper limit is 7 weight%.

The metal oxide fine particle dispersion slurry of this invention may contain nonionic surfactant for the purpose of promoting the leveling after coating.

Although the said nonionic surfactant is not specifically limited, It is preferable that it is nonionic surfactant of HLB value of 10-20. In addition, an HLB value is an index which shows the hydrophilicity and lipophilic property of surfactant, and several calculation methods are proposed. For example, regarding ester type surfactant, when the saponification value is S and the acid value of the fatty acid which comprises surfactant is A, there exists a method of defining the value of 20 (1-S / A) as an HLB value. .

In particular, the nonionic surfactant is preferably a nonionic surfactant in which an alkylene ether is added to an aliphatic chain, and specific examples thereof include polyoxyethylene lauryl ether and polyoxyethylene cetyl ether.

In the metal oxide fine particle dispersion slurry of this invention, the upper limit with preferable content of the said nonionic surfactant is 5 weight%. Although the said nonionic surfactant is good in thermal decomposition property, when added in large quantities, it may adversely affect the performance of the metal oxide thin film manufactured using the obtained metal oxide fine particle dispersion slurry.

The metal oxide fine particle dispersion slurry of this invention may contain an adhesion promoter.

Although the said adhesion promoter is not specifically limited, Aminosilane type silane coupling agent is preferable. As said aminosilane type silane coupling agent, for example, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N 2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl -Butylidene) propylamine and N-phenyl-3-aminopropyl trimethoxysilane.

Moreover, as adhesion promoters other than the said aminosilane type silane coupling agent, 3-glycidoxy propyl trimethoxysilane, 3-glycidoxy propylmethyl diethoxysilane, 3-glycidoxy propyl triethoxy You may use glycidylsilane type silane coupling agents, such as a silane, dimethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyl trimethoxysilane, diphenyldimethoxysilane, etc. These may be used independently and may use 2 or more types together.

The metal oxide fine particle dispersion slurry of this invention may also contain low melting glass fine particles in order to express adhesive force with respect to a glass substrate.

The low melting point glass fine particles are not particularly limited, and for example, silicate glass, lead glass, zinc glass, boron glass, CaO-Al ₂ O ₃ -SiO ₂ -based inorganic glass, MgO-Al ₂ O ₃ -SiO _{2 type} Inorganic glass and LiO ₂ -Al ₂ O ₃ -SiO ₂ -based inorganic glass. Especially, it is preferable that melting | fusing point is low melting-point glass of 600 degrees C or less.

The method of manufacturing the metal oxide fine particle dispersion slurry of this invention is not specifically limited, For example, the method of performing a disintegration process using a disintegration apparatus, such as a three roll mill, after mixing each component. In particular, in a polyol having two or more hydroxyl groups in the molecule, the ratio of the number of carbon atoms to the number of hydroxyl groups in the molecule is less than 5, and the viscosity at room temperature is 100 mPa · s or more, the viscosity at room temperature is 1000 mPa. In the case of using a polyol of s or more, a dispersion state close to the dispersion state obtained by the bead mill treatment may be obtained by subjecting the slurry to three slurry mills.

By adding a binder resin to the metal oxide fine particle dispersion slurry of this invention, the paste more suitable for printing processes, such as screen printing, can be obtained.

The metal oxide fine particle dispersion slurry of this invention, and the metal oxide fine particle dispersion paste containing binder resin are also one of this invention.

Although the said binder resin is not specifically limited, For example, a cellulose resin, a (meth) acrylic resin, a polyether resin, a polyacetal resin, and a polyvinyl acetal resin are preferable. Especially, since a high thermal decomposition property and few residual carbon after sintering, a (meth) acrylic resin is especially preferable.

As said (meth) acrylic resin, For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, tert- butyl (meth) acrylate , Isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) The homopolymer of (meth) acryl monomers, such as an acrylate, and the copolymer of these (meth) acryl monomers and the (meth) acryl monomer which has a polyoxyalkylene structure are mentioned. As said polyoxyalkylene structure, polypropylene oxide, polymethylethylene oxide, polyethylethylene oxide, polytrimethylene oxide, polytetramethylene oxide is mentioned, for example. In addition, in this specification, (meth) acrylate means an acrylate and / or a methacrylate.

It is preferable that the said (meth) acrylic resin has a segment derived from methyl methacrylate. By having a segment derived from methyl methacrylate, a metal oxide fine particle dispersion paste having a viscosity suitable for screen printing can be obtained with a small amount of binder resin. Especially, it is especially preferable to use polymethyl methacrylate (henceforth PMMA) which is a homopolymer of methyl methacrylate as binder resin.

It is preferable that the said (meth) acrylic resin has a polar group at the molecular terminal, and it is particularly preferable to have a carboxylic acid at the molecular terminal.

Moreover, it is more preferable that the said (meth) acrylic resin has a polar group only in a molecular terminal. The polar group at the molecular end is adsorbed by the metal oxide fine particles, inhibits aggregation of the metal oxide fine particles, and serves to enhance dispersibility. Moreover, even if the said (meth) acrylic resin has a polar group in the terminal of a molecule | numerator, there is little influence on thermal decomposition property. However, when (meth) acrylic monomer which has polar groups, such as (meth) acrylic acid and hydroxyethyl (meth) acrylate, is polymerized as a monomer component, the (meth) acrylic resin obtained has a polar group in a side chain, and these (meth ) Acrylic resin is extremely poor in thermal decomposition and has a large amount of residual carbon after sintering. Therefore, when used when producing a transparent electrode or the like, the acrylic resin may adversely affect the light transmittance or conductivity.

However, as long as it is an amount which does not inhibit the thermal decomposition property of the obtained (meth) acrylic resin, you may superpose | polymerize by adding the (meth) acryl monomer which has a polar group. (Meth) acryl monomer which has the said polar group is not specifically limited, For example, (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2- (meth) acryloyl Oxyethyl succinic acid and itaconic acid are mentioned.

When superposing | polymerizing or copolymerizing the said (meth) acrylic resin, the preferable upper limit of the addition amount of the (meth) acryl monomer which has the said polar group is 5 weight%. When the addition amount of the (meth) acryl monomer which has the said polar group exceeds 5 weight%, the thermal decomposition property of the (meth) acrylic resin obtained may become extremely bad, and the residual carbon after sintering may also increase.

The manufacturing method of the said (meth) acrylic resin is not specifically limited, For example, the (meth) acrylic monomer mentioned above is a free radical polymerization method, a living radical polymerization method, an inipher polymerization method, an anion polymerization method, a living The method of superposition | polymerization or copolymerization by a conventionally well-known method, such as an anion polymerization method, is mentioned.

In addition, the manufacturing method of the (meth) acrylic resin which has a polar group only in the said molecular terminal is not specifically limited, For example, in the presence of the chain transfer agent which has a polar group, the (meth) acryl monomer mentioned above is a free radical polymerization method. , (Meth) as described above in the presence of a polymerization initiator having a polar group, a method of polymerization or copolymerization by a conventionally known method such as a living radical polymerization method, an inipher polymerization method, an anion polymerization method, a living anion polymerization method, and the like. The method of superposing | polymerizing or copolymerizing an acryl monomer by a conventionally well-known method, such as a free radical polymerization method, a living radical polymerization method, an inipher polymerization method, an anion polymerization method, a living anion polymerization method, is mentioned. These methods may be used independently and may use 2 or more types together. Moreover, that a polar group was introduce | transduced only into the molecular terminal of the said (meth) acrylic resin can be confirmed by ¹³ C-NMR, for example.

The chain transfer agent which has the said polar group is not specifically limited, For example, mercaptopropanediol which has a hydroxyl group as a polar group, thioglycerol, the mercaptosuccinic acid which has a carboxyl group as a polar group, mercaptoacetic acid, the amino ethane thiol which has an amino group as a polar group Can be mentioned.

The polymerization initiator which has the said polar group is not specifically limited, For example, P-mentan hydroperoxide ("Permenta H", Nichiyu Co., Ltd.), diisopropylbenzene hydroperoxide ("Percumyl P", Nichiyu Co., Ltd.) ), 1,2,3,3-tetramethylbutyl hydroperoxide ("Perocta H", Nichiyu Co., Ltd.), cumene hydroperoxide ("Percumyl H-80", Nichiyu Co., Ltd.), t-butyl Hydroperoxide ("perbutyl H-69", Nichiyu Corporation), cyclohexanone peroxide ("Perhexa H", Nichiyu Corporation), 1,1,3,3- tetramethylbutyl hydroperoxide, t- Butyl hydroperoxide, t-amyl hydroperoxide, Disuccinic acid peroxide ("Perroyl SA", Nichiyu Corporation make) is mentioned. Moreover, you may use various azo initiators containing a nitrogen element or an acidic radical.

The minimum with preferable weight average molecular weight by polystyrene conversion of the said (meth) acrylic resin is 5000, and a preferable upper limit is 50000. If the weight average molecular weight is less than 5000, the metal oxide fine particle dispersion paste which has the viscosity required for screen printing may not be obtained. When a weight average molecular weight exceeds 50000, since the dispersibility of the metal oxide fine particle dispersion paste obtained may fall, or soft yarn will arise easily, printability may deteriorate. The upper limit with more preferable weight average molecular weight is 40000, and a more preferable upper limit is 30000. When the (meth) acrylic resin whose weight average molecular weight by polystyrene conversion is 5000-30000 is used, the image formed by screen printing becomes especially clear.

In addition, the weight average molecular weight by polystyrene conversion is computed by performing GPC measurement using the column LF-804 by SHOKO Corporation, for example as a column.

Although the said cellulose resin is not specifically limited, For example, ethyl cellulose and carboxymethyl cellulose are preferable.

