KR20070008624A - Composition containing inorganic powder, transfer film, and method of forming inorganic sinter - Google Patents

Abstract

An inorganic-powder-containing composition comprising (A) an inorganic powder, (B) an alkali-soluble resin, (C) a specific methacrylate compound, and (D) a photopolymerization initiator. Also provided is a method of forming an inorganic sinter, characterized by using the inorganic-powder- containing composition. ® KIPO & WIPO 2007

Description

Formation method of inorganic powder containing composition, transfer film, and inorganic sintered compact {COMPOSITION CONTAINING INORGANIC POWDER, TRANSFER FILM, AND METHOD OF FORMING INORGANIC SINTER}

The present invention relates to a novel inorganic powder-containing composition and a method for forming an inorganic sintered body using the same. The inorganic powder-containing composition of the present invention is excellent in thermal decomposition property of organic components at the time of firing, and it is difficult for organic components to remain in the inorganic sinter formed. Therefore, it is useful as a field emission display (FED), a plasma display panel (PDP), an inorganic electroluminescent (inorganic EL) member, especially a conductive member formation material, or a partition formation material.

In recent years, with the development of the information society, the use of the display which plays a role of communication and visual information exchange function has been expanded, and its importance is increasing. Among these, flat panel displays, such as a liquid crystal display (LCD), a plasma display panel (PDP), and a field emission display (FED), are developed. Among them, field emission displays are attracting attention because they have excellent performance of self-luminous type, wide viewing angle, high response speed, high precision and low power consumption.

A field emission display is a display which emits electrons in a vacuum from an anode by applying an electric field, and emits light and displays by irradiating the electrons to the phosphor on the anode.

As a pattern formation method of members, such as an electrode or a partition used for such a display, (1) Screen printing method which forms a pattern by screen printing using the composition of paste-form member formation, (2) The composition layer for photosensitive member formation Photolithography method (e.g., Japanese Patent Laid-Open No. Hei 9-142878 and Japanese Patent Laid-Open No. Hei 10-64435) for forming a pattern by irradiating ultraviolet rays through a photo mask and then developing them. Etc. are known. In these methods, after forming a pattern of members, such as an electrode or a partition, it bakes at high temperature, removes organic components, such as resin, and forms members, such as an electrode or a partition.

However, the screen printing method has a problem in that the positional accuracy of the member pattern is inferior, and a member pattern with high precision cannot be formed. Therefore, the member pattern is formed using the said photolithographic method, starting with the member of a large sized board | substrate, and the member with high precision.

In addition, if the removal of the organic component is insufficient during the firing process, the panel performance of the display is reduced. Particularly in field emission displays, it is necessary to vacuum the inside of the panel in order to emit electrons from the cathode, and if there is a large amount of residual organic components in the member such as an electrode or a partition wall, it takes time to obtain a sufficient degree of vacuum or time and time. In addition, there arises a problem that the degree of vacuum is lowered, and thus the brightness of the panel is also lowered (Japanese Patent Laid-Open No. 8-171877). In particular, since the unsaturated compound crosslinked by a photoinitiator is contained in the composition for photosensitive member formation used by the photolithographic method, the removal performance improvement of the organic component at the time of baking is calculated | required.

In order to solve this problem, it is necessary to perform a baking process at high temperature for a long time in order to fully remove an organic component. However, high temperature and long time firing treatments are not preferable because they lead to a big problem of deformation or deterioration of the display substrate. On the other hand, also from the viewpoint of productivity improvement, improvement of the removal performance of the organic component at the time of baking is desired for the purpose of shortening a baking time.

Patent Document 1: Japanese Patent Application Laid-Open No. 9-142878

Patent Document 2: Japanese Patent Application Laid-Open No. 10-64435

Patent Document 3: Japanese Patent Application Laid-Open No. 8-171877

The present invention provides an inorganic powder-containing composition which is excellent in thermal decomposition of an organic component during firing of a member pattern such as an electrode pattern or a partition pattern, and in which an organic component does not easily remain in an inorganic sintered body such as an electrode or a partition wall, and an inorganic sintered body using the same. It aims at providing the formation method.

Moreover, an object of this invention is to provide the transfer film which has the coating film obtained from the said inorganic powder containing composition, and is excellent in handleability and the film thickness uniformity after transfer.

The inorganic powder-containing composition according to the present invention is represented by (A) an inorganic powder, (B) an alkali-soluble resin, (C) a compound represented by the following general formula (1) (hereinafter referred to as "compound (C1)") and a general formula (2) Containing at least one compound selected from the group containing the compound (hereinafter referred to as "compound (C2)") (hereinafter collectively referred to as "compound (C)") and (D) a photoinitiator It is characterized by.

