CN101652407B - Method for production of ceramic molded material - Google Patents
Method for production of ceramic molded material Download PDFInfo
- Publication number
- CN101652407B CN101652407B CN2008800115741A CN200880011574A CN101652407B CN 101652407 B CN101652407 B CN 101652407B CN 2008800115741 A CN2008800115741 A CN 2008800115741A CN 200880011574 A CN200880011574 A CN 200880011574A CN 101652407 B CN101652407 B CN 101652407B
- Authority
- CN
- China
- Prior art keywords
- formula
- ceramic
- polyvinyl acetal
- acetal resin
- manufacture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 CC(C)(C)*N*(*)O*N Chemical compound CC(C)(C)*N*(*)O*N 0.000 description 8
- ADZBLCRDWZGXAI-UHFFFAOYSA-N CC(C)(CC(C)=O)NC(C)=O Chemical compound CC(C)(CC(C)=O)NC(C)=O ADZBLCRDWZGXAI-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
Disclosed are: a method for producing a ceramic molded material, which can produce a crosslinked polyvinyl acetal resin having high mechanical strength and excellent solvent resistance in a simple manner without the need of using any crosslinking agent, and which can overcome the problems such as sheet-attack, strength poverty and unsatisfactory long-term viscosity stability; a method for producing a laminated ceramic capacitor; a method for producing an electrode paste; a method for producing a piezoelectric actuator; a method for producing a solid oxide type of fuel cell; a method for producing a plasma display panel; a ceramic slurry composition; an electrically conductive paste; and a dielectric paste. Specifically, the method for producing a ceramic molded material comprises the steps of applying a ceramic slurry composition comprising a ceramic powder, a polyvinyl acetal resin having at least constituent units represented by the general formulae (1), (2), (3) and (4) and an organic solvent, drying the ceramic slurry composition to form a molded material, and irradiating the molded material with an ultraviolet ray having a wavelength of 200 to 365 nm to cause the crosslinking of the resin. (1)-(4) wherein R1 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; and R2 represents a group having two or more pieces of at least one functional group selected from the group consisting of a functional group represented by the general formula (5), a functional group represented by the general formula (6) and a functional group represented by the general formula (7).
Description
Technical field
The present invention need not to use linking agent; Get final product the cross-linked pioloform resin that manufacturing machine intensity is high, solvent resistance is excellent with easy method, therefore method of manufacture, the method for manufacture of laminated ceramic capacitor, the method for manufacture of electrode paste agent, the method for manufacture of piezoelectric actuator, the method for manufacture of SOFC and method of manufacture and ceramic size composition, conductive paste and the dielectric paste of plasma display of the ceramic molding of the problems such as ageing stability that can solve sheet material corrosion (4sheetattack), undercapacity, viscosity can be provided.
Background technology
At present, polyvinyl acetal resin because the dispersiveness in obdurability, film-forming properties,, the organic powder inorganic etc. at pigment etc., to the excellences such as tackiness of coated face, therefore in various uses, be applied.
As one of purposes of polyvinyl acetal resin, can enumerate laminated ceramic capacitor.Laminated ceramic capacitor is generally made through following operation.At first, in the solution that has obtained in organic solvent, having dissolved adhesive resin, add ceramic material powder, mix, after the deaeration, obtain having the ceramic size composition of certain viscosity with ball mill etc.Use scraper, contrary roll coater etc.; The ceramic size composition that obtains is shaped in the supporting body surface curtain coatings of handling through the demoulding such as polyethylene terephthalate film; After waiting volatile components such as heating up in a steamer organic solvent through heating, peel off, obtain ceramic green sheet from supporter.Then; On the ceramic green sheet that obtains, replace range upon range of polylith and become the electrode paste agent of internal electrode,, make duplexer then with its thermo-compressed through coatings such as silk screen printing or intaglio printings; Carrying out so-called skimming treatment promptly removes the adhesive resin that contains in this duplexer through thermolysis and becomes to grade; The end face that burns till thing at the pottery that is fired into is coated with electrode paste agent and the sintering that becomes outer electrode, forms outer electrode, obtains laminated ceramic capacitor.
Adhesive resin when making this ceramic green sheet adopts polyvinyl acetal resin.But have following problem: when being coated with electrode paste agent on the ceramic green sheet that has used polyvinyl acetal resin, can produce the phenomenon that is called as " sheet material corrosion ", the solvent that promptly contains in the electrode paste agent destroys ceramic green sheet.In addition, in recent years, laminated ceramic capacitor is accompanied by high capacity, and the filmization of ceramic green sheet develops rapidly, and there is following problem in present polyvinyl acetal resin: can't obtain having the ceramic green sheet of abundant intensity, ceramic green sector-meeting breakage etc. when peeling off.
The adhesive resin of the electrode paste agent during as formation internal electrode and outer electrode except that TKK 021 and vinylformic acid, also adopts polyvinyl acetal resin in recent years.But; The performance that is accompanied by laminated ceramic capacitor is increasingly high; The particle diameter of the conductive powder that uses in the electrode paste agent is more and more littler; When adopting polyvinyl acetal resin,, therefore can't make the conductive powder of small particle size fully disperse this problem more remarkable because the soltion viscosity of electrode paste agent is not high enough as adhesive resin.In addition, during high-shear when surface covered improves, the flexibility decrease of electrode paste agent can produce dropping liquid, unequal bad phenomenon after the coating.
In addition, the tackiness agent also used of polyvinyl acetal resin as high performance unit such as piezoelectric actuator.Piezoelectric actuator is also same with the ceramic green sheet that laminated ceramic capacitor is used with the situation of ceramic green sheet, is accompanied by filmization and undercapacity occurs, causes breakage, sheet material corrosive problem thus.
Polyvinyl acetal resin can also be used as the material of the dielectric substrate of SOFC.In the SOFC; Carry the electrode of having held catalyzer such as platinum in dielectric substrate (passing to property of proton film) configuration; Also disposed a pair of dividing plate, interconnected the unit cell of this structure is a plurality of, produced required electric power with the structure that is used to provide fuel.When making dielectric substrate, generally after the dielectric substrate formed body is coated with electrolytical electrolyte solutions such as containing positively charged ion, carry out drying process.But there is following problem:, therefore can the sheet material corrosion phenomenon occur at the dielectric substrate formed body owing to be coated with electrolyte solution repeatedly.Especially under the situation cylindraceous, in the slurry painting process, there is this problem of sheet material corrosion in these coating processes of dipping that adopt more.
Plasma display (below be also referred to as PDP); Make in the discharge space that possesses between glass substrate and the back side glass substrate in front and carry out plasma discharge between electrode; Make the fluor in the uviolizing discharge space that produces by the gas of being enclosed in the discharge space, thereby obtain luminous.
Glass substrate is avoided the plasma body influence for guard electrode overleaf, on electrode, forms dielectric layer, forms the muscle (rib of coating luminescent coating then on its surface; The next door).In addition,,, hide,, form spill striped (stripe) through sandblasting with dry film photoresist about the next door in order to increase the surface-area of luminescent coating.
But with the dry film photoresist of washing such as alkali lye PDP the time, have following problem: the top layer in next door is washed liquid and pollutes.
In recent years; Method of manufacture as PDP; Studying following method: after glass baseplate surface forms dielectric former and next door precursor overleaf, carry out exposure process, developing procedure and sandblasting operation, at last heating together; Thus through only 1 degreasing, burn till, make dielectric layer and next door (together burning till).
But; In together burning till; When using polyvinyl acetal resin as the material of dielectric layer; There is following problem: use paste owing to form, so the solvent that contains in the paste can make the dielectric layer swelling, produce and chap or the sheet material corrosion phenomenon occurs in the present next door of the surface coated of the dielectric former of not carrying out degreasing, burning till.In addition, in the sandblasting operation, there is this problem of reliability decrease of the PDP that obtains in cutting deeply to dielectric layer.
From various angles the method that the intensity that makes the polyvinyl acetal resin that uses these fields and solvent resistance improve is studied; For example following method etc.: after in polyvinyl acetal resin, adding linking agent; Carry out heat treated, make polyvinyl acetal resin at intermolecular cross-linking.
Disclose in the patent documentation 1 polyvinyl acetal resin and isocyanate resin are mixed and the solidified method.The method of making cured film through thermofixation is disclosed in patent documentation 2 and the patent documentation 3.In addition, disclose in the patent documentation 4 polyvinyl butyral acetal after the hydrogen of hydroxyl replaced by N-methylene radical acrylic amide through the rayed of electron rays or ultraviolet ray etc. crosslinked, solidified method.