The said polyether resin is not specifically limited, For example, polyethyleneglycol, polypropylene glycol, polytetramethylene glycol, etc. are mentioned. Especially, since it has a 2 or more hydroxyl group in the said molecule | numerator, the ratio of the number of carbon atoms with respect to the number of hydroxyl groups in a molecule | numerator is less than 5, and compatibility with the polyol whose viscosity at normal temperature is 100 mPa * s or more is favorable. It is preferable that it is a copolymer of polyethyleneglycol and polypropylene glycol.

Although the said polyacetal resin is not specifically limited, The polyacetal resin which has units, such as ethylene, propylene, tetramethylene, is preferable like the said polyether resin.

It is preferable that the said polyvinyl acetal resin is polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with an aldehyde.

It is preferable that the said polyvinyl alcohol is polyvinyl alcohol obtained by saponifying the polymer of vinyl esters, such as vinyl formate, vinyl acetate, a vinyl propionate, and a vinyl pivalate. In view of economics, the vinyl ester is more preferably vinyl acetate.

It is preferable that the said polyvinyl alcohol is also polyvinyl alcohol obtained by saponifying the copolymer of the said vinyl ester and an alpha olefin. By using an alpha olefin, the hydrogen bonding force of a polyvinyl acetal resin falls, As a result, stability with time or printability of the viscosity of the metal oxide fine particle dispersion paste obtained can be improved. As said alpha-olefin, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, hexylene, cyclohexylene, cyclohexylethylene, cyclohexyl propylene is mentioned, for example. Especially, ethylene is preferable.

As the polyvinyl alcohol, a terminally modified polyvinyl alcohol obtained by copolymerizing the vinyl ester and ethylene in the presence of a thiol compound such as thiol acetic acid or mercaptopropionic acid and then saponifying may be used.

When copolymerizing the said polyvinyl alcohol, the minimum with preferable content of the said alpha olefin is 1 mol%, and a preferable upper limit is 20 mol%. If content of the said alpha olefin is less than 1 mol%, the effect of adding the said alpha olefin may not be acquired. When content of the said alpha-olefin exceeds 20 mol%, since the solubility of the said polyvinyl alcohol in water falls, it becomes difficult to perform acetalization reaction, or the hydrophobicity of the polyvinyl acetal resin obtained becomes too strong, and organic Solubility to a solvent may fall.

In the metal oxide fine particle dispersion paste of this invention, the minimum with preferable content of the said binder resin is 1 weight%, and a preferable upper limit is 20 weight%. When content of the said binder resin is less than 1 weight%, the thickening effect by addition of binder resin may not be fully acquired. When content of the said binder resin exceeds 20 weight%, residual carbon after sintering may increase. The minimum with more preferable content of the said binder resin is 3 weight%, and a more preferable upper limit is 15 weight%.

In the metal oxide fine particle dispersion paste of the present invention, among other organic solvents having a boiling point of 140 ° C. or higher as mentioned above, in particular, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol mono Ethyl ether acetate, diethylene glycol monobutyl ether acetate, dihydroterpineol acetate, terpineol acetate, 2-butoxyethyl acetate, 2-ethoxyethyl acetate, 2-methoxyethyl acetate, 2-phenoxyethanol , 2- (methoxymethoxy) ethanol, triethylene glycol monomethyl ether, triethylene glycol, diethylene glycol monobutyl acetate, diethylene glycol monobutyl ether acetate, phenoxy acetate, phenoxyethyl acetate, ethylene glycol monophenyl Ether, diethylene glycol monophenyl ether, ethylene glycol Call monobenzyl ether, diethylene glycol monobenzyl ether, it is preferred to use propylene glycol monomethyl ether, benzyl glycol, phenyl ethyl, methyl, phenyl ethyl acetate, ethyl benzoate, and benzoate. Although the said polyol may be low in solubility with respect to binder resins, such as said (meth) acrylic resin, in combination with these organic solvents, the solubility with respect to binder resin can be improved, maintaining the dispersibility of metal oxide fine particles.

As for the metal oxide fine particle dispersion paste of this invention, the preferable minimum of the viscosity measured using the Brookfield viscometer at 23 degreeC and 10 rpm of probes is 6 Pa.s, and a preferable upper limit is 40 Pa.s. When the said viscosity is less than 6 Pa * s, the said metal oxide fine particle may precipitate and a dispersibility may become low. When the said viscosity exceeds 40 Pa * s, in case of screen-printing using a metal oxide fine particle dispersion paste, twisting may arise.

The method for producing the metal oxide fine particle dispersion paste of the present invention is not particularly limited, and for example, the binder resin and various additives are added to the metal oxide fine particle dispersion slurry of the present invention, The method of performing a dispersion process again is mentioned. Further, the metal oxide fine particles, the organic solvent, and the polymer anionic dispersant are mixed using a mixer such as a bead mill, ball mill, blender mill, and three roll mill, and then the binder resin is further added to the mixer. You may mix by this.

Although the use of the metal oxide fine particle dispersion slurry of this invention and the metal oxide fine particle dispersion paste of this invention is not specifically limited, For example, it is formed as a transparent electrode, such as a plasma display panel, a liquid crystal display panel, a solar cell, a lithium ion battery. It is preferable to use it as a material for manufacturing a metal oxide thin film.

As a manufacturing method of the said metal oxide thin film, the metal oxide fine particle dispersion slurry of this invention or the metal oxide fine particle of this invention is used, for example using various printing methods, such as screen printing, gravure offset printing, a roll coater, and a blade coater. After coating a dispersion paste on a board | substrate, the method of solvent drying or sintering is mentioned.

The manufacturing method of the metal oxide thin film which has the process of coating the metal oxide fine particle dispersion slurry of this invention or the metal oxide fine particle dispersion paste of this invention by screen printing is also one of this invention.

The metal oxide thin film obtained using the manufacturing method of the metal oxide thin film of this invention is also one of this invention. And when magnesium oxide fine particle dispersion paste is used as metal oxide fine particle dispersion paste of this invention, a magnesium oxide thin film is obtained.

When the magnesium oxide thin film obtained in this way is used as a dielectric protective layer of a plasma display, the front plate for plasma displays is obtained. Such a front panel for plasma display is also one of the present invention.

When the metal oxide thin film of this invention is a magnesium oxide thin film, the preferable upper limit of residual carbon after baking a magnesium oxide thin film at 450 degreeC for 30 minutes is 1 weight%. When the residual carbon of magnesium oxide exceeds 1 weight%, the residual carbon after baking may increase, and the lifetime of a plasma display panel may shorten. The upper limit with more preferable residual carbon after baking the said magnesium oxide thin film at 450 degreeC for 30 minutes is 0.5 weight%.

In addition, the method for producing the metal oxide fine particles is not particularly limited, but in the metal oxide thin film of the present invention, since the amount of residual carbon after firing can be reduced, for example, the metal oxide in the process of micronization It is preferable that the composition be made by a gas phase oxidation reaction method in which no carbon is included in the composition.

In the plasma display faceplate of the present invention, when the magnesium oxide thin film is formed, it is necessary to print and fire the magnesium oxide fine particle dispersion paste on the transparent dielectric layer of the plasma display faceplate. In the present invention, a magnesium oxide fine particle dispersion paste is prepared on a transparent dielectric layer made of soda lime glass, borosilicate glass, aluminosilicate glass, barium strontium glass, boric acid, and a glass made of bismuth oxide-molybdenum oxide-alkali metal oxide. It can print and bake favorably.

According to this invention, the metal oxide fine particle dispersion slurry which implemented the outstanding screen printability by improving the dispersibility of metal oxide fine particles can be provided. Moreover, according to this invention, the metal oxide fine particle dispersion paste containing this metal oxide fine particle dispersion slurry, the manufacturing method of the metal oxide thin film using this metal oxide fine particle dispersion slurry, or this metal oxide fine particle dispersion paste, and the metal oxide thin film of The metal oxide thin film obtained by the manufacturing method can be provided.

Although an Example is given to the following and this invention is demonstrated to it in more detail, this invention is not limited only to these Examples.

(Example 1)

(Manufacture of Binder Resin)

In a 2-liter separable flask equipped with a stirrer, a cooler, a thermometer, a bath and a nitrogen gas inlet, 100 parts by weight of methyl methacrylate as a (meth) acrylic monomer, 1.5 parts by weight of mercaptosuccinic acid as a chain transfer agent, And 100 weight part of acetone was mixed as an organic solvent, and the monomer liquid mixture was obtained.

After removing the dissolved oxygen by bubbling the obtained monomer liquid mixture for 20 minutes using nitrogen gas, the inside of the separable flask system was replaced with nitrogen gas, and the temperature was raised until the bath was boiled while stirring. Next, the solution which diluted the polymerization initiator ("Perhexa H" by Nichiyu Corp.) with acetone was added. Moreover, the acetone solution containing a polymerization initiator was added several times during superposition | polymerization. After 7 hours from the start of the polymerization, the polymerization was terminated by cooling to room temperature to obtain an acetone solution of polymethyl methacrylate. The obtained polymethyl methacrylate was analyzed by gel permeation chromatography (GPC) using column LF-804 manufactured by SHOKO as a column. As a result, the weight average molecular weight in terms of polystyrene was 20,000.

(Production of Metal Oxide Fine Particle Dispersion Paste)

2,2,4-trimethyl-1,3-pentanediol monoisobutylate, propylene glycol monophenyl ether, and 1,6-hexanediol (final) so as to finally have a composition ratio of the metal oxide fine particle dispersion paste of Table 1 A polymer anionic dispersant ("DISPERBYK-111" manufactured by BICKEMI Co., Ltd.), and ITO particles (manufactured by CI Chemical Co., Ltd., average particle diameter 30 nm) in a vehicle in which the ratio of carbon atoms to base number = 3, solid at room temperature is mixed. Was added, and the bead mill treatment was performed for 6 hours using zirconia particles having a particle diameter of 1 mm as a bead mill (“RMB-08” manufactured by Imex Corporation) and a medium. Subsequently, the acetone solution of polymethylmethacrylate obtained by the above (manufacturing of binder resin) was added so that the resin solid content was 17% by weight, and acetone was removed by vacuum desolvent treatment to obtain a metal oxide fine particle dispersion paste.