In formula 1, R <^1> is a hydrogen atom, a hydroxyl group, a C1-C4 alkyl group, or a C1-C4 hydroxyalkyl group.

In formula 2, R ² is (CH ₂ CH ₂ O) _a , (CH ₂ CH (CH ₃ ) O) _b , CH ₂ CH (OH) CH ₂ O, CH ₂ CH ₂ CH (CH ₃ ) O or carbon number It is an alkylene group of 2-18. a and b are each independently a number from 1 to 12.

It is preferable that the said inorganic powder (A) is electroconductive inorganic powder or glass powder.

It is preferable that the said alkali-soluble resin (B) is a methacrylate copolymer.

The transfer film which concerns on this invention is characterized by including a support film and the layer formed on the support film using the said inorganic powder containing composition.

The method for forming the inorganic sintered body according to the present invention,

(i) forming a layer on the substrate using the inorganic powder-containing composition,

(ii) exposing the layer to light by irradiating the desired pattern, crosslinking the exposed portion, and insolubilizing the alkaline developer;

(iii) using an alkaline developer to dissolve and remove unexposed portions to form a pattern,

(iv) firing the pattern

It is characterized by.

In the formation method of the said inorganic sintered compact, an electrode can be formed by forming a layer using a conductive inorganic powder containing composition. Moreover, a partition can be formed by forming a layer using a glass powder containing composition.

Effect of the Invention

The inorganic powder-containing composition according to the present invention is excellent in thermal decomposition property of organic components at the time of member pattern firing, and it is difficult for organic components to remain in inorganic sintered bodies such as electrodes or partition walls formed.

As for the transfer film which concerns on this invention, the layer obtained from the said inorganic powder containing composition was formed on the support film, and it is excellent in handleability. By using this transfer film, the coating film for member formation excellent in the film thickness uniformity can be obtained.

Further, the method for forming the inorganic sintered body according to the present invention is preferably used for the formation of a field emission display (FED), a plasma display panel (PDP), an inorganic electroluminescence (inorganic EL), in particular an electrode or a partition.

Best Mode for Carrying Out the Invention

Hereinafter, the present invention will be described in detail.

<Inorganic powder containing composition>

The inorganic powder containing composition which concerns on this invention contains (A) inorganic powder, (B) alkali-soluble resin, (C) the compound represented by the said General formula (1), (2) and photoinitiator (D).

(A) inorganic powder

As an inorganic powder used for this invention, electroconductive inorganic powder, glass powder, etc. are mentioned.

Examples of the glass powder include (1) a mixture of zinc oxide, boron oxide, and silicon oxide (ZnO-B ₂ O ₃ -SiO _{2 type} ), (2) a mixture of lead oxide, boron oxide, and silicon oxide (PbO-B ₂ O ₃ -SiO ₂ system), (3) lead oxide, boron oxide, silicon oxide and a mixture of aluminum oxide (PbO-B ₂ O ₃ -SiO ₂ -Al ₂ O ₃ system), (4) lead oxide, zinc oxide , A mixture of boron oxide and silicon oxide (PbO-ZnO-B ₂ O ₃ -SiO _{2 type} ), and the like. These glass powder can also be used individually by 1 type or in mixture of 2 or more types. It is preferable that the softening point of glass powder exists in the range of 400-600 degreeC from a baking temperature in inorganic sintered compact formation. Moreover, it is preferable that the average particle diameter of glass powder exists in the range of 0.5-2.5 micrometers.

The glass powder can be used in combination with inorganic oxides such as aluminum oxide, chromium oxide, manganese oxide, titanium oxide, zirconium oxide, silicon oxide, cerium oxide and cobalt oxide, for example. The content of the inorganic oxide to be used in combination is preferably 30% by weight or less based on the total amount of the inorganic powder (A) (glass powder + inorganic oxide).

Examples of the conductive inorganic powder include particles such as Ag, Au, Cu, Al, Ag-Pd alloys, Cr, and Ni. These conductive inorganic powders can be used individually or in combination of 2 or more types. The particle diameter of the conductive inorganic powder is preferably 10 µm or less from the viewpoint of providing sufficient conductivity to the electrode obtained.