But in these methods; Must be when solidifying or in polyvinyl acetal resin, add the composition that linking agent or polymerization starter etc. are used to cause crosslinking reaction in advance; Therefore have following problem: the storage stability under the solution state is not good enough, or composition residual that is used to cause crosslinking reaction causes painted, deterioration etc.In addition, also there is the problem that causes complex proceduresization.
In the method for patent documentation 2 and patent documentation 3, carry out crosslinking reaction through thermofixation, but when being applied material and can't heating when thermo-labile or on the operation, existence can't be used or because of crosslinked insufficient problem such as cause that raw cook breaks.In addition, of the embodiment of patent documentation 3, when not heating, exist crosslinked till needs wait problem for a long time.In addition, when irradiation electron rays or X ray, existence can cause problems such as polyvinyl acetal resin decomposition.
Therefore, hope that the method that need not to add the cross-linked pioloform resin that linking agents such as Photoepolymerizationinitiater initiater or Acrylic Acid Monomer also can obtain having sufficient degree of crosslinking, solvent resistance is excellent is arranged.
Patent documentation 1: Japanese Patent Laid is opened the 2006-156493 communique
Patent documentation 2: Japanese Patent Laid table 2006-522863 communique
Patent documentation 3: Japanese Patent Laid table 2006-523754 communique
Patent documentation 4: the fair 7-14973 communique of Japanese Patent Laid
Summary of the invention
The present invention is in view of above-mentioned present situation; Need not to use linking agent; Get final product the cross-linked pioloform resin that manufacturing machine intensity is high, solvent resistance is excellent with easy method, therefore the method for manufacture of the ceramic molding of the problems such as ageing stability that can solve sheet material burn into undercapacity, viscosity, the method for manufacture of laminated ceramic capacitor, the method for manufacture of electrode paste agent, the method for manufacture of piezoelectric actuator, the method for manufacture of SOFC and method of manufacture and ceramic size composition, conductive paste and the dielectric paste of plasma display can be provided.
The method of manufacture of ceramic molding of the present invention comprises following operation: be coated with the operation of following ceramic size composition, said ceramic size composition contains ceramic powder, has the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least; With above-mentioned ceramic size composition exsiccant operation; And, through the ultraviolet ray of illumination wavelength in 200～365nm scope, carry out crosslinked operation.
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
The method of manufacture of laminated ceramic formed body of the present invention is to ceramic green sheet with electrode paste agent is alternately laminated and thermo-compressed and the duplexer that obtains carry out degreasing, the method for manufacture of the laminated ceramic formed body that burns till; It comprises following operation: be coated with the operation of following ceramic size composition, said ceramic size composition contains ceramic powder, has the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least; With above-mentioned ceramic size composition exsiccant operation; And, through the ultraviolet ray of illumination wavelength in 200～365nm scope, carry out crosslinked operation.
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
The method of manufacture of laminated ceramic capacitor of the present invention is to ceramic green sheet with electrode paste agent is alternately laminated and thermo-compressed and the duplexer that obtains carry out degreasing, the method for manufacture of the laminated ceramic capacitor that burns till; It comprises following operation: be coated with the operation of following ceramic size composition, said ceramic size composition contains ceramic powder, has the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least; With above-mentioned ceramic size composition exsiccant operation; And, through the ultraviolet ray of illumination wavelength in 200～365nm scope, carry out crosslinked operation.
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
Ceramic size composition of the present invention contains ceramic powder, has the polyvinyl acetal resin and an organic solvent of the structural unit of formula (1), (2), (3) and (4) expression at least.
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
The method of manufacture of electrode paste agent of the present invention comprises following operation: prepare the operation of following electrode paste agent compsn, said electrode paste agent compsn contains conductive powder, has the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least; And the operation of viscosity is regulated in the ultraviolet ray in 200～365nm scope to above-mentioned electrode paste agent compsn illumination wavelength.
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
Conductive paste of the present invention contains conductive powder, has the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least.
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
The method of manufacture of piezoelectric actuator of the present invention is to ceramic green sheet with electrode paste agent is alternately laminated and thermo-compressed and the duplexer that obtains carry out degreasing, the method for manufacture of the piezoelectric actuator that burns till; It comprises following operation: be coated with the operation of following ceramic size composition, said ceramic size composition contains ceramic powder, has the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least; With above-mentioned ceramic size composition exsiccant operation; And, through the ultraviolet ray of illumination wavelength in 200～365nm scope, carry out crosslinked operation.
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
The method of manufacture of SOFC of the present invention is; After the coating of dielectric substrate formed body contains electrolytical electrolyte solution making dielectric substrate; Method of manufacture at the SOFC of above-mentioned dielectric substrate multilayer electrode; Wherein, Above-mentioned dielectric substrate formed body obtains through following method: following formed body is obtained formed body with the resin combination moulding, and the ultraviolet ray in 200～365nm scope makes it crosslinked to above-mentioned formed body illumination wavelength then, said formed body contain with resin combination have formula (1) at least, the polyvinyl acetal resin and the organic solvent of the structural unit shown in (2), (3) and (4).
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
The method of manufacture of plasma display of the present invention is; After glass baseplate surface forms dielectric former and next door precursor overleaf; To above-mentioned dielectric former and above-mentioned next door precursor together carry out degreasing, the method for manufacture of the plasma display that burns till; It comprises following operation: be coated with the operation of following dielectric paste, said dielectric paste contains dielectric medium, has the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least; With above-mentioned dielectric paste exsiccant operation; And, the ultraviolet operation of illumination wavelength in 200～365nm scope.
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
Dielectric paste of the present invention contains dielectric medium, has the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least.
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
The method of manufacture of the plasma display of other type; It comprises following operation: be coated with the operation of following next door with paste, said next door contain with paste have formula (1) at least, the polyvinyl acetal resin and the organic solvent of the structural unit shown in (2), (3) and (4); With above-mentioned next door with paste exsiccant operation; And, through the ultraviolet ray of illumination wavelength in 200～365nm scope, carry out crosslinked operation.
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
Below, the present invention is elaborated.
The method of manufacture of ceramic molding of the present invention comprises following operation: be coated with the operation of following ceramic size composition, said ceramic size composition contains ceramic powder, has the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least; With above-mentioned ceramic size composition exsiccant operation; And, through the ultraviolet ray of illumination wavelength in 200～365nm scope, carry out crosslinked operation.
Result that the present inventor concentrates on studies finds: after will containing the ceramic size composition coating, drying of the polyvinyl acetal resin of the structural unit with regulation; Illumination wavelength is the ultraviolet ray in 200～365nm scope; When making polyvinyl acetal crosslinked, do not use linking agent, can obtain having the cross-linked pioloform resin of high-crosslinking-degree with simple method; This cross-linked pioloform resin has sufficient mechanical; And solvent resistance is also fine, thereby can solve the problem of sheet material corrosion and undercapacity, thereby has accomplished the present invention.
Adopt method of manufacture of the present invention, can obtain the excellent cross-linked pioloform resin of solvent resistance, the sheet material corrosion of the ceramic green sheet that therefore can prevent effectively to obtain.In addition, the cross-linked pioloform resin that obtains has sufficient mechanical, even under the situation with the ceramic green sheet filmization, also is difficult for producing problems such as breakage.
Among the present invention; Ceramic molding obtains through following method: be coated with following ceramic size composition and dry; The ultraviolet ray of illumination wavelength in 200～365nm scope carried out crosslinked; Thereby obtain ceramic molding, said ceramic size composition contains ceramic powder, has the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least.
Need to prove that ceramic molding also comprises ceramic duplexer etc. except that above-mentioned ceramic green sheet.
Above-mentioned polyvinyl acetal resin has the structural unit shown in formula (1), (2), (3) and (4) at least.
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
In the above-mentioned polyvinyl acetal resin, the preferred lower limit of the content of the vinyl alcohol units shown in the above-mentioned general formula (1) is 17 moles of %, and preferred upper limit is 40 moles of %.When 17 moles of % of less than, the solvability in the organic solvent that when dissolving, uses descends sometimes.When surpassing 40 moles of %, because moisture absorption easily, therefore when using as adhesive resin, storage stability descends sometimes.
In the above-mentioned polyvinyl acetal resin, the preferred lower limit of the unitary content of acetal shown in the above-mentioned general formula (2) is 35 moles of %, and preferred upper limit is 80 moles of %.When 35 moles of % of less than, insoluble sometimes in the organic solvent that when dissolving, uses.When surpassing 80 moles of %, the residual hydroxyl quantitative change is few, and the intensity of the cross-linked pioloform resin that obtains descends sometimes.