(Example 2)

(Manufacture of Binder Resin)

In the same manner as in Example 1, an acetone solution of polymethyl methacrylate was obtained.

(Production of Metal Oxide Fine Particle Dispersion Paste)

Finally, α-terpineol, diethylene glycol monobutyl ether acetate, 1,4-butanediol (a ratio of the number of carbon atoms to the number of hydroxyl groups = 2, normal temperature so as to have a composition ratio of the metal oxide fine particle dispersion paste shown in Table 1) A polymer anionic dispersant ("leodol L-95" manufactured by Kao Corporation) in a vehicle in which a viscosity of 128 mPa · s) and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate were blended; And SnO ₂ particles (“S-2000” manufactured by JEMCO Co., Ltd., average particle diameter: 30 nm), and bead mills using zirconia particles having a particle diameter of 1 mm as bead mills (“RMB-08” manufactured by Imex Corporation) and media. The treatment was carried out for 6 hours. Subsequently, the acetone solution of polymethylmethacrylate obtained by the above (manufacturing of binder resin) was added so that the resin solid content was 17% by weight, and acetone was removed by vacuum desolvent treatment to obtain a metal oxide fine particle dispersion paste.

(Example 3)

(Manufacture of Binder Resin)

In the same manner as in Example 1, an acetone solution of polymethyl methacrylate was obtained.

(Production of Metal Oxide Fine Particle Dispersion Paste)

2,2,4-trimethyl-1,3-pentanediol monoisobutylate, 3-methyl-1,5-pentanediol (relative to the number of hydroxyl groups) so that the composition ratio of the metal oxide fine particle dispersion paste A polymer anionic dispersant (" RS-710 " manufactured by Toho Chemical Co., Ltd.), and TiO ₂ particles, in a vehicle containing a ratio of carbon atoms = 3, a viscosity of 173 mPa · s at normal temperature, and propylene glycol monophenyl ether Nippon Aerosil Co., Ltd. "P-25" and an average particle diameter of 20 nm were added, and the bead mill process was performed using the zirconia particle of 1 mm of particle diameters as a bead mill ("RMB-08" by Imex Corporation) and a media. It was carried out for 6 hours. Subsequently, the acetone solution of polymethyl methacrylate obtained in the above (manufacture of binder resin) was added so that the resin solid content was 13% by weight, and acetone was removed by vacuum desolvent treatment to obtain a metal oxide fine particle dispersion paste.

(Example 4)

(Manufacture of Binder Resin)

In the same manner as in Example 1, an acetone solution of polymethyl methacrylate was obtained.

(Production of Metal Oxide Fine Particle Dispersion Paste)

2,2,4-trimethyl-1,3-pentanediol monoisobutylate, 2,4-diethyl-1,5-pentanediol (hydroxyl) so as to finally have a composition ratio of the metal oxide fine particle dispersion paste of Table 1 A polymer anionic dispersant (ED-216 manufactured by Kusumoto Chemical Co., Ltd.), in a vehicle containing a ratio of carbon atoms to base number = 4.5, viscosity at room temperature of 1650 mPa · s), and propylene glycol monophenyl ether. And MgO particles ("Magnesia" manufactured by Ube Materialeria Co., Ltd., average particle size: 50 nm), and bead mill treatment using zirconia particles having a particle diameter of 1 mm as a bead mill (`` RMB-08 '' manufactured by Imex Corporation) and media. Was carried out for 6 hours. Subsequently, the acetone solution of polymethyl methacrylate obtained in the above (manufacture of binder resin) was added so that the resin solid content was 13% by weight, and acetone was removed by vacuum desolvent treatment to obtain a metal oxide fine particle dispersion paste.

(Example 5)

(Manufacture of Binder Resin)

In a 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a bath and a nitrogen gas inlet, 100 parts by weight of methyl methacrylate as a (meth) acrylic monomer, 0.4 part by weight of mercaptosuccinic acid as a chain transfer agent, and an organic solvent 100 weight part of ethyl acetate were mixed, and the monomer liquid mixture was obtained.

After removing the dissolved oxygen by bubbling the obtained monomer liquid mixture for 20 minutes using nitrogen gas, the inside of the separable flask system was replaced with nitrogen gas, and the temperature was raised until the bath was boiled while stirring. Next, the solution which diluted the polymerization initiator ("Per hexa H" by Nichiyu Corp.) with ethyl acetate was added. In addition, the ethyl acetate solution containing a polymerization initiator was added several times during superposition | polymerization.

After 7 hours from the start of the polymerization, the polymerization was terminated by cooling to room temperature to obtain an ethyl acetate solution of polymethyl methacrylate. The obtained polymethyl methacrylate was analyzed by gel permeation chromatography (GPC) using column LF-804 manufactured by SHOKO as a column. As a result, the weight average molecular weight in terms of polystyrene was 50,000.

(Production of Metal Oxide Fine Particle Dispersion Paste)

Terpineol acetate and 2,2,4-trimethyl-1,3-pentanediol mono to finally obtain a composition ratio of the metal oxide fine particle dispersion paste of Table 1 with respect to the ethyl acetate solution of the obtained polymethylmethacrylate. Solvent substitution was carried out with isobutylate, and polymethyl methacrylate was dispersed using a high speed disperser to obtain a vehicle.

Glycerine (the ratio of the number of carbon atoms to the number of hydroxyl groups = 1, the viscosity of 1412 mPa · s at normal temperature) so that the composition ratio of the metal oxide fine particle dispersion paste of Table 1 finally, a polymeric anionic dispersant (Daiichi Kogyo Pharmaceutical Co., Ltd.) Manufacture "Sharol AH") and ZnO particles ("50A" by Sakai Chemical Co., Ltd., 20 nm of average particle diameters) were kneaded with a high speed disperser, and the high viscosity metal oxide fine particle dispersion slurry was obtained. After the obtained high viscosity metal oxide fine particle dispersion slurry was kneaded with three roll mills to make it low-viscosity, it was mixed with the said vehicle, fully kneaded using a high speed stirring apparatus, and processed again using a three roll mill, and a metal oxide was carried out. A fine particle dispersion paste was obtained.

(Comparative Example 1)

(Production of Metal Oxide Fine Particle Dispersion Paste)

(Alpha) -terpineol, a polymeric anionic dispersing agent ("DISPERBYK-111" by BICKEM Co., Ltd.), and ITO particle | grains (Cai Chemicals make, average particle diameter 30nm) so that it may become the composition ratio of the metal oxide fine particle dispersion paste of Table 1 finally. ) Was blended, and bead mill treatment was performed for 6 hours using bead mills (" RMB-08 " manufactured by IMEX Corporation) and zirconia particles having a particle diameter of 1 mm. Subsequently, ethyl cellulose (STD100, weight average molecular weight 90,000) was added to 3% by weight, ethyl cellulose was dispersed using a high speed disperser, sufficiently kneaded using a high speed stirring device, and then treated using a three roll mill. Was carried out to obtain a metal oxide fine particle dispersion paste.

(Comparative Example 2)

(Production of Metal Oxide Fine Particle Dispersion Paste)

Finally, a polymer anionic dispersant ("L-95" manufactured by Kao Corporation) and SnO ₂ particles ("S-2000" manufactured by JEMCO Corporation, average particle diameter 30 nm) so as to have a composition ratio of the metal oxide fine particle dispersion paste of Table 1 finally. Except having used, it carried out similarly to the comparative example 1, and obtained metal oxide fine particle dispersion paste.

(Comparative Example 3)

(Production of Metal Oxide Fine Particle Dispersion Paste)

Finally, so that the composition ratio of the metal oxide fine particle dispersion paste shown in Table 1, α- terpineol, no ongye polymer dispersing agent (Toho Chemical Co. Preparation "RS710"), and TiO ₂ particles (manufactured by Nippon Oh jilsa prepared "P-25 in the , And an average particle diameter of 20 nm) was obtained in the same manner as in Comparative Example 1 to obtain a metal oxide fine particle dispersion paste.

(Comparative Example 4)

(Production of Metal Oxide Fine Particle Dispersion Paste)

(Alpha) -terpineol, a polymeric anionic dispersing agent ("ED-216" by Kusumoto Chemical Co., Ltd.), and MgO particle | grains ("Magnesia by Ube Materialiers company") so that it may become a composition ratio of the metal oxide fine particle dispersion paste of Table 1 finally. , And an average particle diameter of 50 nm) was obtained in the same manner as in Comparative Example 1 to obtain a metal oxide fine particle dispersion paste.

(Comparative Example 5)

(Production of Metal Oxide Fine Particle Dispersion Paste)

(Alpha) -terpineol, a polymeric anionic dispersing agent ("Sharol AH" by Dai-ichi Chemical Co., Ltd.), and ZnO particle | grains ("50A" by Sakai Chemical company), so that it may become a composition ratio of the metal oxide fine particle dispersion paste of Table 1 finally. Except having used the average particle diameter of 20 nm), it carried out similarly to the comparative example 1, and obtained metal oxide fine particle dispersion paste.

<Evaluation>

The following evaluation was performed about the metal oxide fine particle dispersion paste obtained in Examples 1-5 and Comparative Examples 1-5. The results are shown in Table 1 and Table 2.

(1) screen printability

Using a metal oxide fine particle dispersion paste, a screen printing machine ("MT-320TV" manufactured by Microtec Co., Ltd., gap = 2.0 mm, squeegee speed = 50 mm / s, scraper speed = 50 mm / s, squeegee pressure = 0.25 MPa, scraper pressure) = 0.17 MPa, back pressure = 0.10 MPa), screen making (Tokyo Process Service Co., Ltd. "SX230", 20 micrometers of emulsion, screen frame 320 mm x 320 mm), printed board (150 mm x 150 mm of soda glass), Thickness was 15 mm) and screen printing was performed in the environment of the temperature of 23 degreeC, and 50% of humidity using the printed image (Line / Space = 50 micrometer / 150 micrometer). Ten continuous printings were performed, and the printed image of the tenth obtained sheet was observed with a stereo microscope, and evaluated as follows.