The said conductive inorganic powder can be used together with a glass frit. As the composition of the glass frit, for example, in addition to the glass powders (1) to (4), (5) a mixture of bismuth oxide, boron oxide, silicon oxide and aluminum oxide (Bi ₂ O ₃ -B ₂ O ₃ -SiO ₂ -Al ₂ O ₃ system), and the like. It is preferable that the softening point of these glass frits exists in the range of 400-600 degreeC. Content of the glass frit used together is 50 mass% or less with respect to inorganic powder (A) whole quantity (conductive inorganic powder + glass frit), Preferably it is 30 mass% or less.

The inorganic powder-containing composition according to the present invention becomes a conductive composition when the inorganic powder (A) contains a glass powder and contains a glass paste composition and conductive inorganic powder.

(B) alkali soluble resin:

"Alkali-soluble" in this specification means the property which melt | dissolves with an alkaline developing solution and has solubility to the extent that the developing process using an alkaline developing solution is performed.

As such alkali-soluble resin, (meth) acrylic-type resin, hydroxy styrene resin, a novolak resin, polyester resin, etc. are mentioned, for example. Among these alkali-soluble resins, preferred are (meth) acrylic resins such as copolymers of the following monomers (a) and monomers (c), copolymers of monomers (a), monomers (b) and monomers (c). Can be. More preferably, it is preferable that it is the methacrylate copolymer which copolymerized the methacrylate monomer from the point which is excellent in the thermal decomposition property at the time of baking.

Monomer (a): Carboxyl group-containing monomers

Acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, succinic acid mono (2- (meth) acryloyloxyethyl), hexahydrophthalic acid mono (2- ( Meth) acryloyloxyethyl), mono phthalate (2- (meth) acryloyloxyethyl), ω-carboxy-polycaprolactone mono (meth) acrylate, and the like.

Monomer (b): hydroxyl-containing monomers

Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate; Phenolic hydroxyl group containing monomers, such as o-hydroxy styrene, m-hydroxy styrene, and p-hydroxy styrene.

Monomer (c): Other copolymerizable monomers

Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-lauryl (meth) acrylate, benzyl (meth) acrylate, and glycid (meth) acrylate (Meth) acrylic acid esters other than monomer (a), such as dill and dicyclopentanyl (meth) acrylate; Aromatic vinyl monomers such as styrene and α-methylstyrene: conjugated dienes such as butadiene and isoprene; Macromonomers having a polymerizable unsaturated group such as a (meth) acryloyl group at one end of a polymer chain such as polystyrene, methyl poly (meth) acrylate, ethyl poly (meth) acrylate and benzyl poly (meth) acrylate.

The copolymer of the said monomer (a) and monomer (c) or the copolymer of monomer (a), monomer (b), and monomer (c) has alkali solubility by presence of the structural unit derived from monomer (a). do. Among these, the copolymer of a monomer (a), a monomer (b), and a monomer (c) is especially preferable at the point which is excellent in the dispersion stability of an inorganic powder (A), and excellent in the solubility to the alkali developing solution mentioned later.

The copolymer of the monomer (a) and the monomer (c) preferably contains a structural unit derived from the monomer (a) in an amount of 5 to 60% by mass, particularly preferably 10 to 40% by mass. However, the total amount of the structural unit derived from monomer (a) and monomer (c) shall be 100 mass%. In addition, the copolymer of the monomer (a), the monomer (b) and the monomer (c) preferably has a structural unit derived from the monomer (a) of 5 to 60 mass%, particularly preferably 10 to 40 mass% It is contained in an amount and preferably contains a structural unit derived from the monomer (b) in an amount of 1 to 50% by mass, particularly preferably 5 to 30% by mass. However, the total amount of the structural unit derived from a monomer (a), a monomer (b), and a monomer (c) is made into 100 mass%. It is especially preferable that the structural unit derived from each said monomer is the said range from the point which is excellent in the dispersion stability of an inorganic particle, and excellent in the solubility to the alkaline developing solution mentioned later.

Alkali-soluble resin (B) can be manufactured by copolymerizing the said monomer (a) and monomer (c) or monomer (a), monomer (b), and monomer (c) by a conventionally well-known method. At this time, the copolymer of the monomer (a) and the monomer (c) preferably has the monomer (a) in an amount of 5 to 60 mass%, particularly preferably based on 100% by weight of the total amount of the monomer (a) and the monomer (c). Is prepared using an amount of 10 to 40 mass%. In addition, the copolymer of the monomer (a), the monomer (b) and the monomer (c) is preferably a monomer (a) to 100 mass% of the total amount of the monomer (a), the monomer (b) and the monomer (c). Is used in an amount of 5 to 60 mass%, particularly preferably 10 to 40 mass%, and monomer (b) is preferably 1 to 50 mass%, particularly preferably 5 to 30 mass%. It is especially preferable that the usage-amount of each monomer is the said range from the point which can obtain the copolymer which has the said structural unit.