Need to prove; In this manual, as the method for calculation of acetalizing degree, owing to the acetal radical of polyvinyl acetal resin is obtained by 2 hydroxyl acetalations; Therefore adopt and calculate, calculate the mole % of acetalizing degree by the method for the number of 2 hydroxyls of acetalation.
In the acetal unit shown in the above-mentioned general formula (2), R
1Preferred package hydrogen atoms, methyl and/or butyl.Wherein, R
1Preferably comprise methyl and/or butyl.Through using such polyvinyl acetal resin; The unitary sterically hindered well balanced that reaches of the intramolecular hydrogen bond power of vinyl alcohol units and acetal; Therefore crosslinking reaction can be carried out with less energy, the cross-linked pioloform resin of all excellents such as physical strength, solvent resistance, gentle right property, tackiness can be obtained.
In the above-mentioned polyvinyl acetal resin, the preferred lower limit of the unitary content of ethanoyl shown in the above-mentioned general formula (3) is 0.1 mole of %, and preferred upper limit is 25 moles of %.When exceeding above-mentioned scope, the decreased solubility of material polyethylene alcohol, acetalation become difficult.Be limited to 15 moles of % on preferred.
In the above-mentioned polyvinyl acetal resin, the structural unit shown in the above-mentioned general formula (4) has bridging property, through the ultraviolet ray of illumination wavelength in 200～365nm scope, forms crosslinking structure with functional group in other the molecule.Therefore, the cross-linked pioloform resin after the curing not only has high mechanical strength, also has the elasticity of appropriateness.
In the structural unit shown in the above-mentioned general formula (4), R
2Preferably have direct bonded part between at least a kind of functional group that is selected from the group that constitutes by functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7), or through 1 part that is different from the functional groups that is selected from least a kind of functional group in the functional group shown in functional group shown in the functional group shown in the formula (5), the formula (6) and the formula (7).
-NH- (6)
-NH
2 (7)
In the structural unit shown in the above-mentioned general formula (4), as above-mentioned R
2, for example can enumerate the group shown in the group shown in the formula (8), the formula (9) etc.
In the above-mentioned polyvinyl acetal resin, the preferred lower limit of the content of the structural unit shown in the above-mentioned general formula (4) is 0.01 mole of %, and preferred upper limit is 50 moles of %.When 0.01 mole of % of less than, can't fully obtain the effect that produces by forming crosslinking structure, cause physical strength to descend sometimes.When surpassing 50 moles of %, the degree of crosslinking of the crosslinked body that obtains is too high, and pliability descends sometimes.
The preferred lower limit of the polymerization degree of above-mentioned polyvinyl acetal resin is 200, and preferred upper limit is 400.Through making the polymerization degree in above-mentioned scope, the excellences such as physical strength of the crosslinked body that obtains.
As the method for making above-mentioned polyvinyl acetal resin, for example making above-mentioned R
2During for the polyvinyl acetal resin of the group shown in the general formula (8), can enumerate with the method for modified polyvinyl alcohol acetalation, with method of addition beta-dicarbonyl behind the unmodified Polyvinyl acetal etc. with beta-dicarbonyl.The method that preferably will have the modified polyvinyl alcohol acetalation of beta-dicarbonyl.
Addition method as above-mentioned beta-dicarbonyl does not have particular restriction, can use present known method, for example can be set forth in methyl-sulphoxide (DMSO) solution method of adding 4-methylene radical-2-oxetanone etc. etc.
Method as above-mentioned acetalation; There is not particular restriction; Can adopt present known method, for example can be set forth under the existence of acid catalyst the method for adding various aldehyde in the aqueous solution to modified polyvinyl alcohol, alcoholic solution, water/mixed alkoxide solution, methyl-sulphoxide (DMSO) solution etc.
As the aldehyde that uses in the above-mentioned acetalation; Do not have particular restriction, for example can enumerate formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal, enanthaldehyde, 2-ethyl hexanal, hexamethylene aldehyde, Furan Aldehydes, oxalic dialdehyde, LUTARALDEHYDE, phenyl aldehyde, 2-tolyl aldehyde, 3-tolyl aldehyde, 4-tolyl aldehyde, PARA HYDROXY BENZALDEHYDE, m-hydroxybenzaldehyde, phenylacetic aldehyde, beta-phenyl propionic aldehyde etc.Wherein, preferably acetaldehyde and butyraldehyde are used separately respectively, or with acetaldehyde and butyraldehyde and usefulness.
As above-mentioned acid catalyst, there is not particular restriction, can use in organic acid, the mineral acid any, for example can enumerate acetate, tosic acid, nitric acid, sulfuric acid, hydrochloric acid etc.
For above-mentioned acetalation is stopped, preferably neutralizing with alkali.As above-mentioned alkali, there is not particular restriction, for example can enumerate sodium hydroxide, Pottasium Hydroxide, ammonia, sodium acetate, yellow soda ash, sodium hydrogencarbonate, salt of wormwood, saleratus etc.
With the front and back of operation, preferred water etc. are with the modified polyvinyl acetal resin washing that obtains in above-mentioned.In addition, in order to prevent to sneak into the impurity that contains in the washing water, more preferably wash with pure water.
Among the present invention, the operation through being coated with above-mentioned ceramic size composition, with above-mentioned ceramic size composition exsiccant operation and the ultraviolet operation of illumination wavelength in 200～365nm scope makes above-mentioned polyvinyl acetal resin crosslinked.
Among the present invention, through rayed but not thermal treatment makes above-mentioned polyvinyl acetal resin crosslinked, thereby can obtain having also good cross-linked pioloform resin of sufficient mechanical and solvent resistance with simple method.
Through using above-mentioned polyvinyl acetal resin, need not to use electron rays or X ray can obtain the high cross-linked pioloform resin of degree of crosslinking.In addition, except that rayed, according to circumstances, all right combined heated, cooling, electron rays irradiation, x-ray bombardment etc.
When the not enough 200nm of the above-mentioned wavelength of irradiation ultraviolet, can cause the decomposition of resin, when irradiation surpasses 365nm ultraviolet, crosslinked insufficient.The ultraviolet ray of above-mentioned wavelength in 200～365nm scope can be continuous spectrum light, also can be line spectrum light.When above-mentioned ultraviolet ray is the continuous spectrum light time, as long as comprise the ultraviolet ray of wavelength in 200～365nm scope at least.
Light source during as the above-mentioned wavelength of irradiation ultraviolet in 200～365nm scope; As long as the ultraviolet ray that can produce above-mentioned wavelength; Do not have particular restriction, for example can use ultrahigh pressure mercury lamp, high voltage mercury lamp, low pressure mercury lamp, metal halid lamp, Excimer lamp, cold-cathode tube, UV-LED lamp, halogen lamp, high-frequency induction type UV lamp etc.
As the ceramic powder that in the method for manufacture of ceramic molding of the present invention, uses, organic solvent, there is not particular restriction, can use as the raw material of ceramic molding material commonly used.As above-mentioned ceramic powder, for example can enumerate barium titanate, zirconic acid, aluminum oxide, lead zirconates etc.As above-mentioned organic solvent, preferred alcohols or aliphatic hydrocarbon.As softening agent, for example preferably use aliphatic ester, polyalcohols softening agent etc., wherein, preferably use adipic acid ester, triethyleneglycol ester.
Laminated ceramic formed body of the present invention; Be to ceramic green sheet with electrode paste agent is alternately laminated and thermo-compressed and the duplexer that obtains carry out degreasing, the method for manufacture of the laminated ceramic formed body that burns till; It comprises following operation: be coated with the operation of following ceramic size composition, said ceramic size composition contains ceramic powder, has the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least; With above-mentioned ceramic size composition exsiccant operation; And, through the ultraviolet ray of illumination wavelength in 200～365nm scope, carry out crosslinked operation.
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
In this specification sheets,, for example can enumerate laminated ceramic inducer, electrical condenser, range upon range of piezoelectric actuator, range upon range of resistor, range upon range of thermistor etc. as the laminated ceramic formed body.
The method of manufacture of laminated ceramic capacitor of the present invention is to ceramic green sheet with electrode paste agent is alternately laminated and thermo-compressed and the duplexer that obtains carry out degreasing, the method for manufacture of the laminated ceramic capacitor that burns till; Comprise: be coated with the operation of following ceramic size composition, said ceramic size composition contains ceramic powder, has the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least; With above-mentioned ceramic size composition exsiccant operation; And, carry out crosslinked operation through the ultraviolet ray of illumination wavelength in 200～365nm scope.