○ There was no variation in the thickness of the print image

△ The thickness of the print image was uneven or the print image was very thin.

No ink was applied to the printed board by clogging

(2) sinterability

The metal oxide fine particle dispersion paste was coated on the glass substrate using the applicator set to 5 mils, dried for 30 minutes in the 150 degreeC ventilation oven, and baked for 30 minutes in the 450 degreeC electric furnace. Residual carbon (ppm) was measured with the carbon sulfur analyzer manufactured by Horiba. In addition, the baked color was visually confirmed and evaluated as follows.

○ was colorless

△ It became pale yellow

× showed a brown baked color

(3) storage stability

After the metal oxide fine particle dispersion paste was left standing in a constant temperature chamber at 23 ° C. for 2 weeks, the state of the paste was visually confirmed and evaluated as follows.

○ No layer separation or sedimentation of metal oxide fine particles

A clear solution leaked out, but could be redispersed

Separated into 2 layers, and the metal oxide fine particles precipitated

(Example 6)

12 parts by weight of 1,6-hexanediol (ratio of carbon atoms to number of hydroxyl groups = 3, solid at room temperature), 5 parts by weight of propylene glycol, 1 part by weight of surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.), and a polymer After blending 2 parts by weight of an anionic dispersant ("DISPERBYK-111" manufactured by BIC Chem Co., Ltd.) and mixing using a high speed disperser, 20 parts by weight of ITO particles (manufactured by CI Chemical Co., Ltd., average particle size 30 nm) were added to the three rolls. The treatment was performed until the viscosity was low and smooth with a mill. Subsequently, 30 weight part of 1, 6- hexanediol and 30 weight part of propylene glycol monophenyl ethers were added, and it stirred with the high speed stirrer to obtain metal oxide fine particle dispersion slurry.

(Example 7)

12 parts by weight of 2-ethyl-1,3-hexanediol (ratio of carbon atoms to number of hydroxyl groups = 4, viscosity at room temperature of 323 mPa · s) and 1 part by weight of surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.) 2 parts by weight of a polymeric anionic dispersant ("L-95" manufactured by Kao Corporation) and 20 parts by weight of SnO ₂ particles ("S-2000" manufactured by JEMCO Co., Ltd., average particle diameter 30 nm) were added to provide a viscosity in three roll mills. The treatment was carried out until it was low and smooth. Subsequently, 53 parts by weight of 2-ethyl-1,3-hexanediol and 7 parts by weight of ethyl benzoate were added, followed by stirring with a high speed stirrer to obtain a metal oxide fine particle dispersion slurry.

(Example 8)

30 parts by weight of 3-methyl-1,5-pentanediol (ratio of carbon atoms to number of hydroxyl groups = 3, viscosity at room temperature of 173 mPa · s) and 1 part by weight of surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.) 2 parts by weight of a polymeric anionic dispersant (&quot; RS710 &quot; manufactured by Toho Chemical Co., Ltd.) and 40 parts by weight of TiO ₂ particles (&quot; P-25 &quot; The process was performed until it became low and became smooth. Then, 12 parts by weight of 3-methyl-1,5-pentanediol and 15 parts by weight of ethylene glycol monophenyl ether were added, followed by stirring with a high speed stirrer to obtain a metal oxide fine particle dispersion slurry.

(Example 9)

2,4-diethyl-1,5-pentanediol (ratio of carbon atoms to hydroxyl number = 4.5, viscosity at room temperature 1650 mPa · s) 20 parts by weight, surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.) 1 part by weight, 2 parts by weight of a polymer anionic dispersant ("ED-216" manufactured by Kusumoto Chemical Co., Ltd.), and 30 parts by weight of MgO particles ("magnesia" manufactured by Ube Materialeria Co., Ltd., average particle size 50 nm) were added. The process was performed until the viscosity was low and it became smooth with a roll mill. Then, 33 parts by weight of 2,4-diethyl-1,5-pentanediol and 20 parts by weight of propylene glycol monophenyl ether were added, followed by stirring with a high speed stirrer to obtain a metal oxide fine particle dispersion slurry.

(Example 10)

6 parts by weight of glycerin (ratio of carbon atoms to number of hydroxyl groups = 1, viscosity at 1212 mPas) at room temperature, 6 parts by weight of α-terpineol, and 1 part by weight of surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.) 2 parts by weight of a polymeric anionic dispersant ("Sharol AH" manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.), and 30 parts by weight of ZnO particles ("50A" manufactured by Sakai Chemical Co., Ltd., 20 nm in average particle diameter) were added. The process was performed until it became smooth. Next, 21 parts by weight of α-terpineol and 20 parts by weight of terpineol acetate were added, followed by stirring with a high speed stirrer to obtain a metal oxide fine particle dispersion slurry.

<Evaluation>

The following evaluation was performed about the metal oxide fine particle dispersion slurry obtained in Examples 6-10. The results are shown in Tables 3 and 4.

(1) screen printability

Using a metal oxide fine particle dispersion slurry, a screen printing machine ("MT-320TV" manufactured by Microtec Co., Ltd., gap = 2.0 mm, squeegee speed = 50 mm / s, scraper speed = 50 mm / s, squeegee pressure = 0.25 MPa, scraper pressure) = 0.17 MPa, back pressure = 0.10 MPa), screen making ("ST500CAL" manufactured by Tokyo Process Service, Inc., 2 μm of emulsion, screen frame 320 mm × 320 mm), printed board (150 mm × 150 mm soda glass, thickness 15 mm) , Screen printing was performed in the environment of the temperature of 23 degreeC, and 50% of humidity using the printed image (Line / Space = 50 micrometer / 150 micrometer). Ten continuous printings were performed, and the printed image of the tenth obtained sheet was observed with a stereo microscope, and evaluated as follows.

○ There was no variation in the thickness of the print image

△ The thickness of the print image was uneven or the print image was very thin.

No ink was applied to the printed board due to blockage

(2) sinterability

The metal oxide fine particle dispersion slurry was coated on the glass substrate using the applicator set to 5 mils, dried for 30 minutes in a 150 degreeC ventilation oven, and baked for 30 minutes in the 450 degreeC electric furnace. Residual carbon (ppm) was measured with the carbon sulfur analyzer manufactured by Horiba. In addition, the baked color was visually confirmed and evaluated as follows.

○ was colorless

△ It became pale yellow

× showed a brown baked color

(3) storage stability

After the metal oxide fine particle dispersion slurry was allowed to stand in a constant temperature chamber at 23 ° C. for 2 weeks, the state of the slurry was visually confirmed and evaluated as follows.

○ No layer separation or sedimentation of metal oxide fine particles

A clear solution leaked out, but could be redispersed

Separated into 2 layers, and the metal oxide fine particles precipitated

(Example 11)

2,4-diethyl-1,5-pentanediol (ratio of carbon atoms to hydroxyl number = 4.5, viscosity at room temperature 1650 mPa · s) 12 parts by weight, surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.) 1 part by weight and 2 parts by weight of a polymer anionic dispersant ("DISPERBYK-111" manufactured by BICCHEM Corporation) were mixed and mixed using a high speed disperser, and then 20 parts by weight of ITO particles (Cai Chemical Co., Ltd., average particle diameter 30 nm). It added and processed until it had a low viscosity and became smooth with three roll mills. Subsequently, ethyl cellulose (STD10, manufactured by WAKO Chemical Co., Ltd.) previously dissolved in a 1: 1 mixture of 2,4-diethyl-1,5-pentanediol and propylene glycol monophenyl ether was added so as to obtain a resin solid content of Table 5. 2,4-diethyl-1,5-pentanediol and propylene glycol monophenyl ether were further added, and it stirred with a high speed stirrer to obtain the metal oxide fine particle dispersion paste.

(Example 12)

12 parts by weight of 3-methyl-1,5-pentanediol (ratio of carbon atoms to number of hydroxyl groups = 3, viscosity 250 mPa · s at normal temperature), 1 part by weight of surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.) 2 parts by weight of a polymeric anionic dispersant ("L-95" manufactured by Kao Corporation) and 20 parts by weight of SnO ₂ particles ("S-2000" manufactured by JEMCO Co., Ltd., average particle diameter 30 nm) were added to provide a viscosity in three roll mills. The treatment was carried out until it was low and smooth. Subsequently, ethyl cellulose (STD10, manufactured by WAKO Chemical Co., Ltd.) previously dissolved in a 1: 1 mixture of 3-methyl-1,5-pentanediol and propylene glycol monophenyl ether was added to obtain a resin solid content of Table 5, and 3 -Methyl-1,5-pentanediol and the propylene glycol monophenyl ether solution were further added, and it stirred with the high speed stirrer to obtain the metal oxide fine particle dispersion paste.

(Example 13)

30 parts by weight of 2-ethyl-1,3-hexanediol (ratio of carbon atoms to number of hydroxyl groups = 4, viscosity at room temperature of 323 mPa · s) and 1 part by weight of surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.) 2 parts by weight of a polymeric anionic dispersant (&quot; RS710 &quot; manufactured by Toho Chemical Co., Ltd.), and 60 parts by weight of TiO ₂ particles (&quot; P-25 &quot; The process was performed until it became low and became smooth. Subsequently, ethyl cellulose (STD10, manufactured by WAKO Chemical Co., Ltd.) previously dissolved in a 2-ethyl-1,3-hexanediol solution was added to obtain a resin solid content of Table 5, and the 2-ethyl-1,3-hexanediol solution was added. It was further added and stirred with a high speed stirrer to obtain a metal oxide fine particle dispersion paste.