As alkali-soluble resin (B), a resin obtained by addition polymerization of glycidyl methacrylate or (meth) acryloyloxyethyl isocyanate to the alkali-soluble resin and having an unsaturated group introduced into the alkali-soluble resin can also be used.

The weight average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 5,000 to 5,000,000, more preferably 10,000 to 300,000. When Mw exists in the said range, since it is excellent in the solubility with respect to alkaline developing solution, and the film strength is fully maintained when forming a transfer film, it is preferable.

In addition, content of alkali-soluble resin (B) used for this invention is 1-200 mass parts normally with respect to 100 mass parts of inorganic powder (A), Preferably it is 5-100 mass parts, Especially preferably, 10 To 80 parts by mass.

(C) methacryloyl group containing compound

Compound (C) to be used in the present invention is at least one compound selected from the group consisting of the compound represented by the formula (1) and the compound represented by the formula (2), and of the coating film obtained from the inorganic powder-containing composition according to the present invention. It has the effect of bridge | crosslinking an exposure part.

Examples of the compound (C1) represented by the general formula (1) include trimethacrylates such as trimethylolpropane triacrylate, pentaerythritol trimethacrylate, and glycerin trimethacrylate. These can be used individually or in combination of 2 or more types. Among them, trimethylolpropane trimethacrylate is particularly preferred.

Examples of the compound (C2) represented by the formula (2) include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, propylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 1, 3-butanedioldimethacrylate, 1,4-butanedioldimethacrylate, neopentylglycoldimethacrylate, 1,6-hexanedioldimethacrylate, 1,9-nonanedioldimethacrylate, 1, And dimethacrylates such as 10-decanediol dimethacrylate and glycerol dimethacrylate. These can be used individually or in combination of 2 or more types. Among these, especially preferred are ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, propylene glycol dimethacrylate and glycerol dimethacrylate.

In addition, although either compound (C1) and compound (C2) can also be used as a compound (C), it is preferable to use together. When used together, Preferably mass ratio is the ratio of (C1): C2) = 0.2-0.8: 0.8-0.2, Especially preferably, it is 0.4-0.7: 0.6-0.3. However, the sum total of compound (C1) and (C2) is set to one. If the mass ratio is in the above-described range, since the pattern precision of the inorganic sintered compact formed is excellent, it is preferable.

Content of a compound (C) is 100 mass parts or less with respect to 100 mass parts of alkali-soluble resin (B), and it is preferable that it is 20-80 mass parts. If it is less than 20 mass parts, the pattern formation of an inorganic sintered compact may become difficult by the hardening defect of an exposure part. Moreover, when it exceeds 100 mass parts, the pattern distortion of the inorganic sintered compact at the time of baking may become large.

(D) photoinitiator

Examples of the photopolymerization initiator (D) include benzyl, benzoin, benzophenone, camphorquinone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, and 2,2-dimeth Methoxy-2-phenylacetophenone, 2-methyl- [4 '-(methylthio) phenyl] -2-morpholino-1-propanone and 2-benzyl-2-dimethylamino-1- (4-morpholin Carbonyl compounds such as nophenyl) -butan-1-one; Azo compounds or azide compounds such as azoisobutyronitrile and 4-azidebenzaldehyde; Organic sulfur compounds such as mercaptan disulfide; Organic peroxides such as benzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide and paramethane hydroperoxide; 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -1,3,5-triazine and 2- [2- (2-furanyl) ethylenyl] -4,6-bis Trihalo methanes such as (trichloromethyl) -1,3,5-triazine; And imidazole dimers such as 2,2'-bis (2-chlorophenyl) 4,5,4 ', 5'-tetraphenyl 1,2'-biimidazole. These can be used individually or in combination of 2 or more types.

Content of a photoinitiator (D) is 1-100 mass parts normally with respect to 100 mass parts of compounds (C), Preferably it is 5-50 mass parts. When content is the said range, since the pattern precision of the inorganic sintered compact formed is excellent, it is preferable.

(E) solvent

The inorganic powder-containing composition according to the present invention usually contains a solvent in order to impart proper fluidity or plasticity and good film formability. As such a solvent, it is preferable that the affinity with inorganic powder (A) and the solubility of alkali-soluble resin are favorable, an appropriate viscosity can be provided to an inorganic powder containing composition, and it can evaporate easily by drying.

As a particularly preferable solvent, ketones, alcohols and esters having a standard boiling point (boiling point at 1 atmosphere) are 100 to 200 ° C.