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
Shown in Figure 1 is the schema of an example of the manufacturing process of laminated ceramic capacitor of the present invention.Need to prove that the manufacturing process of laminated ceramic capacitor is not limited to the situation of Fig. 1.
Shine the ultraviolet operation of above-mentioned wavelength in 200～365nm scope, can be between each operation shown in Figure 1 (c～j) or with each operation (C～H) only carry out 1 time also can carry out more than 2 times simultaneously.Carry out under the situation of above-mentioned uviolizing operation at c～e, C, D, E, when printing electrode paste, can obtain to prevent sheet material corrosive effect.
In addition; Carry out under the situation of above-mentioned uviolizing operation at c～j, C～H; Ceramic green sheet can improve the intensity of polyvinyl acetal resin, in the operation that ceramic green sheet is peeled off from PET film etc., range upon range of operation, operation of crimping etc., can be obtained to prevent the effect of bad phenomenon such as breaking.
In above-mentioned uviolizing operation, can be above shone thing, below, lateral direction shine above-mentioned ultraviolet ray, also can be from a plurality of directions irradiations.When from following irradiation, at interval PET film etc. shines.
As the ceramic powder that in the method for manufacture of laminated ceramic capacitor of the present invention, uses, organic solvent, there is not particular restriction, can use as the raw material of laminated ceramic capacitor material commonly used.If adopt the present invention; Then need not initiator also can carry out crosslinked; But in ceramic size composition, also can add acryloid or epoxidation agent, urethanum, isocyanic ester, silane coupling agent, initiator etc., in operation (a, b, c), can spray initiator or isocyanic ester etc.
To the thermo-compressed operation in the method for manufacture of laminated ceramic capacitor of the present invention, duplexer degreasing, the operation of burning till are not had particular restriction, can adopt present known method.
In the method for manufacture of the method for manufacture of the method for manufacture of ceramic molding of the present invention, laminated ceramic formed body or laminated ceramic capacitor, use, contain ceramic powder, have the polyvinyl acetal resin of the structural unit shown in formula (1), (2), (3) and (4) and a ceramic size composition of organic solvent at least; Crosslinked through the ultraviolet ray of illumination wavelength in 200～365nm scope, not only had the excellent ceramic green sheet of sufficient mechanical and solvent resistance.This ceramic size composition also is one of the present invention.
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
The method of manufacture of electrode paste agent of the present invention comprises: prepare the operation of following electrode paste agent compsn, said electrode paste agent compsn contains conductive powder, has the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least; And to above-mentioned electrode paste agent compsn illumination wavelength the operation of viscosity is regulated in the ultraviolet ray in 200～365nm scope.
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
Result that the present inventor concentrates on studies finds: to the ultraviolet ray of electrode paste agent compsn illumination wavelength in 200～365nm scope of the polyvinyl acetal resin that contains the structural unit with regulation; When making polyvinyl acetal resin crosslinked; Can obtain having the cross-linked pioloform resin of high-crosslinking-degree; Therefore the soltion viscosity of electrode paste agent fully improves, even the conductive powder of small particle size also can fully disperse.Find in addition: even during the high-shear when surface covered improves, the elasticity of electrode paste agent can not descend yet, the dropping liquid in the time of preventing to be coated with, the generation of unequal bad phenomenon, thus accomplished the present invention.
The conductive powder that uses in the method for manufacture as electrode paste agent of the present invention does not have particular restriction, can be employed in conductive powder commonly used in the electrode paste agent.
In addition; About having the polyvinyl acetal resin and the ultraviolet operation of illumination wavelength in 200～365nm scope of the structural unit shown in formula (1), (2), (3) and (4) at least; With same in the method for manufacture of ceramic molding of the present invention, therefore omit its detailed description.
In the method for manufacture of electrode paste agent of the present invention, use, contain conductive powder, have the polyvinyl acetal resin of the structural unit shown in formula (1), (2), (3) and (4) and an electrode paste agent compsn of organic solvent at least; Through the ultraviolet ray of illumination wavelength in 200～365nm scope and crosslinked; Soltion viscosity fully improves; The dispersiveness and the coating of conductive powder are improved, therefore can use as conductive paste.This conductive paste also is one of the present invention.
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
The method of manufacture of piezoelectric actuator of the present invention is to ceramic green sheet with electrode paste agent is alternately laminated and thermo-compressed and the duplexer that obtains carry out degreasing, the method for manufacture of the piezoelectric actuator that burns till; It comprises following operation: be coated with the operation of following ceramic size composition, said ceramic size composition contains ceramic powder, has the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least; With above-mentioned ceramic size composition exsiccant operation; And, through the ultraviolet ray of illumination wavelength in 200～365nm scope, carry out crosslinked operation.
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
Result that the present inventor concentrates on studies finds: after the ceramic size composition that will contain the polyvinyl acetal resin of the structural unit with regulation is processed sheet-like formed body; The ultraviolet ray of illumination wavelength in 200～365nm scope; When making polyvinyl acetal resin crosslinked; Obtain having the cross-linked pioloform resin of high-crosslinking-degree, this cross-linked pioloform resin is owing to having sufficient mechanical, even therefore under the situation of filmization; Also be difficult for breakage or sheet material corrosive problem take place, thereby accomplished the present invention.
The polyvinyl acetal resin and the ultraviolet operation of illumination wavelength in 200～365nm scope that have the structural unit shown in formula (1), (2), (3) and (4) at least in the method for manufacture of piezoelectric actuator of the present invention; With same in the method for manufacture of ceramic molding of the present invention, therefore omit its detailed description.
The method of manufacture of SOFC of the present invention is; After the coating of dielectric substrate formed body contains electrolytical electrolyte solution making dielectric substrate; Method of manufacture at the SOFC of above-mentioned dielectric substrate multilayer electrode; Wherein, Above-mentioned dielectric substrate formed body obtains through following method: following formed body is obtained formed body with the resin combination moulding, and the ultraviolet ray in 200～365nm scope makes it crosslinked to above-mentioned formed body illumination wavelength then, said formed body contain with resin combination have formula (1) at least, the polyvinyl acetal resin and the organic solvent of the structural unit shown in (2), (3) and (4).
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
Result that the present inventor concentrates on studies finds: after the formed body that will contain the polyvinyl acetal resin of the structural unit with regulation obtains sheet-like formed body with the resin combination moulding; The ultraviolet ray of illumination wavelength in 200～365nm scope; When making polyvinyl acetal resin crosslinked, can obtain the excellent cross-linked pioloform resin of solvent resistance, when therefore above-mentioned polyvinyl acetal resin being used as the material of dielectric substrate formed body; Even be coated with electrolyte solution repeatedly; Be not prone to the sheet material corrosion phenomenon at the dielectric substrate formed body yet, and when making the fuel electrodes layer, be not prone to the sheet material corrosion phenomenon, thereby accomplished the present invention.
As the ionogen that in the method for manufacture of SOFC of the present invention, uses, electrode, there is not particular restriction, can use present material known.
In addition; At least the polyvinyl acetal resin and the ultraviolet operation of illumination wavelength in 200～365nm scope that have the structural unit shown in formula (1), (2), (3) and (4); With same in the method for manufacture of ceramic molding of the present invention, therefore omit its detailed description.
The method of manufacture of plasma display of the present invention is; After glass baseplate surface forms dielectric former and next door precursor overleaf; To above-mentioned dielectric former and above-mentioned next door precursor together carry out degreasing, the method for manufacture of the plasma display that burns till; It comprises following operation: be coated with the operation of following dielectric paste, said dielectric paste contains dielectric medium, has the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least; With above-mentioned dielectric paste exsiccant operation; And crosslinked operation is carried out in the ultraviolet ray of illumination wavelength in 200～365nm scope.
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
Result that the present inventor concentrates on studies finds: after will containing the dielectric paste coating, drying of the polyvinyl acetal resin of the structural unit with regulation; The ultraviolet ray of illumination wavelength in 200～365nm scope; When making polyvinyl acetal resin crosslinked; Can obtain the cross-linked pioloform resin of degree of crosslinking height, solvent resistance excellence; Under the situation that therefore can not only prevent effectively to burn till together when forming the next door precursor dielectric former produce the sheet material corrosion, and the cross-linked pioloform resin that obtains has sufficient mechanical, even therefore in subsequent handling, carry out the sandblasting operation; Cutting also is difficult to arrive dielectric layer, thereby has accomplished the present invention.