(Example 14)

20 parts by weight of 2-ethyl-1,3-hexanediol (ratio of carbon atoms to number of hydroxyl groups = 4, viscosity at room temperature of 323 mPa · s) and 1 part by weight of surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.) , 2 parts by weight of a polymer anionic dispersant ("ED-216" manufactured by Kusumoto Chemical Co., Ltd.), and 40 parts by weight of MgO particles ("Magnesia" manufactured by Ube Materials Co., Ltd., average particle size 50 nm) were added to the viscosity in three roll mills. The process was performed until it became low and became smooth. Subsequently, ethyl cellulose (STD10, manufactured by WAKO Chemical Co., Ltd.) previously dissolved in a 2-ethyl-1,3-hexanediol solution was added to obtain a resin solid content of Table 5, and the 2-ethyl-1,3-hexanediol solution was added. It was further added and stirred with a high speed stirrer to obtain a metal oxide fine particle dispersion paste.

(Example 15)

20 parts by weight of 2-ethyl-1,3-hexanediol (ratio of carbon atoms to number of hydroxyl groups = 4, viscosity at room temperature of 323 mPa · s) and 1 part by weight of surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.) 2 parts by weight of a polymeric anionic dispersant (&quot; Sharol AH &quot; manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) and 40 parts by weight of ZnO particles (&quot; 50A &quot; manufactured by Sakai Chemical Co., Ltd., average particle size 20 nm) were added. The process was performed until it became smooth. Subsequently, ethyl cellulose (STD10, manufactured by WAKO Chemical Co., Ltd.) previously dissolved in a 1: 1 mixture of 2-ethyl-1,3-hexanediol and ethylene glycol monophenyl ether was added so as to obtain a resin solid content of Table 5, and -Ethyl-1,3-hexanediol and ethylene glycol monophenyl ether were further added, and it stirred with the high speed stirrer to obtain the metal oxide fine particle dispersion paste.

(Example 16)

(Manufacture of Binder Resin)

60 parts by weight of isobutyl methacrylate (IBMA, manufactured by Mitsubishi Rayon Co., Ltd.) as a (meth) acryl monomer, in a 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath and a nitrogen gas inlet, and a methyl methacrylate ( 10 parts by weight of MMA, manufactured by Mitsubishi Rayon, 30 parts by weight of a methacrylate monomer having a polyethylene chain (PEOMA, Nichiyu Co., Ltd. "PME-1000"), 1.5 parts by weight of mercaptosuccinic acid as a chain transfer agent, and acetone as an organic solvent. 100 weight part was mixed and the monomer liquid mixture was obtained.

After removing the dissolved oxygen by bubbling the obtained monomer liquid mixture for 20 minutes using nitrogen gas, the inside of the separable flask system was replaced with nitrogen gas, and the temperature was raised until the bath was boiled while stirring. Next, the solution which diluted the polymerization initiator ("Perhexa H" by Nichiyu Corp.) with acetone was added. Moreover, the acetone solution containing a polymerization initiator was added several times during superposition | polymerization. After 7 hours from the start of polymerization, the polymerization was terminated by cooling to room temperature to obtain an acetone solution of (meth) acrylic resin. The obtained polymethyl methacrylate was analyzed by gel permeation chromatography (GPC) using column LF-804 manufactured by SHOKO as a column. As a result, the weight average molecular weight in terms of polystyrene was 20,000.

(Production of Metal Oxide Fine Particle Dispersion Paste)

2,4-diethyl-1,5-pentanediol (the ratio of the number of carbon atoms to the number of hydroxyl groups = 4.5, and the viscosity at normal temperature is 1650 mPa * so that it may become the composition ratio of the metal oxide fine particle dispersion paste of Table 5 finally. s), 0.5 part by weight of a surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.), a polymer anionic dispersant ("DISPERBYK-111" manufactured by BICKEMIC COMPANY), and ITO particles (CI Chemicals) in a vehicle containing propylene glycol monophenyl ether. Co., Ltd., the average particle diameter of 30 nm) was added, and bead mill processing was performed for 6 hours using bead mills (“RMB-08” manufactured by IMEX Corporation) and zirconia particles having a particle diameter of 1 mm as media. Subsequently, the acetone solution of the (meth) acrylic resin obtained by the above (manufacturing of the binder resin) was added so that the resin solid content was 17% by weight, and acetone was removed by vacuum desolvent treatment to obtain a metal oxide fine particle dispersion paste.

(Example 17)

(Manufacture of Binder Resin)

In the same manner as in Example 16, an acetone solution of a (meth) acrylic resin was obtained.

(Production of Metal Oxide Fine Particle Dispersion Paste)

2-ethyl-1,3-hexanediol (the ratio of the number of carbon atoms to the number of hydroxyl groups = 4, the viscosity at room temperature of 323 mPa · s) so as to be the composition ratio of the metal oxide fine particle dispersion paste of Table 5 finally, and In a vehicle containing ethylene glycol monophenyl ether, 0.5 part by weight of a surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.), a polymer anionic dispersant ("Leodol L-95" manufactured by Kao Corporation), and SnO ₂ particles (JEMCO Corporation) Manufacture "S-2000" and the average particle diameter of 30 nm were added, and the bead mill process was performed for 6 hours using the zirconia particle of 1 mm of particle diameters as a bead mill ("RMB-08" by IMEX) and a medium. Subsequently, the acetone solution of the (meth) acrylic resin obtained by the above (manufacturing of the binder resin) was added so that the resin solid content was 17% by weight, and acetone was removed by vacuum desolvent treatment to obtain a metal oxide fine particle dispersion paste.

(Example 18)

(Manufacture of Binder Resin)

In the same manner as in Example 16, an acetone solution of a (meth) acrylic resin was obtained.

(Production of Metal Oxide Fine Particle Dispersion Paste)

Finally, 2-ethyl-1,3-hexanediol (the ratio of the number of carbon atoms to the number of hydroxyl atoms = 4, the viscosity at room temperature of 323 mPa · s) is blended so as to have a composition ratio of the metal oxide fine particle dispersion paste shown in Table 5. a vehicle, a surfactant (manufactured by "BL25" Nikko Chemicals Inc.) 0.5 part by weight, the polymer not ongye dispersing agent (Toho Chemical Co. Preparation "RS-710"), and TiO ₂ particles (manufactured by Nippon Oh jilsa prepared "P-25" in the And 20 nm of average particle diameters were added, and bead mill processing was performed for 6 hours using the zirconia particle of a particle diameter of 1 mm as a bead mill (IRMX-made "RMB-08") and a medium. Subsequently, the acetone solution of the (meth) acrylic resin obtained by the above (manufacturing of the binder resin) was added so that the resin solid content was 13% by weight, and acetone was removed by vacuum desolvent treatment to obtain a metal oxide fine particle dispersion paste.

(Example 19)

(Manufacture of Binder Resin)

In the same manner as in Example 16, an acetone solution of a (meth) acrylic resin was obtained.

(Production of Metal Oxide Fine Particle Dispersion Paste)

Finally, 2-ethyl-1,3-hexanediol (the ratio of the number of carbon atoms to the number of hydroxyl atoms = 4, the viscosity at room temperature of 323 mPa · s) is blended so as to have a composition ratio of the metal oxide fine particle dispersion paste shown in Table 5. In one vehicle, 0.5 weight part of surfactant ("BL25" by Nikko Chemical Co., Ltd.), a polymeric anionic dispersant ("ED-216" by Kusumoto Chemical Co., Ltd.), and MgO particle | grains ("Magnesia" by Ube Materials Co., Ltd.), average A particle diameter of 50 nm) was added, and the bead mill treatment was performed for 6 hours using a zirconia particle having a particle diameter of 1 mm as a bead mill (“RMB-08” manufactured by IMAX Corporation) and a medium. Subsequently, the acetone solution of the (meth) acrylic resin obtained by the above (manufacturing of the binder resin) was added so that the resin solid content was 13% by weight, and acetone was removed by vacuum desolvent treatment to obtain a metal oxide fine particle dispersion paste.

(Example 20)

(Manufacture of Binder Resin)

In the same manner as in Example 16, an acetone solution of a (meth) acrylic resin was obtained.

(Production of Metal Oxide Fine Particle Dispersion Paste)

3-methyl-1,5-pentanediol (the ratio of the number of carbon atoms to the number of hydroxyl groups = 3, the viscosity at room temperature 250 mPa * s) so that it may become the composition ratio of the metal oxide fine particle dispersion paste of Table 5 finally, and To a vehicle containing propylene glycol monophenyl ether, 0.5 part by weight of a surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.), a polymer anionic dispersant ("Sharol AH" manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.), and ZnO particles (manufactured by Sakai Chemical Co., Ltd.) "50A" and an average particle diameter of 20 nm were added, and the bead mill treatment was performed for 6 hours using bead mills ("RMB-08" manufactured by IMEX Corporation) and zirconia particles having a particle diameter of 1 mm as media. Subsequently, the acetone solution of the (meth) acrylic resin obtained by the above (manufacturing of the binder resin) was added so that the resin solid content was 13% by weight, and acetone was removed by vacuum desolvent treatment to obtain a metal oxide fine particle dispersion paste.

<Evaluation>

The following evaluation was performed about the metal oxide fine particle dispersion paste obtained in Examples 11-20. The results are shown in Tables 5 and 6.

(1) screen printability

Using a metal oxide fine particle dispersion paste, a screen printing machine ("MT-320TV" manufactured by Microtec Co., Ltd., gap = 2.0 mm, squeegee speed = 50 mm / s, scraper speed = 50 mm / s, squeegee pressure = 0.25 MPa, scraper pressure) = 0.17 MPa, back pressure = 0.10 MPa), screen making ("ST500CAL" manufactured by Tokyo Process Service, Inc., 2 μm of emulsion, screen frame 320 mm × 320 mm), printed board (150 mm × 150 mm soda glass, thickness 15 mm) , Screen printing was performed in the environment of the temperature of 23 degreeC, and 50% of humidity using the printed image (Line / Space = 50 micrometer / 150 micrometer). Ten continuous printings were performed, and the printed image of the tenth obtained sheet was observed with a stereo microscope, and evaluated as follows.