Diethyl ketone, methyl butyl ketone, dipropyl ketone, cyclohexanone, etc. are mentioned as said ketones.

As said alcohol, Alcohol, such as n-pentanol, 4-methyl- 2-pentanol, cyclohexanol, and diacetone alcohol; Ether alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether.

As said ester, Saturated aliphatic monocarboxylic-acid alkylesters, such as n-butyl acetate and amyl acetate; Lactic acid esters such as ethyl lactate and lactic acid-n-butyl; Ether esters such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and ethyl-3-ethoxypropionate, and the like.

These solvents can be used individually or in combination of 2 or more types.

Among these, methylbutyl ketone, cyclohexanone, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate, and the like are preferable.

Examples of solvents other than the solvents exemplified above include terebin oil, ethyl cellosolve, methyl cellosolve, terpineol, butyl carbitol acetate, butyl carbitol, isopropyl alcohol, benzyl alcohol, and the like.

Content of the solvent (E) in the inorganic powder containing composition which concerns on this invention can be suitably selected within the range from which favorable film formation property (fluidity or plasticity) is obtained.

For example, it is 1-90 mass% normally with respect to the inorganic powder containing composition whole quantity, Preferably it is 5-70 mass%.

(F) additive

In addition, the inorganic powder-containing composition according to the present invention includes, as an optional component, a plasticizer, a dispersant, a development accelerator, an adhesion aid, an antihalation agent, a leveling agent, a storage stabilizer, an antifoaming agent, an antioxidant, an ultraviolet absorber, a sensitizer, and a chain transfer agent. Various additives may be contained.

(Production method of the composition)

The inorganic powder-containing composition according to the present invention is roll kneaded with the inorganic powder (A), the alkali-soluble resin (B), the compound (C), the photopolymerization initiator (D) and, if necessary, the solvent (E) and the additive (F). It can manufacture by kneading | mixing using kneading machines, such as group, a mixer, a homo mixer, a ball mill, and a bead mill.

The inorganic powder-containing composition prepared as described above is a paste-like composition having fluidity suitable for application, and its viscosity is usually 100 to 1,000,000 cp, preferably 500 to 300,000 cp.

<Transfer film>

The transfer film which concerns on this invention is comprised from a support film and the layer obtained from the said inorganic powder containing composition on this support film. Such a transfer film is obtained by apply | coating the said inorganic powder containing composition on a support film, for example, and drying this coating film. It is preferable that the support film which comprises a transfer film has a heat resistance and solvent resistance, and is a resin film which has flexibility. When a support film has flexibility, a paste composition can be apply | coated by a roll coater, and an inorganic powder containing composition can be preserve | saved and supplied in the state wound up to roll shape. Examples of the resin forming the support film include fluorine-containing resins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride and polyfluoroethylene, nylon and cellulose. Etc. can be mentioned. The thickness of a support film is 20-100 micrometers, for example.

A mold release process may be given to the surface of the support film to which an inorganic powder containing composition is apply | coated. Thereby, peeling operation of a support film can be performed easily in the transfer process mentioned later.

As a method of apply | coating an inorganic powder containing composition on a support film, it is necessary to be able to form the coating film excellent in the uniformity of film thickness efficiently. Specifically, the coating method by a roll coater, the coating method by a doctor blade, the coating method by a curtain coater, the coating method by a die coater, the coating method by a wire coater, etc. are mentioned as a preferable thing.

The drying conditions of the coating film apply | coated as mentioned above are about 0.5 to 30 minutes at 50-150 degreeC, for example, and the residual ratio (content rate in the coating film after drying) of the solvent after drying is normally within 2 mass%. to be.

Although the thickness of the coating film formed on the support film as mentioned above also differs according to the content rate or size of an inorganic powder (A), the use of an inorganic sintered compact, etc., if it is a coating film for electrode formation or a coating film for partition formation, 5 to 50 µm. Moreover, a polyethylene film, a polyvinyl alcohol-type film, etc. are mentioned as a protective film layer which may be provided in the surface of the coating film for inorganic sintered compact formation.

<Formation method of inorganic sintered body>

The method for forming the inorganic sintered body according to the present invention,

(i) forming a layer on the substrate using the inorganic powder-containing composition,

(ii) irradiating the target pattern with radiation to expose the layer, crosslinking the exposed portion and insolubilizing the alkaline developer;

(iii) using an alkaline developer to dissolve and remove unexposed portions to form a pattern,

(iv) firing the pattern

It is characterized by.