As in the method for manufacture of plasma display of the present invention, using back side glass substrate, next door precursor, there is not particular restriction, can use present material known.
In addition; At least the polyvinyl acetal resin and the ultraviolet operation of illumination wavelength in 200～365nm scope that have the structural unit shown in formula (1), (2), (3) and (4); With same in the method for manufacture of ceramic molding of the present invention, therefore omit its detailed description.
Use in the method for manufacture of plasma display of the present invention, contain dielectric medium, have the polyvinyl acetal resin of the structural unit shown in formula (1), (2), (3) and (4) and a dielectric paste of organic solvent at least; Through the ultraviolet ray of illumination wavelength in 200～365nm scope and crosslinked, the dielectric layer that obtains having sufficient solvent resistance and physical strength.
This dielectric paste also is one of the present invention.
The method of manufacture of the plasma display of the present invention of other type comprises: be coated with the operation of following next door with paste, said next door contain with paste have formula (1) at least, the polyvinyl acetal resin and the organic solvent of the structural unit shown in (2), (3) and (4); With above-mentioned next door with paste exsiccant operation; And, carry out crosslinked operation through the ultraviolet ray of illumination wavelength in 200～365nm scope.
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Expression has the group that is selected from least a kind of functional group in the group that is made up of functional group shown in the functional group shown in the formula (5), the formula (6) and the functional group shown in the formula (7) that amounts to more than 2.
-NH- (6)
-NH
2 (7)
Method of manufacture as the plasma display of the present invention of other type; Particularly; For example can adopt following method etc.: will contain have formula (1) at least, the next door of the polyvinyl acetal resin of the structural unit shown in (2), (3) and (4) and organic solvent with paste be coated with, drying; After forming the next door precursor, to the ultraviolet ray of next door precursor illumination wavelength in 200～365nm scope that obtains.Then, range upon range of resist layer carries out the patterning of resist layer through carrying out exposure imaging, forms the next door through carrying out sandblasting then, and resist layer is peeled off.
In the present invention of other type, can obtain the excellent cross-linked pioloform resin of solvent resistance, therefore with washing resist layers such as alkali lye the time, can prevent that the top layer in next door is washed the liquid washing.In addition, the cross-linked pioloform resin that obtains has full intensity, and shape-holding property is excellent.
According to the present invention; Need not to use linking agent; Get final product the cross-linked pioloform resin that manufacturing machine intensity is high, solvent resistance is excellent with easy method, therefore the method for manufacture of the ceramic molding of the problems such as ageing stability that can solve sheet material burn into undercapacity, viscosity, the method for manufacture of laminated ceramic capacitor, the method for manufacture of electrode paste agent, the method for manufacture of piezoelectric actuator, the method for manufacture of SOFC and method of manufacture and ceramic size composition, conductive paste and the dielectric paste of plasma display can be provided.
Description of drawings
Fig. 1 is the schema of an example of the manufacturing process of expression laminated ceramic capacitor of the present invention.
Embodiment
Below, enumerate embodiment and illustrate in greater detail the present invention, but the invention is not restricted to these embodiment.
(embodiment 1)
(making of modified polyvinyl acetal resin)
With saponification deg 98.8%, have the R shown in the above-mentioned general formula (8)
2Structural unit content be that modified polyvinyl alcohol 100 weight parts of 2 moles of % are heated in the zero(ppm) water of 1200 weight parts after the dissolving, remain in 20 ℃, to wherein adding 70% nitric acid, 10 weight parts, add butyraldehyde 16 weight parts then.Then, be cooled to 10 ℃, add butyraldehyde 45 weight parts.After resin is separated out, kept 30 minutes, add nitric acid 60 weight parts then, be warming up to 35 ℃, kept 3 hours.Reaction was washed 10 hours with the distillation current after finishing, and added sodium hydroxide, with the pH regulator to 8 of solution.Solution after keeping 6 hours under 50 ℃, is cooled off.
Then, with zero(ppm) water solution stream is washed 2 hours after, dehydration, drying obtain modified polyvinyl acetal resin.The residual hydroxyl amount of the modified polyvinyl acetal resin that obtains (the structural unit content shown in the above-mentioned general formula (1)) is 30 moles of %; Butyral unit content (the structural unit content shown in the above-mentioned general formula (2)) is 67 moles of %; Ethanoyl unit content (structural unit content shown in the above-mentioned general formula (3)) is 1 mole of %, has the R shown in the above-mentioned general formula (8)
2Structural unit content (the structural unit content shown in the above-mentioned general formula (4)) be 2 moles of %.
(making of ceramic size composition)
In the mixed solvent of toluene 15 weight parts and ethanol 15 weight parts, add modified polyvinyl acetal resin 8 weight parts that obtain, stirring and dissolving adds Witcizer 300 10 weight parts as softening agent, stirring and dissolving then.In the resin solution that obtains, add barium titanate (BT-03, median size 0.3 μ m, Sakai chemical industrial company system) 100 weight parts as ceramic powder, mixed 48 hours with ball mill, obtain ceramic size composition.
(making of ceramic green sheet)
On the PET film of handling through the demoulding, it is 2 μ m that the ceramic size composition that uses the spreader coating to obtain makes its dried thickness, after air-dry at normal temperatures 1 hour, with metal halid lamp (gloomy (セ Application) special light sources Co., Ltd. system) irradiation 3000mJ/cm
2(irradiation time is 30 seconds) wavelength ultraviolet ray in 200～365nm scope obtains ceramic green sheet.
(embodiment 2)
(making of modified polyvinyl acetal resin)
With saponification deg 99%, have the R shown in the above-mentioned general formula (9)
2Structural unit content be that modified polyvinyl alcohol 100 weight parts of 4 moles of % are heated in the zero(ppm) water of 1200 weight parts after the dissolving, remain in 20 ℃, to wherein adding 70% nitric acid, 10 weight parts, add butyraldehyde 16 weight parts then.Then, be cooled to 10 ℃, add butyraldehyde 45 weight parts.After resin is separated out, kept 30 minutes, add nitric acid 60 weight parts then, be warming up to 35 ℃, kept 3 hours.Reaction was washed 10 hours with the distillation current after finishing, and added sodium hydroxide, with the pH regulator to 8 of solution.Solution after keeping 6 hours under 50 ℃, is cooled off.
Then, with zero(ppm) water solution stream is washed 2 hours after, dehydration, drying obtain modified polyvinyl acetal resin.The residual hydroxyl amount of the modified polyvinyl acetal resin that obtains is 28 moles of %, and butyral unit content is 67 moles of %, and ethanoyl unit content is 1 mole of %, has the R shown in the above-mentioned general formula (9)
2Structural unit content (the structural unit content shown in the above-mentioned general formula (4)) be 4 moles of %.
(making of ceramic green sheet)
The modified polyvinyl acetal resin that use obtains is operated with embodiment 1 in addition equally, makes ceramic green sheet.
(embodiment 3)
(making of modified polyvinyl acetal resin)
With saponification deg 98.8%, have the R shown in the above-mentioned general formula (8)
2Structural unit content be that modified polyvinyl alcohol 100 weight parts of 2 moles of % are heated in the zero(ppm) water of 1200 weight parts after the dissolving, cooling to wherein adding 70% nitric acid, 76 weight parts, is added butyraldehyde 40 weight parts, acetaldehyde 15 weight parts then.After resin is separated out, kept 30 minutes, be warming up to 35 ℃ then, kept 3 hours.Reaction was washed 10 hours with the distillation current after finishing, and added sodium hydroxide, with the pH regulator to 8 of solution.Solution after keeping 6 hours under 50 ℃, is cooled off.
Then, with zero(ppm) water solution stream is washed 2 hours after, dehydration, drying obtain modified polyvinyl acetal resin.The residual hydroxyl amount of the modified polyvinyl acetal resin that obtains is 28 moles of %, and butyral unit content is 38 moles of %, and ethanoyl unit content is 1 mole of %, ethylidene ether unit (R
1: methyl) content is 31 moles of %, has the R shown in the above-mentioned general formula (8)
2Structural unit content (the structural unit content shown in the above-mentioned general formula (4)) be 2 moles of %.
(making of ceramic green sheet)
The modified polyvinyl acetal resin that use obtains is operated with embodiment 1 in addition equally, makes ceramic green sheet.
(embodiment 4)
Use the method same with embodiment 3; After making modified polyvinyl acetal resin, be coated with on the PET film of handling through the demoulding with spreader, making its dried thickness is 2 μ m; After air-dry at normal temperatures 1 hour, with metal halid lamp (the different light source of cent Co., Ltd. system) irradiation 1000mJ/cm
2(irradiation time is 10 seconds) wavelength ultraviolet ray in 200～365nm scope obtains ceramic green sheet.