○ There was no variation in the thickness of the print image

△ The thickness of the print image was uneven or the print image was very thin.

No ink was applied to the printed board due to blockage

(2) sinterability

The metal oxide fine particle dispersion paste was coated on the glass substrate using the applicator set to 5 mils, dried for 30 minutes in the 150 degreeC ventilation oven, and baked for 30 minutes in the 450 degreeC electric furnace. Residual carbon (ppm) was measured with the carbon sulfur analyzer manufactured by Horiba. In addition, the baked color was visually confirmed and evaluated as follows.

○ was colorless

△ It became pale yellow

× showed a brown baked color

(3) storage stability

After the metal oxide fine particle dispersion paste was left standing in a constant temperature chamber at 23 ° C. for 2 weeks, the state of the paste was visually confirmed and evaluated as follows.

○ No layer separation or sedimentation of metal oxide fine particles

A clear solution leaked out, but could be redispersed

Separated into 2 layers, and the metal oxide fine particles precipitated

(Example 21)

(Manufacture of Binder Resin)

An acetone solution of (meth) acrylic resin (polymethyl methacrylate) was obtained in the same manner as in Example 1 except that the amount of the chain transfer agent added in Example 1 was 1.2 parts by weight.

2-ethyl-1,3-hexanediol was added to the obtained solution, and the 2-ethyl-1,3-hexanediol solution of polymethyl methacrylate was obtained by performing the vacuum desolvent process.

(Production of Metal Oxide Fine Particle Dispersion Paste)

Finally, 2-ethyl-1,3-hexanediol (the ratio of the number of carbon atoms to the number of hydroxyl atoms = 4, the viscosity at room temperature of 323 mPa · s) so as to have a composition ratio of the metal oxide fine particle dispersion paste shown in Table 7, the interface An activator ("BL25" manufactured by Nikko Chemical Co., Ltd.), a polymer anionic dispersant ("ED-216" manufactured by Kusumoto Chemical Co., Ltd.), and MgO particles ("Magnesia" manufactured by Ube Materialeria, Inc., average particle diameter 50 nm) are mixed, The bead mill was performed for 6 hours using zirconia particles having a particle diameter of 1 mm as a bead mill (“RMB-08” manufactured by Imex Corporation) and the media.

Subsequently, the 2-ethyl-1,3-hexanediol solution of the polymethylmethacrylate obtained by said (production of binder resin) was added so that resin solid content might become the quantity of Table 7, and the metal oxide fine particle dispersion paste was obtained.

(Example 22)

(Manufacture of Binder Resin)

2-ethyl-1 of the (meth) acrylic resin in the same manner as in Example 21 except that isobutyl methacrylate (IBMA, manufactured by Mitsubishi Rayon) was used instead of methyl methacrylate as the (meth) acryl monomer. A 3-hexanediol solution was obtained.

(Production of Metal Oxide Fine Particle Dispersion Paste)

Finally, 2-ethyl-1,3-hexanediol (the ratio of the number of carbon atoms to the number of hydroxyl atoms = 4, the viscosity at room temperature of 323 mPa · s) so as to have a composition ratio of the metal oxide fine particle dispersion paste shown in Table 7, the interface 2-ethyl-1 of the (meth) acrylic resin obtained by the activator ("BL25" by Nikko Chemical Co., Ltd.), and MgO particles ("Magnesia" by Ube Materials Co., Ltd., average particle diameter 50nm), and the said (preparation of binder resin). The, 3-hexanediol solution was mixed, and bead mill treatment was carried out for 6 hours using zirconia particles having a particle diameter of 1 mm as a bead mill (“IMB-08” manufactured by Imex Corporation) and the media, thereby dispersing the metal oxide fine particle dispersion paste. Got it.

(Example 23)

(Manufacture of Binder Resin)

As a (meth) acryl monomer, 60 parts by weight of isobutyl methacrylate (IBMA, manufactured by Mitsubishi Rayon), 10 parts by weight of methyl methacrylate (MMA, manufactured by Mitsubishi Rayon), and a methacrylate monomer having a polyethylene chain (PEOMA A 2-ethyl-1,3-hexanediol solution of (meth) acrylic resin was obtained in the same manner as in Example 21 except that 30 parts by weight of Nichiyu Co., Ltd. "PME-1000") was used.

(Production of Metal Oxide Fine Particle Dispersion Paste)

Finally, 2-ethyl-1,3-hexanediol (the ratio of the number of carbon atoms to the number of hydroxyl atoms = 4, the viscosity at room temperature of 323 mPa · s) so as to have a composition ratio of the metal oxide fine particle dispersion paste shown in Table 7, the interface 2-ethyl-1 of the (meth) acrylic resin obtained by the activator ("BL25" by Nikko Chemical Co., Ltd.), and MgO particles ("Magnesia by Ube Materials Co., Ltd., average particle diameter 50nm), and said (Manufacture of binder resin). The, 3-hexanediol solution was mixed, and bead mill treatment was carried out for 6 hours using zirconia particles having a particle diameter of 1 mm as a bead mill (“IMB-08” manufactured by Imex Corporation) and the media, thereby dispersing the metal oxide fine particle dispersion paste. Got it.

(Example 24)

50 parts by weight of 2-ethyl-1,3-hexanediol (ratio of carbon atoms to number of hydroxyl groups = 4, viscosity at room temperature of 323 mPa · s) and 1 part by weight of surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.) 2 parts by weight of a polymer anionic dispersant ("DISPERBYK-111" manufactured by BIC Chem Corporation) and 30 parts by weight of MgO particles ("Magnesia" manufactured by Ube Materialeria Co., Ltd., average particle size 50 nm) were added, and a bead mill ("Imex Corporation" RMB-08 ") and the bead mill process were performed for 6 hours using zirconia particle of particle diameter of 1 mm as a media, and the metal oxide fine particle dispersion solution was obtained.

2-ethyl-1,3-hexane of ethyl cellulose in which 3 parts by weight of ethyl cellulose (STD100, manufactured by WAKO Chemical Co., Ltd.) was dissolved in 14 parts by weight of 2-ethyl-1,3-hexanediol in the obtained metal oxide fine particle dispersion solution The diol solution was added and stirred with a high speed stirrer to obtain a metal oxide fine particle dispersion paste.

(Comparative Example 6)

The metal oxide fine particle dispersion paste of Table 7 was obtained like Example 21 except having used alpha-terpineol instead of 2-ethyl-1,3-hexanediol as an organic solvent.

(Comparative Example 7)

The metal oxide fine particle dispersion paste of Table 7 was obtained like Example 22 except having used (alpha)-terpineol instead of 2-ethyl-1, 3- hexanediol as an organic solvent.

(Comparative Example 8)

As an organic solvent, the metal oxide fine particle dispersion paste of Table 7 was obtained like Example 23 except having used (alpha)-terpineol instead of 2-ethyl-1, 3- hexanediol.

(Comparative Example 9)

The metal oxide fine particle dispersion paste of Table 7 was obtained like Example 24 except having used (alpha)-terpineol instead of 2-ethyl-1,3-hexanediol as an organic solvent.

<Evaluation>

A conventional plasma display front plate is obtained by laminating a transparent dielectric layer composed of a transparent electrode (ITO) or a bus electrode (silver) on a substrate glass, and printing and firing a metal oxide fine particle dispersion paste. Subsequently, the sample which printed and baked the metal oxide fine particle dispersion paste on the laminated body which laminated | stacked the transparent dielectric layer on the substrate glass was evaluated, and it was set as the performance test of the front plate for plasma displays.

(Particle size distribution)

The obtained metal oxide fine particle dispersion paste was diluted with the ethanol solution, and particle size distribution was measured with the particle size distribution meter (LA-910 by Horiba Corporation).

( _Circle) and the case where D90 is 0.5 micrometer or less were made when (Dmax) was 0.5 micrometer or less, and the case where D90 exceeded 0.5 micrometer was made into x.

(Light transmittance)

<Production of Transparent Dielectric Layer>

A glass paste containing B ₂ O ₃ , Li ₂ O, Bi ₂ O ₃ and MoO ₃ as a main component, ethyl cellulose, and terpineol on the substrate glass was applied using a blade coater method, and then applied at 100 ° C. It dried on 30 minutes of conditions, and baked at the temperature of softening point +10 degreeC for 10 minutes, and formed the transparent dielectric layer of thickness 30micrometer.

<Production of Metal Oxide Fine Particle Sintered Film>

Using the metal oxide fine particle dispersion pastes obtained in Examples 21 to 24 and Comparative Examples 6 to 9, printing by a screen printing machine ("MT-320TV" manufactured by Microtec Co., Ltd.) was carried out under the following conditions. On the substrate glass which laminated | stacked the transparent dielectric layer obtained by the above, the dry film of the 10 cmx10 cm metal oxide fine particle dispersion paste was obtained.

<Printing conditions>

Gap: 2.0 mm, Squeegee Speed: 50 mm / s, Scraper Speed: 50 mm / s, Squeegee Pressure: 0.25 MPa, Scraper Pressure: 0.17 MPa, Back Pressure: 0.10 MPa, Screen Engraving ("ST500CAL" manufactured by Tokyo Process Service, Inc.) Emulsion 2 μm, screen frame 320 mm × 320 mm), printed substrate (150 mm × 150 mm soda glass, thickness 15 mm), temperature: 23 ° C., humidity: 50%, drying conditions: 150 ° C. × 10 minutes.

The obtained dry film was heated up to 400 degreeC at the temperature increase rate of 10 degree-C / min using muffle (Adovantec company make, FUW230PA), and after hold | maintaining for 30 minutes, it stood to cool and obtained the sintered film of metal oxide fine particles.

In addition, when using the metal oxide fine particle dispersion paste obtained in Example 24 and the comparative example 9, it heated up to 500 degreeC.