In the method for forming the inorganic sintered body, when the glass paste composition is used as the inorganic powder-containing composition, partition walls can be formed, and when the conductive composition is used, conductive members such as electrodes can be formed.

As a method of forming a layer (coating film for inorganic sintered body formation) using an inorganic powder containing composition on a board | substrate, the method of apply | coating an inorganic powder containing composition on a board | substrate, or for forming an inorganic sintered compact on a board | substrate using the transfer film concerning this invention. The method of transferring a coating film is mentioned. Among these, the method of using a transfer film is preferable, and since the coating film for inorganic sintered compact formation excellent in film thickness uniformity can be formed easily, the film thickness uniformity of the formed inorganic sintered compact pattern can be aimed at.

Although it does not specifically limit as radiation used, Ultraviolet rays, such as a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and a g line | wire, i-line stepper, are mentioned. Moreover, an electron beam, a laser beam, etc. are mentioned.

When radiation is an ultraviolet-ray, it is preferable to irradiate normally through the photomask which has a target pattern. In this case, the dosage is usually 50 to 2000 mJ / cm 2.

In the case of an electron beam, a laser beam, etc., it is preferable to irradiate to the target pattern directly.

As the active ingredient of the alkaline developer, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, and diphosphate Inorganic alkaline compounds such as sodium hydrogen, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate and ammonia; Tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine and ethanolamine Organic alkaline compounds, such as these, etc. are mentioned.

An alkaline developing solution can be manufactured by dissolving 1 type, or 2 or more types of the said alkaline compound in water etc. The density | concentration of the alkaline compound in alkaline developing solution is 0.001-10 mass% normally, Preferably it is 0.01-5 mass%.

In addition, after the development process by alkaline developing solution is performed, the water washing process is performed normally.

Hereinafter, although the Example of this invention is described, this invention is not limited to these Examples. In addition, "part" represents a "mass part" below.

<Measurement method of weight average molecular weight>

The weight average molecular weight is the weight average molecular weight of polystyrene conversion measured by Tosoh Corporation gel permeation chromatography (GPC) (device model name: HLC-802A).

Synthesis Example 1

<Synthesis of alkali-soluble resin>

The compounds shown in Table 1 were mixed, and the mixture was placed in an autoclave equipped with a stirrer, stirred until uniform at room temperature under nitrogen atmosphere, then polymerized at 80 ° C. for 3 hours, and further at 100 ° C. for 1 hour. The reaction was continued for a while, and then cooled to room temperature to obtain a solution of the copolymer (P1).

Propylene Glycol Monomethyl Ether 180 copies Monomethyl succinate (2-methacryloyloxyethyl) Part 35 Methacrylic acid 2-hydroxypropyl Part 15 N-butyl methacrylate 50 copies Azobisisobutyronitrile Part Two

The obtained copolymer (P1) had a polymerization conversion of 97% and a polystyrene reduced weight average molecular weight (Mw) of 70,000.

Synthesis Example 2

<Synthesis of alkali-soluble resin>

A copolymer (P2) was obtained in the same manner as in Synthesis Example 1 except that 35 parts of hexahydrophthalic acid mono (2-methacryloyloxyethyl) was used instead of monosuccinate (2-methacryloyloxyethyl). The obtained copolymer (P2) had a polymerization conversion of 97% and a polystyrene reduced weight average molecular weight (Mw) of 66,000.

<Production of Conductive Composition and Electrode>

Example 1

The compound shown in Table 2 was mixed, and this mixture was knead | mixed by the disperser and the electrically conductive composition (S1) was manufactured.

Ag powder (average particle size 2 ㎛) 100 copies Bi ₂ O ₃ -B ₂ O ₃ -SiO ₂ -Al ₂ O ₃ -based glass frit (softening point 560 ℃, average particle diameter 2.0 ㎛)  Part Three Copolymer (P1) (solid content conversion) 50 copies Trimethylolpropanetrimethacrylate Part 12.5 Propylene Glycol Dimethacrylate Part 12.5 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Part 10 Propylene Glycol Monomethyl Ether 150 copies

The obtained electroconductive composition (E1) was apply | coated using the die coater on the support film (200 mm in width, 30 m in length, 38 micrometers in thickness) which consists of PET films, a coating film is dried at 100 degreeC for 5 minutes, a solvent is removed, and thickness is A transfer film (F _E 1) having a coating film for forming an electrode of 10 μm was produced.

The coating film for electrode formation of the obtained transfer film (F _E1 ) was overlapped so that it might contact the surface of a glass substrate, it was thermally crimped | bonded by the heating roller, and it transferred, and formed the coating film for electrode formation on a glass substrate. In the crimping conditions, the surface temperature of the heating roller was 90 ° C, the roll pressure was 2 kg / cm 2, and the moving speed of the heating roller was 0.5 m / min.