(embodiment 5)
(making of modified polyvinyl acetal resin)
With saponification deg 98.8%, have the R shown in the above-mentioned general formula (8)
2Structural unit content be that modified polyvinyl alcohol 100 weight parts of 4 moles of % are heated in the zero(ppm) water of 1200 weight parts after the dissolving, cooling to wherein adding 70% nitric acid, 75 weight parts, is added butyraldehyde 20 weight parts, acetaldehyde 36 weight parts then.After resin is separated out, kept 30 minutes, be warming up to 35 ℃ then, kept 3 hours.Reaction was washed 10 hours with the distillation current after finishing, and added sodium hydroxide, with the pH regulator to 8 of solution.Solution after keeping 6 hours under 50 ℃, is cooled off.
Then, with zero(ppm) water solution stream is washed 2 hours after, dehydration, drying obtain modified polyvinyl acetal resin.The residual hydroxyl amount of the modified polyvinyl acetal resin that obtains is 27 moles of %, and butyral unit content is 10 moles of %, ethylidene ether unit (R
1: methyl) content is 58 moles of %, and ethanoyl unit content is 1 mole of %, has the R shown in the above-mentioned general formula (8)
2Structural unit content (the structural unit content shown in the above-mentioned general formula (4)) be 4 moles of %.
(making of ceramic green sheet)
The modified polyvinyl acetal resin that use obtains is operated with embodiment 1 in addition equally, makes ceramic green sheet.
(embodiment 6)
Use the method same with embodiment 5; After making modified polyvinyl acetal resin, be coated with on the PET film of handling through the demoulding with spreader, making its dried thickness is 2 μ m; After air-dry at normal temperatures 1 hour, with metal halid lamp (the different light source of cent Co., Ltd. system) irradiation 3000mJ/cm
2(irradiation time is 10 seconds) wavelength obtains ceramic green sheet in the ultraviolet ray of 230～400nm.
(embodiment 7)
(making of modified polyvinyl acetal resin and ceramic size composition)
Use the method same, make modified polyvinyl acetal resin with embodiment 3.
In the mixed solvent of toluene 15 weight parts and ethanol 15 weight parts, add modified polyvinyl acetal resin 8 weight parts that obtain, stirring and dissolving adds Octyl adipate 7 weight parts as softening agent, stirring and dissolving then.In the resin solution that obtains, add aluminum oxide 100 weight parts as ceramic powder, mixed 48 hours with ball mill, obtain ceramic size composition.
(making of ceramic green sheet)
The ceramic size composition that use obtains is operated with embodiment 1 in addition equally, makes ceramic green sheet.
(embodiment 8)
(making of modified polyvinyl acetal resin and ceramic size composition)
Use the method same, make modified polyvinyl acetal resin with embodiment 3.
In the mixed solvent of toluene 15 weight parts and ethanol 15 weight parts, add modified polyvinyl acetal resin 8 weight parts that obtain, stirring and dissolving adds dioctyl sebacate 7 weight parts as softening agent, stirring and dissolving then.In the resin solution that obtains, add aluminum oxide 100 weight parts as ceramic powder, mixed 48 hours with ball mill, obtain ceramic size composition.
(making of ceramic green sheet)
The ceramic size composition that use obtains is operated with embodiment 1 in addition equally, makes ceramic green sheet.
(embodiment 9)
(making of modified polyvinyl acetal resin and ceramic size composition)
Use the method same, make modified polyvinyl acetal resin with embodiment 3.
In the mixed solvent of toluene 15 weight parts and ethanol 15 weight parts, add modified polyvinyl acetal resin 8 weight parts that obtain, stirring and dissolving adds Witcizer 300 10 weight parts as softening agent, stirring and dissolving then.In the resin solution that obtains, add aluminum oxide 100 weight parts as ceramic powder, mixed 48 hours with ball mill, obtain ceramic size composition.
(making of ceramic green sheet)
On the PET film of handling through the demoulding, it is 2 μ m that the ceramic size composition that uses the spreader coating to obtain makes its dried thickness, after air-dry at normal temperatures 1 hour, with metal halid lamp (the different light source of cent Co., Ltd. system) irradiation 3000mJ/cm
2(irradiation time is 30 seconds) wavelength ultraviolet ray in 200～365nm scope obtains ceramic green sheet.
(comparative example 1)
(making of polyvinyl acetal resin)
With Z 150PH 100 weight parts of saponification deg 99.5% in the zero(ppm) water of 1200 weight parts, heat the dissolving after, remain in 20 ℃, to wherein adding 70% nitric acid, 10 weight parts, add butyraldehyde 16 weight parts then.Then, be cooled to 10 ℃, add butyraldehyde 45 weight parts.After resin is separated out, kept 30 minutes, add nitric acid 60 weight parts then, be warming up to 35 ℃, kept 3 hours.Reaction was washed 10 hours with the distillation current after finishing, and added sodium hydroxide, with the pH regulator to 8 of solution.Solution after keeping 6 hours under 50 ℃, is cooled off.After with zero(ppm) water solution stream being washed 2 hours, dehydration, drying obtain polyvinyl acetal resin.
The residual hydroxyl amount of the polyvinyl acetal resin that obtains is 32 moles of %, and butyral unit content is 67 moles of %, and ethanoyl unit content is 1 mole of %.
(making of ceramic size composition and ceramic green sheet)
The polyvinyl acetal resin that use obtains is operated with embodiment 1 in addition equally, obtains ceramic size composition and ceramic green sheet.
(comparative example 2)
With Z 150PH 100 weight parts of saponification deg 99.5% in the zero(ppm) water of 1200 weight parts, heat the dissolving after, remain in 20 ℃, to wherein adding 70% nitric acid, 70 weight parts, add butyraldehyde 35 weight parts, acetaldehyde 20 weight parts then.After resin is separated out, kept 30 minutes, be warming up to 35 ℃ then, kept 3 hours.Reaction was washed 10 hours with the distillation current after finishing, and added sodium hydroxide, with the pH regulator to 8 of solution.Solution after keeping 6 hours under 50 ℃, is cooled off.After with zero(ppm) water solution stream being washed 2 hours, dehydration, drying obtain polyvinyl acetal resin.
The residual hydroxyl amount of the polyvinyl acetal resin that obtains is 28 moles of %, and butyral unit content is 31 moles of %, ethylidene ether unit (R
1: methyl) content is 40 moles of %, and ethanoyl unit content is 1 mole of %, uses the polyvinyl acetal resin that obtains, and operates equally with embodiment 1 in addition, obtains ceramic green sheet.
(comparative example 3)
Use the method same with embodiment 1; After making polyvinyl acetal resin and ceramic size composition; On the PET film of handling through the demoulding, it is 2 μ m that the ceramic size composition that uses the spreader coating to obtain makes its dried thickness, after air-dry at normal temperatures 1 hour; Descended dry 30 minutes at 80 ℃ with baking oven, make ceramic green sheet.
(comparative example 4)
Use the method same with embodiment 1; After making modified polyvinyl acetal resin and ceramic size composition; On the PET film of handling through the demoulding, it is 2 μ m that the ceramic size composition that uses the spreader coating to obtain makes its dried thickness, after air-dry at normal temperatures 1 hour; Descended dry 6 hours at 100 ℃ with baking oven, make ceramic green sheet.
(comparative example 5)
Use the method same with embodiment 1; After making modified polyvinyl acetal resin and ceramic size composition, on the PET film of handling through the demoulding, it is 2 μ m that the ceramic size composition that uses the spreader coating to obtain makes its dried thickness; After air-dry at normal temperatures 1 hour, irradiation 3000mJ/cm
2(irradiation time is 10 seconds) wavelength light in 380～600nm scope obtains ceramic green sheet.
(comparative example 6)
(making of polyvinyl acetal resin and ceramic size composition)
Use the method same, make polyvinyl acetal resin with comparative example 2.
In the mixed solvent of toluene 15 weight parts and ethanol 15 weight parts, add polyvinyl acetal resin 8 weight parts that obtain, stirring and dissolving adds dioctyl sebacate 7 weight parts as softening agent, stirring and dissolving then.In the resin solution that obtains, add aluminum oxide 100 weight parts as ceramic powder, mixed 48 hours with ball mill, obtain ceramic size composition.
(making of ceramic green sheet)
The ceramic size composition that use obtains is operated with embodiment 1 equally, makes ceramic green sheet.