The thickness of the obtained sintered film was measured using the stylometer (P-16, the KLA-tencor company make). Subsequently, total light transmittance (n = 3) was measured by the method based on JISK6714 and JISK6718 using the haze meter (TC-H3DPK, the Tokyo Denshoku company make). (Circle) and the case where the obtained value is 90% or more (circle) and the case where it is less than 90% 88% or more were made into (circle) and the case where it is less than 88% and 85% or more were made into the case where (triangle | delta) and less than 85%.

In addition, the total light transmittance in the state which provided the transparent dielectric layer in the substrate glass was 91%.

(Density)

In the SEM photograph (20000 times) of the obtained metal oxide fine particle sintered film, all the interparticle space | gap seen in the visual field (6 micrometer x 5 micrometers) was confirmed at 5 visual fields.

(Circle) and the confirmed case were made into the case where the clearance gap of 100 nm or more was not confirmed.

(Dispersibility)

In the SEM photograph (5000 times) of the obtained metal oxide fine particle sintered film, the presence or absence of the magnesium oxide which aggregated in the visual field (24 micrometers x 20 micrometers) was confirmed at 5 visual fields.

(Circle) and the confirmed case were made into the case where the aggregate was not confirmed.

(Example 25)

2-ethyl-1,3-hexanediol (the ratio of the number of carbon atoms to the number of hydroxyl groups = 4, viscosity at room temperature 323 mPa · s) 70 parts by weight, MgO particles (`` Magnesia manufactured by Ube Materialeria '', average particle diameter 50 nm) 30 weight part was added, the bead mill process was performed for 6 hours using the zirconia particle of 1 mm of particle diameters as a bead mill (IRMX-made "RMB-08") and a media, and the metal oxide fine particle dispersion slurry was obtained. .

(Example 26)

70 parts by weight of ethanol, 30 parts by weight of MgO particles (&quot; magnesia manufactured by Ube Materials, 50 nm) was added, and a zirconia particle having a particle diameter of 1 mm was used as a bead mill (“RMB-08” manufactured by Imex Corporation) and the media. The bead mill treatment was performed for 6 hours using, to obtain a metal oxide fine particle dispersion slurry.

To the obtained slurry solution, 70 parts by weight of 2-ethyl-1,3-hexanediol (ratio of carbon atoms to hydroxyl number = 4, viscosity at room temperature of 323 mPa · s) was added, and ethanol was removed by vacuum desolvent treatment. To obtain a metal oxide fine particle dispersion slurry.

(Example 27)

70 parts by weight of ethanol, 30 parts by weight of TiO ₂ particles ("P-25" manufactured by Nippon Aerosol Co., Ltd., average 20 nm) were added, and the particle diameter 1 was used as a bead mill ("RMB-08" manufactured by IMAX Corporation) and a medium. Bead mill treatment was performed for 6 hours using mm zirconia particles to obtain metal oxide fine particle dispersion slurry.

To the obtained slurry solution, 70 parts by weight of 2-ethyl-1,3-hexanediol (ratio of carbon atoms to hydroxyl number = 4, viscosity at room temperature of 323 mPa · s) was added, and ethanol was removed by vacuum desolvent treatment. To obtain a metal oxide fine particle dispersion slurry.

(Example 28)

Metal oxide fine particle dispersion slurry shown in Table 9 in the same manner as in Example 26, except that 2,4-diethyl-1,5-pentanediol was used instead of 2-ethyl-1,3-hexanediol as the organic solvent. Got.

(Example 29)

Metal oxide fine particle dispersion slurry of Table 9 was obtained like Example 26 except having used 1, 4- butanediol instead of 2-ethyl-1,3-hexanediol as an organic solvent.

(Example 30)

70 parts by weight of ethanol, 30 parts by weight of MgO particles (&quot; magnesia manufactured by Ube Materials, 50 nm) was added, and a zirconia particle having a particle diameter of 1 mm was used as a bead mill (“RMB-08” manufactured by Imex Corporation) and the media. The bead mill treatment was performed for 6 hours using, to obtain a metal oxide fine particle dispersion slurry.

40 parts by weight of 2-ethyl-1,3-hexanediol (ratio of carbon atoms to number of hydroxyl groups = 4, viscosity at room temperature of 323 mPa · s) and 30 parts by weight of isobornylcyclohexanol were added to the resulting slurry solution. Then, ethanol was removed by vacuum desolvent treatment to obtain a metal oxide fine particle dispersion slurry.

(Example 31)

As the organic solvent, instead of 40 parts by weight of 2-ethyl-1,3-hexanediol and 30 parts by weight of isobornylcyclohexanol, 50 parts by weight of 2,4-diethyl-1,5-pentanediol and isobornyl Metal oxide fine particle dispersion slurry of Table 9 was obtained like Example 30 except having used 20 weight part of cyclohexanol.

(Example 32)

The metal oxide fine particle dispersion slurry of Table 9 was obtained like Example 30 except having used 1, 4- butanediol instead of 2-ethyl-1,3-hexanediol as an organic solvent.

(Example 33)

85 parts by weight of ethanol and 15 parts by weight of MgO particles ("Magnesia" manufactured by Ube Materialeria Co., Ltd., an average particle diameter of 50 nm) were added, and a zirconia particle having a particle diameter of 1 mm was used as a bead mill ("RMB-08" manufactured by Imex Corporation) and a medium. The bead mill treatment was performed for 6 hours using, to obtain a metal oxide fine particle dispersion slurry.

60 parts by weight of 2,4-diethyl-1,5-pentanediol (ratio of carbon atoms to hydroxyl number = 4.5, viscosity at room temperature of 1650 mPa · s), isobornylcyclohexanol 25 Parts by weight were added and ethanol was removed by vacuum desolvent treatment to obtain a metal oxide fine particle dispersion slurry.

(Example 34)

Metal oxide fine particle dispersion slurry of Table 9 was obtained like Example 25 except having used the zirconia particle of 0.3 mm of particle diameters as a bead mill media.

(Comparative Examples 10-11)

Metal oxide fine particle dispersion slurry was obtained like Example 26 except having used the organic solvent of Table 9 instead of 2-ethyl-1,3-hexanediol as an organic solvent.

(Comparative Example 12)

Metal oxide fine particle dispersion slurry of Table 9 was obtained like Example 30 except having used butyl carbitol instead of 2-ethyl-1,3-hexanediol as an organic solvent.

<Evaluation>

The following evaluation was performed about the metal oxide fine particle dispersion slurry obtained in Examples 25-34 and Comparative Examples 10-12. The results are shown in Table 9 and Table 10.

(Particle size distribution)

The obtained metal oxide fine particle dispersion slurry was diluted with the ethanol solution, and particle size distribution was measured with the particle size distribution analyzer (LA-910 by Horiba Corporation).

( _Circle) and the case where D90 is 0.5 micrometer or less were made when (Dmax) was 0.5 micrometer or less, and the case where D90 exceeded 0.5 micrometer was made into x.

(Storage stability)

After the metal oxide fine particle dispersion slurry was allowed to stand in a constant temperature chamber at 23 ° C. for 2 weeks, the state of the slurry was visually confirmed and evaluated as follows.

○ No layer separation or sedimentation of metal oxide fine particles

A clear solution leaked out, but could be redispersed

Separated into 2 layers, and the metal oxide fine particles precipitated

(Screen printability)

Using a metal oxide fine particle dispersion slurry, a screen printing machine ("MT-320TV" manufactured by Microtec Co., Ltd., gap = 2.0 mm, squeegee speed = 50 mm / s, scraper speed = 50 mm / s, squeegee pressure = 0.25 MPa, scraper pressure) = 0.17 MPa, back pressure = 0.10 MPa), screen making ("ST500CAL" manufactured by Tokyo Process Service, Inc., 2 μm of emulsion, screen frame 320 mm × 320 mm), printed board (150 mm × 150 mm soda glass, thickness 15 mm) , Screen printing was performed in the environment of the temperature of 23 degreeC, and 50% of humidity using the printed image (Line / Space = 50 micrometer / 150 micrometer). Ten continuous printings were performed, and the printed image of the tenth obtained sheet was observed with a stereo microscope, and evaluated as follows. In addition, the thickness of the sintered film obtained as mentioned later was measured using the stylometer (P-16, the KLA-tencor company make).

○ There was no variation in the thickness of the print image

△ There was variation in the thickness of the print image

No ink was applied to the printed board due to blockage

(Sintering)

Using an applicator set at 5 mils, the metal oxide fine particle dispersion slurry was coated on a glass substrate, dried in a blowing oven at 150 ° C. for 30 minutes, and then baked in a 450 ° C. electric furnace for 30 minutes to form a metal oxide sintered film. . Thereafter, the residual carbon (ppm) of the sintered film was measured by a carbon sulfur analyzer (manufactured by Horiba, Ltd.). In addition, the baked color was visually confirmed and evaluated as follows.

○ was colorless

△ It became pale yellow

× showed a brown baked color

(Light transmittance)

About the obtained metal oxide sintered film, the total light transmittance (n = 3) was measured by the method based on JISK6714 and JISK6718 using the haze meter (TC-H3DPK, the Tokyo Denshoku company make). (Circle) and the case where the obtained value is 90% or more (circle) and the case where it is less than 90% 88% or more were made into (circle) and the case where it is less than 88% and 85% or more were made into the case where (triangle | delta) and less than 85%.

(Density)

Regarding the SEM photograph (20000 times) of the obtained metal oxide sintered film, all the interparticle clearances seen in the visual field (6 micrometers x 5 micrometers) were confirmed at 5 visual fields. (Circle) and the confirmed case were made into the case where the clearance gap of 100 nm or more was not confirmed.

(Dispersibility)

Regarding the SEM photograph (5000 times) of the obtained metal oxide sintered film, the presence or absence of the magnesium oxide which aggregated in the visual field (24 micrometers x 20 micrometers) was confirmed at five views.

(Circle) and the confirmed case were made into the case where the aggregate was not confirmed.