Subsequently, 400 mJ / cm <2> ultraviolet-ray (i-ray: wavelength 365nm) is exposed to the coating film for electrode formation formed on the glass substrate from the support film side through a photomask (L / S = 100/400 micrometer stripe pattern). After making it, the support film was peeled off.

Then, the ultraviolet unexposed part was removed by performing the image development process by the shower method which makes 0.6 mass% aqueous sodium carbonate (30 degreeC) the developing solution, and then showered with ultrapure water for 1 minute. Furthermore, the drying process was performed and the electrode pattern was formed on the board | substrate.

Then, the glass substrate in which this electrode pattern was formed was baked for 15 minutes in the baking furnace in the temperature atmosphere of 590 degreeC, the organic component was removed and the electrode was formed.

On the other hand, the conductive composition (E1) cured with ultraviolet light of 400 mJ / ㎠ was placed on a thermobalance, and the weight loss was measured by heating at a rate of 20 ℃ / min, the weight loss was completed to 380 ℃, the organic component The thermal decomposition property of was good.

Example 2

Conductive composition (E2) was prepared in the same manner as in Example 1 except that 50 parts of the copolymer (P2) obtained in Synthesis Example 2 were used instead of the copolymer (P1) obtained in Synthesis Example 1, and then formation of an electrode was performed. It was done. As a result, an electrode could be formed in the same manner as in Example 1.

In addition, when the weight loss was measured in the same manner as in Example 1, the weight loss was completed up to 380 ° C. as in Example 1, and the thermal decomposition property of the organic component was good.

Example 3

Conductive composition (E3) was prepared in the same manner as in Example 1 except that 12.5 parts of glycerol dimethacrylate was used instead of propylene glycol dimethacrylate, and an electrode was then formed. As a result, an electrode could be formed in the same manner as in Example 1.

In addition, when the weight loss was measured in the same manner as in Example 1, the weight loss was completed up to 380 ° C. as in Example 1, and the thermal decomposition property of the organic component was good.

Comparative Example 1

Conductive composition (CE1) was prepared in the same manner as in Example 1 except that 12.5 parts of trimethylolpropane triacrylate instead of trimethylolpropane trimethacrylate and 12.5 parts of propylene glycol diacrylate were used instead of propylene glycol dimethacrylate. It produced and the electrode was formed after that. As a result, similarly to Example 1, the target electrode could be formed.

However, when the weight loss was measured in the same manner as in Example 1, the weight reduction was high at 460 ° C., and the thermal decomposition property of the organic component was inferior.

<Production of Glass Paste Composition and Bulkhead>

Example 4

The glass paste composition (G1) was manufactured by mixing the compound shown in Table 3, and kneading this mixture with a disperser.

Glass powder (Bi ₂ O ₃ -B ₂ O ₃ -SiO ₂ -Al ₂ O ₃ system, softening point 560 ℃, average particle diameter 2.0 ㎛) 100 copies Copolymer (P1) (solid content conversion) 40 copies Trimethylolpropanetrimethacrylate Part 10 Propylene Glycol Dimethacrylate Part 10 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Part 8 Propylene Glycol Monomethyl Ether 120 copies

The obtained glass paste composition (G1) was apply | coated using the die coater on the support film (200 mm in width, 30 m in length, 38 micrometers in thickness) which consists of PET films, a coating film is dried at 100 degreeC for 5 minutes, and a solvent is removed, A transfer film (F _G 1) having a coating film for forming a glass sintered body having a thickness of 10 μm was manufactured.

And superimposed so as to contact the surface of the glass substrate for coating film formation Glass sintered body of the transfer film (F _G 1) thus obtained, subjected to transfer by heat-pressing a heating roller to form a glass sintered body for forming the coating film on the glass substrate. In the crimping conditions, the surface temperature of the heating roller was 90 ° C, the roll pressure was 2 kg / cm 2, and the moving speed of the heating roller was 0.5 m / min.

Next, about the coating film for glass sintered compact formation formed on the glass substrate, ultraviolet-ray (i-ray: wavelength 365nm) of 800 mJ / cm <2> was received from the support film side through a photomask (L / S = 200/200 micrometer stripe pattern). After exposing, the support film was peeled off.

Then, the ultraviolet unexposed part was removed by performing the image development process by the shower method which makes 0.6 mass% aqueous sodium carbonate (30 degreeC) the developing solution, and then showered with ultrapure water for 1 minute. Furthermore, drying process was performed and the partition pattern was formed on the board | substrate.