(comparative example 7)
Use the method same with comparative example 1; After making polyvinyl acetal resin; In the mixed solvent of toluene 15 weight parts and ethanol 15 weight parts, add modified polyvinyl acetal resin 8 weight parts that obtain, stirring and dissolving; Add Witcizer 300 10 weight parts then, stirring and dissolving as softening agent.In the resin solution that obtains, add aluminum oxide 100 weight parts as ceramic powder, mixed 48 hours with ball mill, obtain ceramic size composition.
On the PET film of handling through the demoulding, it is 2 μ m that the ceramic size composition that uses the spreader coating to obtain makes its dried thickness, after air-dry at normal temperatures 1 hour, with metal halid lamp (the different light source of cent Co., Ltd. system) irradiation 3000mJ/cm
2(irradiation time is 10 seconds) wavelength ultraviolet ray in 200～365nm scope obtains ceramic green sheet.
(evaluation)
(1) has or not the corrosion of generation sheet material
Ceramic green sheet is not peeled off from the PET film, on ceramic green sheet, dripped (about 0.02g) Terpineol 350 or dihydroterpineol with water absorption tube, the state of the ceramic green sheet of visual inspection after 10 seconds has or not the corrosion of generation sheet material by following standard evaluation.
Zero: do not observe gauffer and hole on the raw cook.
*: observe gauffer or hole on the raw cook.
(2) intensity evaluation (breaking point stress, elastic modulus detection)
The ceramic green sheet that obtains in embodiment and the comparative example is peeled off from the PET film,, used the tension force stretching trier, measure breaking point stress, Young's modulus the raw cook of peeling off.Test film uses the test film of long 20mm * wide 50mm, and trial speed is 25mm/ minute.
(3) intensity evaluation (separability when containing solvent)
On ceramic green sheet, drip (about 0.02g) Terpineol 350 with water absorption tube, peel off from the PET film after 10 seconds, naked eyes are estimated the separability of ceramic green sheet.
Zero: can be intactly with ceramic green sheet glass.
*: the local or all visible of ceramic green sheet breaks.
[table 1]
(embodiment 10)
(making of polyvinyl acetal resin compsn)
Use T.K.HomoDisper (fmodel, special machine chemical industry corporate system), the modified polyvinyl acetal resin that obtains among the embodiment 15 weight parts and lindenol 95 weight parts were heated while stirring in 80 ℃ oil bath 3 hours, dissolving.Stirred 1 hour down at 80 ℃, obtain the modified polyvinyl acetal resin compsn.
(making of electrode paste agent)
In modified polyvinyl acetal resin compsn 100 weight parts that obtain, add nickel by powder (2020SS, Mitsui Metal Co., Ltd.'s corporate system) 130 weight parts as conductive powder, mixing with three rollers.Then, to the electrode paste agent compsn after mixing, use metal halid lamp (the different light source of cent Co., Ltd. system) irradiation 3000mJ/m
2(irradiation time 30 seconds) wavelength ultraviolet ray in 200～365nm scope obtains electrode paste agent.
(embodiment 11)
Use the modified polyvinyl acetal resin that obtains among the embodiment 2, all operate equally in addition, make electrode paste agent with embodiment 10.
(embodiment 12)
Use the modified polyvinyl acetal resin that obtains among the embodiment 3, all operate equally in addition, make electrode paste agent with embodiment 10.
(embodiment 13)
Use the modified polyvinyl acetal resin that obtains among the embodiment 4, all operate equally in addition, make electrode paste agent with embodiment 10.
(embodiment 14)
Use the modified polyvinyl alcohol that obtains among the embodiment 4 resin that contracts,, use metal halid lamp (the different light source of cent Co., Ltd. system) with irradiation energy 1000mJ/m to the electrode paste agent compsn after mixing
2(irradiation time 10 seconds) illumination wavelength ultraviolet ray in 200～365nm scope is operated with embodiment 10 in addition equally, makes electrode paste agent.
(comparative example 8)
Use the polyvinyl acetal resin that obtains in the comparative example 1, all operate equally in addition, make electrode paste agent with embodiment 10.
(comparative example 9)
Use the polyvinyl acetal resin that obtains in the comparative example 2, all operate equally in addition, make electrode paste agent with embodiment 10.
(comparative example 10)
In (making of electrode paste agent) of embodiment 10, do not shine 3000mJ/m
2The ultraviolet ray of wavelength in 200～365nm scope of (irradiation time 30 seconds) operated with embodiment 10 in addition equally, makes electrode paste agent.
(evaluation)
(viscosimetric analysis)
To the electrode paste agent that obtains, use rotational rheometer (Gemini150, Bohlin corporate system) and cone-plate (diameter 40mm, 1 ° of cone angle), be that 20 ℃, velocity of shear are to measure viscosity under the condition of 10s in the mensuration temperature.
[table 2]
| Viscosity (Pas) | |
| Embodiment 10 | 65 |
| Embodiment 11 | 55 |
| Embodiment 12 | 68 |
| Embodiment 13 | 60 |
| Embodiment 14 | 69 |
| Comparative example 8 | 47 |
| Comparative example 9 | 50 |
| Comparative example 10 | 46 |
(embodiment 15)
(making in next door)
With the modified polyvinyl acetal resin that obtains among the embodiment 18 weight parts, as Terpineol 350 30 weight parts of organic solvent, (the Asahi Glass corporate system, IWF-DT430) 50 weight parts mix frit (glass frit).Paste is used in the next door that coating obtains on the PET film, air-dry at normal temperatures 1 hour, behind the precursor of making next door, uses metal halid lamp (the different light source of cent Co., Ltd. system), irradiation 3000mJ/cm
2(irradiation time 30 seconds) wavelength ultraviolet ray in 200～365nm scope.
On the next door precursor, 50 ℃ of laminated sandblasts with dry film photoresist (the chemical industry corporate system is answered in Tokyo, BF603) after, the configuration exposed mask, after shining, carry out patterning, sandblast.Then, wash, make the next door with 2% aqueous sodium carbonate.
(embodiment 16)
Use the modified polyvinyl acetal resin that obtains among the embodiment 2, all operate equally in addition, form the next door with embodiment 15.
(embodiment 17)
Use the modified polyvinyl acetal resin that obtains among the embodiment 3, all operate equally in addition, form the next door with embodiment 15.
(embodiment 18)
Use the modified polyvinyl acetal resin that obtains among the embodiment 3, all operate equally in addition, form the next door with embodiment 15.
(embodiment 19)
Use the modified polyvinyl acetal resin that obtains among the embodiment 3, irradiation 1000mJ/cm
2(irradiation time 10 seconds) wavelength ultraviolet ray in 200～365nm scope is all operated with embodiment 15 in addition equally, forms the next door.
(comparative example 11)
Use the polyvinyl acetal resin that obtains in the comparative example 1, all operate equally in addition, form the next door with embodiment 15.
(comparative example 12)
Use the polyvinyl acetal resin that obtains in the comparative example 2, all operate equally in addition, form the next door with embodiment 15.
(comparative example 13)
Adopt the method same with embodiment 15, make the next door with paste after, the dry film photoresist that obtains is coated on the PET film with resin combination, after air-dry at normal temperatures 1 hour, again in baking oven in 80 ℃ dry 30 minutes down, form the next door.
(comparative example 14)
Adopt the method same with embodiment 15, make the next door with paste after, the next door that obtains is coated on the PET film with paste, after air-dry at normal temperatures 1 hour, again in baking oven in 100 ℃ dry 6 hours down, form the next door.
(evaluation)
(1) evaluation of neutralizing treatment property
With the state in the next door after the washing of optics observation by microscope 0.2% aqueous sodium carbonate, estimate by following standard.
Zero: do not find fragmentation or crack.
*: visible fragmentation or crack.
[table 3]
| Neutralizing treatment property | |
| Embodiment 15 | ○ |
| Embodiment 16 | ○ |
| Embodiment 17 | ○ |
| Embodiment 18 | ○ |
| Embodiment 19 | ○ |
| Comparative example 11 | × |
| Comparative example 12 | × |
| Comparative example 13 | × |
| Comparative example 14 | × |
As embodiment, comparative example; Ceramic green sheet, electrode paste agent have been enumerated; The powder that uses in Pb-based lanthanumdoped zirconate titanates that for example in using piezoelectric actuator, uses or the SOFC be the dielectric medium of yttria-stabilized zirconia, PDP use in paste replacement ceramic powder such as frit the time, also obtained same result.