(Example 35)

(Manufacture of Binder Resin)

In a 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a bath and a nitrogen gas inlet, 100 parts by weight of isobutyl methacrylate as a (meth) acrylic monomer, 2.5 parts by weight of mercaptosuccinic acid as a chain transfer agent, and an organic solvent As the mixture, 100 parts by weight of ethanol were mixed to obtain a monomer mixture.

After removing the dissolved oxygen by bubbling the obtained monomer liquid mixture for 20 minutes using nitrogen gas, the inside of the separable flask system was replaced with nitrogen gas, and the temperature was raised until the bath was boiled while stirring. Subsequently, the solution which diluted the polymerization initiator ("Perhexa H" by Nichiyu Corp.) with ethanol was added. In addition, an ethanol solution containing a polymerization initiator was added several times during the polymerization. After 7 hours from the start of polymerization, the polymerization was terminated by cooling to room temperature to obtain an ethanol solution of polyisobutyl methacrylate. The obtained polyisobutyl methacrylate was analyzed by gel permeation chromatography (GPC) using column LF-804 manufactured by SHOKO as a column. As a result, the weight average molecular weight in terms of polystyrene was 10,000.

(Production of Metal Oxide Fine Particle Dispersion Paste)

2-ethyl-1,3-hexanediol (the ratio of the number of carbon atoms to the number of hydroxyl groups = 4, the viscosity at room temperature 323 mPa * s) so that it may become the composition ratio of the metal oxide fine particle dispersion paste of Table 11 finally, 2 TiO ₂ particles (Nippon Aerosol Co., Ltd., average particle size) in a vehicle containing, 2-dimethyl-1,3-propanediol (ratio of carbon atoms to hydroxyl number = 2.5, solid at room temperature) and benzyl alcohol 20 nm) was added, and the bead mill process was performed for 6 hours using the zirconia particle of 1 mm of particle diameters as a bead mill (IRMX-made "RMB-08") and a medium. Subsequently, the ethanol solution of the polyisobutyl methacrylate obtained by the said (manufacturing of binder resin) was added so that resin solid content might be 15 weight%, ethanol was removed by the vacuum desolvent process, and the metal oxide fine particle dispersion paste was obtained.

(Example 36)

(Manufacture of Binder Resin)

In a 2 l separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath and a nitrogen gas inlet, 100 parts by weight of isobutyl methacrylate as a (meth) acrylic monomer, 0.5 part by weight of mercaptosuccinic acid as a chain transfer agent, and an organic solvent As the mixture, 100 parts by weight of ethanol were mixed to obtain a monomer mixture.

After removing the dissolved oxygen by bubbling the obtained monomer liquid mixture for 20 minutes using nitrogen gas, the inside of the separable flask system was replaced with nitrogen gas, and the temperature was raised until the bath was boiled while stirring. Subsequently, the solution which diluted the polymerization initiator ("Perhexa H" by Nichiyu Corp.) with ethanol was added. In addition, an ethanol solution containing a polymerization initiator was added several times during the polymerization. After 7 hours from the start of polymerization, the polymerization was terminated by cooling to room temperature to obtain an ethanol solution of polyisobutyl methacrylate. The obtained polyisobutyl methacrylate was analyzed by gel permeation chromatography (GPC) using column LF-804 manufactured by SHOKO as a column. As a result, the weight average molecular weight in terms of polystyrene was 40,000.

(Production of Metal Oxide Fine Particle Dispersion Paste)

The metal oxide fine particle dispersion paste was obtained like Example 35 except having added the ethanol solution of the polyisobutyl methacrylate obtained by the said (manufacturing of binder resin) so that resin solid content might be 11 weight%.

(Example 37)

(Production of Silicon Particles)

20 ml of dioctyl ether and 500 µl of oleic acid were added to a three-neck flask, and Ar gas was flowed into the flask for 15 minutes. Thereafter, the flask was placed under reduced pressure with a vacuum pump, heated to 100 ° C, and cured for 1 hour, and then returned to normal pressure with Ar gas. The flask was heated to 280 ° C, 100 mg of silicon iodide and 1 ml of THF were added thereto, stirred for 30 minutes, cooled to room temperature by air cooling in the presence of Ar gas, and silicon particles having a mean particle size of 50 nm (Si-SiO). Got.

100 mg of 2,4-diethyl-1,5-pentanediol (the ratio of the number of carbon atoms to the number of hydroxyl groups = 4.5, the viscosity of 1650 mPa * s at normal temperature) was added to the ether solution of the obtained silicon particle, and after stirring The ether was removed by vacuum desolvent treatment to obtain a metal oxide fine particle dispersion slurry.

(Example 38)

When preparing the silicon particles, the flask was heated to 280 ° C, 100 mg of silicon iodide and 1 ml of THF were added and stirred for 30 minutes, followed by addition of 5 ml of 1-dodecene in the presence of Ar gas to prevent oxidation. A metal oxide fine particle dispersion slurry was obtained in the same manner as in Example 37 except that the treatment was performed to obtain silicon particles (Si-SiOC _n H _m ) having an average particle diameter of 50 nm.

<Evaluation>

The following evaluation was performed about the metal oxide fine particle dispersion paste or metal oxide fine particle dispersion slurry obtained in Examples 35-38. The results are shown in Tables 11 and 12.

(1) screen printability

Using a metal oxide fine particle dispersion paste or a metal oxide fine particle dispersion slurry, a screen printing machine (Microtech Co., Ltd. "MT-320TV", gap = 2.0 mm, squeegee speed = 50 mm / s, scraper speed = 50 mm / s, squeegee pressure = 0.25 MPa, scraper pressure = 0.17 MPa, back pressure = 0.10 MPa), screen making ("ST500CAL" manufactured by Tokyo Process Service, Inc., emulsion 2 µm, screen frame 320 mm x 320 mm), printed board (soda glass 150 mm x 150) Mm, thickness 15 mm) and screen printing were performed in the environment of the temperature of 23 degreeC, and 50% of humidity using the printed image (Line / Space = 50 micrometer / 150 micrometer). Ten continuous printings were performed, and the printed image of the tenth obtained sheet was observed with a stereo microscope, and evaluated as follows.

○ There was no variation in the thickness of the print image

△ The thickness of the print image was uneven or the print image was very thin.

No ink was applied to the printed board due to blockage

(2) sinterability

Using an applicator set at 5 mils, the metal oxide fine particle dispersion paste or the metal oxide fine particle dispersion slurry was coated on a glass substrate, dried in a blowing oven at 150 ° C. for 30 minutes, and then fired in an electric furnace at 450 ° C. for 30 minutes. Residual carbon (ppm) was measured with the carbon sulfur analyzer manufactured by Horiba. In addition, the baked color was visually confirmed and evaluated as follows.

○ was colorless

△ It became pale yellow

× showed a brown baked color

(3) storage stability

After the metal oxide fine particle dispersion paste or the metal oxide fine particle dispersion slurry was allowed to stand in a constant temperature chamber at 23 ° C. for 2 weeks, the state of the paste or slurry was visually confirmed and evaluated as follows.

○ No layer separation or sedimentation of metal oxide fine particles

A clear solution leaked out, but could be redispersed

Separated into 2 layers, and the metal oxide fine particles precipitated

Industrial availability

According to this invention, the metal oxide fine particle dispersion slurry which implemented the outstanding screen printability by improving the dispersibility of metal oxide fine particles can be provided. Moreover, according to this invention, the metal oxide fine particle dispersion paste containing this metal oxide fine particle dispersion slurry, the manufacturing method of the metal oxide thin film using this metal oxide fine particle dispersion slurry, or this metal oxide fine particle dispersion paste, and the metal oxide thin film of The metal oxide thin film obtained by the manufacturing method can be provided.

Claims (11)

A metal oxide fine particle dispersion slurry containing metal oxide fine particles and an organic solvent,
The metal oxide fine particles have an average particle diameter of 10 to 100 nm,
The organic solvent has a polyol having two or more hydroxyl groups in one molecule, a ratio of the number of carbon atoms to the number of hydroxyl groups in the molecule is less than 5, and a viscosity at room temperature of 100 mPa · s or more. Metal oxide fine particle dispersion slurry. The method of claim 1,
Polyol is a group consisting of glycerin, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol and 1,6-hexanediol Metal oxide fine particle dispersion slurry, characterized in that at least one selected from. The method according to claim 1 or 2,
The metal oxide fine particles contain at least one selected from the group consisting of zinc oxide, antimony oxide, silicon oxide, tin oxide, indium oxide, titanium oxide, iron oxide, magnesium oxide and metal oxides doped with other metals. A metal oxide fine particle dispersion slurry. The metal oxide fine particle dispersion paste as described in any one of Claims 1, 2, or 3, and binder resin. The method of claim 4, wherein
The binder resin is at least one member selected from the group consisting of ethyl cellulose, (meth) acrylic resin, polyether resin, polyacetal resin, and polyvinyl acetal resin. The method according to claim 4 or 5,
Binder resin is a (meth) acrylic resin which has a carboxylic acid in a molecule terminal, The metal oxide fine particle dispersion paste characterized by the above-mentioned. The metal oxide fine particle dispersion slurry as described in any one of Claims 1, 2, or 3, or the metal oxide fine particle dispersion paste as described in any one of Claims 4, 5, or 6. It has a process to apply | coat by the manufacturing method of the metal oxide thin film characterized by the above-mentioned. It is obtained using the manufacturing method of the metal oxide thin film of Claim 7, The metal oxide thin film characterized by the above-mentioned. The method of claim 8,
A metal oxide thin film, which is a magnesium oxide thin film. The method of claim 9,
The residual carbon after baking for 30 minutes at 450 degreeC is 1 weight% or less, The metal oxide thin film characterized by the above-mentioned. The metal oxide thin film of Claim 9 or 10 is provided as a dielectric protective layer, The front panel for plasma displays characterized by the above-mentioned.