Thereafter, the glass substrate on which the partition pattern was formed was calcined for 15 minutes in a firing furnace under a temperature atmosphere of 590 ° C, and organic components were removed to form a partition wall containing the glass sintered body.

Meanwhile, the glass paste composition (G1) cured with ultraviolet light of 800 mJ / cm 2 was placed on a thermobalance, and the temperature loss was measured by increasing the temperature at a rate of 20 ° C./min. The thermal decomposition of the component was good.

Example 5

A glass paste composition (G2) was produced in the same manner as in Example 4 except that 40 parts of the copolymer (P2) obtained in Synthesis Example 2 was used instead of the copolymer (P1) obtained in Synthesis Example 1, and then, a partition was formed. Was performed. As a result, a partition wall could be formed in the same manner as in Example 4.

In addition, when the weight loss was measured in the same manner as in Example 4, the weight loss was completed up to 380 ° C. as in Example 4, and the thermal decomposition property of the organic component was good.

Example 6

A glass paste composition (G3) was produced in the same manner as in Example 4 except that 12.5 parts of glycerol dimethacrylate was used instead of propylene glycol dimethacrylate, and a partition was then formed. As a result, the partition wall could be formed similarly to Example G. As shown in FIG.

In addition, when the weight loss was measured in the same manner as in Example 4, the weight loss was completed up to 380 ° C. as in Example 4, and the thermal decomposition property of the organic component was good.

Comparative Example 2

Glass paste composition (CG1) in the same manner as in Example 4, except that 10 parts of trimethylolpropane triacrylate instead of trimethylolpropane trimethacrylate and 10 parts of propylene glycol diacrylate were used instead of propylene glycol dimethacrylate. Was manufactured and the partition was formed after that. As a result, similarly to Example 4, the target partition wall could be formed.

However, when the weight loss was measured in the same manner as in Example 4, the weight reduction was high at 460 ° C., and the thermal decomposition property of the organic component was inferior.

The present invention relates to a novel inorganic powder-containing composition. The inorganic powder-containing composition according to the present invention is excellent in thermal decomposition property of the organic component at the time of firing, and it is difficult for the organic component to remain in the inorganic sintered body such as the formed electrode or partition wall. Therefore, it is useful as a member formation material, especially an electrode formation material or a partition formation material for field emission display (FED), plasma display panel (PDP), and inorganic electroluminescence (inorganic EL).

Claims (8)

(A) an inorganic powder, (B) an alkali-soluble resin, (C) at least one compound selected from the group containing a compound represented by the following formula (1) and a compound represented by the following formula (2), and (D) a photoinitiator Inorganic powder containing composition characterized by the above-mentioned. <Formula 1>

In formula, R <^1> is a hydrogen atom, a hydroxyl group, a C1-C4 alkyl group, or a C1-C4 hydroxyalkyl group. <Formula 2>

Wherein R ² is (CH ₂ CH ₂ O) _a , (CH ₂ CH (CH ₃ ) O) _b , CH ₂ CH (OH) CH ₂ O, CH ₂ CH ₂ CH (CH ₃ ) O or C 2 To 18 alkylene group. a and b are each independently a number from 1 to 12. The inorganic powder-containing composition according to claim 1, wherein the inorganic powder (A) is a conductive inorganic powder. The inorganic powder-containing composition according to claim 1, wherein the inorganic powder (A) is a glass powder. The inorganic powder-containing composition according to claim 1, wherein the alkali-soluble resin (B) is a methacrylate copolymer. A transfer film comprising a support film and a layer formed on the support film by using the inorganic powder-containing composition according to any one of claims 1 to 4. (i) forming a layer on the substrate using the inorganic powder-containing composition according to any one of claims 1 to 4, (ii) irradiating the target pattern with radiation to expose the layer, crosslinking the exposed portion and insolubilizing the alkaline developer; (iii) using an alkaline developer to dissolve and remove unexposed portions to form a pattern, (iv) firing the pattern A method of forming an inorganic sintered body, characterized by the above-mentioned. The inorganic sintered compact obtained by forming a layer using the inorganic powder containing composition of Claim 2, and the obtained inorganic sintered compact is an electrode, The formation method of the inorganic sintered compact of Claim 6 characterized by the above-mentioned. The inorganic sintered compact obtained by forming a layer using the inorganic powder containing composition of Claim 3, and the inorganic sintered compact obtained is a partition wall, The formation method of the inorganic sintered compact of Claim 6 characterized by the above-mentioned.