The possibility of utilizing in the industry
According to the present invention; Need not to use linking agent; Get final product the cross-linked pioloform resin that manufacturing machine intensity is high, solvent resistance is excellent with easy method, therefore the method for manufacture of the ceramic molding of the problems such as ageing stability that can solve sheet material burn into undercapacity, viscosity, the method for manufacture of laminated ceramic capacitor, the method for manufacture of electrode paste agent, the method for manufacture of piezoelectric actuator, the method for manufacture of SOFC and method of manufacture and ceramic size composition, conductive paste and the dielectric paste of plasma display can be provided.
Claims (11)
1. the method for manufacture of ceramic molding is characterized in that, comprising:
Be coated with the operation of following ceramic size composition, said ceramic size composition contains ceramic powder, has the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least;
With said ceramic size composition exsiccant operation; And
Through the ultraviolet ray of illumination wavelength in 200～365nm scope, carry out crosslinked operation,
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Group shown in the expression formula (9),
2. the method for manufacture of laminated ceramic formed body is characterized in that,
It is to ceramic green sheet with electrode paste agent is alternately laminated and thermo-compressed and the duplexer that obtains carry out degreasing, the method for manufacture of the laminated ceramic formed body that burns till, comprising:
Be coated with the operation of following ceramic size composition, said ceramic size composition contains ceramic powder, has the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least;
With said ceramic size composition exsiccant operation; And
Through the ultraviolet ray of illumination wavelength in 200～365nm scope, carry out crosslinked operation,
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Group shown in the expression formula (9),
3. the method for manufacture of laminated ceramic capacitor is characterized in that,
It is to ceramic green sheet and electrode paste agent is alternately laminated and thermo-compressed and the duplexer that obtains carry out degreasing, burn till the method for manufacture of laminated ceramic capacitor, comprising:
Be coated with the operation of following ceramic size composition, said ceramic size composition contains ceramic powder, has the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least;
With said ceramic size composition exsiccant operation; And
Through the ultraviolet ray of illumination wavelength in 200～365nm scope, carry out crosslinked operation,
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Group shown in the expression formula (9),
4. a ceramic size composition is characterized in that,
Contain ceramic powder, have the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least,
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Group shown in the expression formula (9),
5. the method for manufacture of electrode paste agent is characterized in that, comprising:
The operation for preparing following electrode paste agent compsn, said electrode paste agent compsn contain conductive powder, have the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least; And
The operation of viscosity is regulated in ultraviolet ray in 200～365nm scope to said electrode paste agent compsn illumination wavelength,
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Group shown in the expression formula (9),
6. a conductive paste is characterized in that,
Contain conductive powder, have the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least,
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Group shown in the expression formula (9),
7. the method for manufacture of piezoelectric actuator is characterized in that,
It is to ceramic green sheet with electrode paste agent is alternately laminated and thermo-compressed and the duplexer that obtains carry out degreasing, the method for manufacture of the piezoelectric actuator that burns till, comprising:
Be coated with the operation of following ceramic size composition, said ceramic size composition contains ceramic powder, has the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least;
With said ceramic size composition exsiccant operation; And
Through the ultraviolet ray of illumination wavelength in 200～365nm scope, carry out crosslinked operation,
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Group shown in the expression formula (9),
8. the method for manufacture of SOFC is characterized in that,
It is after dielectric substrate formed body coating contains electrolytical electrolyte solution and makes dielectric substrate, in the method for manufacture of the SOFC of said dielectric substrate multilayer electrode,
Wherein, said dielectric substrate formed body obtains through following method:
Following formed body is obtained formed body with the resin combination moulding; Ultraviolet ray in 200～365nm scope makes it crosslinked to said formed body illumination wavelength then; Said formed body contain with resin combination have formula (1) at least, the polyvinyl acetal resin and the organic solvent of the structural unit shown in (2), (3) and (4)
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Group shown in the expression formula (9),
9. the method for manufacture of plasma display is characterized in that,
It is overleaf glass baseplate surface form behind dielectric former and the next door precursor with said dielectric former and said next door precursor together carry out degreasing, the method for manufacture of the plasma display that burns till, comprising:
Be coated with the operation of following dielectric paste, said dielectric paste contains dielectric medium, has the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least;
With said dielectric paste exsiccant operation; And
Through the ultraviolet ray of illumination wavelength in 200～365nm scope, carry out crosslinked operation,
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Group shown in the expression formula (9),
10. a dielectric paste is characterized in that,
Contain dielectric medium, have the polyvinyl acetal resin and an organic solvent of the structural unit shown in formula (1), (2), (3) and (4) at least,
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Group shown in the expression formula (9),
11. the method for manufacture of plasma display is characterized in that, comprising:
Be coated with the operation of following next door with paste, said next door contain with paste have formula (1) at least, the polyvinyl acetal resin and the organic solvent of the structural unit shown in (2), (3) and (4);
With said next door with paste exsiccant operation; And
Through the ultraviolet ray of illumination wavelength in 200～365nm scope, carry out crosslinked operation,
In the formula, R
1Expression Wasserstoffatoms or carbonatoms are 1～20 alkyl, R
2Group shown in the expression formula (9),
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP103775/2007 | 2007-04-11 | ||
| JP2007103775 | 2007-04-11 | ||
| JP2007137213 | 2007-05-23 | ||
| JP137213/2007 | 2007-05-23 | ||
| JP2007258081 | 2007-10-01 | ||
| JP258081/2007 | 2007-10-01 | ||
| PCT/JP2008/057183 WO2008126919A1 (en) | 2007-04-11 | 2008-04-11 | Method for production of ceramic molded material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101652407A CN101652407A (en) | 2010-02-17 |
| CN101652407B true CN101652407B (en) | 2012-11-07 |
Family
ID=41674132
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008800116072A Active CN101652408B (en) | 2007-04-11 | 2008-04-11 | Method for production of crosslinked polyvinyl acetal resin, and crosslinked polyvinyl acetal resin |
| CN2008800115741A Active CN101652407B (en) | 2007-04-11 | 2008-04-11 | Method for production of ceramic molded material |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008800116072A Active CN101652408B (en) | 2007-04-11 | 2008-04-11 | Method for production of crosslinked polyvinyl acetal resin, and crosslinked polyvinyl acetal resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN101652408B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106909024B (en) * | 2017-03-28 | 2020-03-13 | 辽宁靖帆新材料有限公司 | Photosensitive resin composition and application thereof |
-
2008
- 2008-04-11 CN CN2008800116072A patent/CN101652408B/en active Active
- 2008-04-11 CN CN2008800115741A patent/CN101652407B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN101652408B (en) | 2012-07-18 |
| CN101652408A (en) | 2010-02-17 |
| CN101652407A (en) | 2010-02-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4354911B2 (en) | Cross-linked polyvinyl acetal | |
| CN1809598B (en) | Binder resin for coating paste | |
| TWI452074B (en) | Crosslinked polyvinyl acetal porous powder, its preparation and use | |
| TWI483977B (en) | Inorganic fine particle dispersion paste | |
| JP5336846B2 (en) | Method for producing crosslinked polyvinyl acetal resin and crosslinked polyvinyl acetal resin | |
| US20130148263A1 (en) | Polyvinyl acetal resin, slurry composition prepared therefrom, ceramic green sheet, and multilayer ceramic capacitor | |
| KR900001478B1 (en) | Dielectric compositions | |
| JP5503144B2 (en) | Manufacturing method of ceramic molded body | |
| CN103842313A (en) | Slurry composition, ceramic green sheet, and layered ceramic capacitor | |
| JP5224722B2 (en) | Resin composition, conductive paste and ceramic paste | |
| CN101652407B (en) | Method for production of ceramic molded material | |
| JP2003301187A (en) | Lubricant for making hole in substrate and lubricating sheet for making hole in substrate | |
| JP2009088410A (en) | Method of manufacturing multilayer ceramic capacitor | |
| JP2015231924A (en) | Slurry composition for manufacturing laminate ceramic capacitor and ceramic green sheet | |
| CN114808473A (en) | Low-temperature-resistant self-adhesive rubber asphalt waterproof coiled material and preparation method thereof | |
| JP6372689B2 (en) | Conductive paste and conductive pattern forming method | |
| WO2013081077A1 (en) | Conductive paste and multilayer ceramic capacitor | |
| JP2013187022A (en) | Conductive paste | |
| JP2010118470A (en) | Conductive paste for laminated ceramic capacitor | |
| JP2020056015A (en) | Polyvinyl acetal resin, composition for ceramic green sheet, ceramic green sheet and laminated ceramic capacitor | |
| KR100597149B1 (en) | Lead-free Transparent Dielectric Composition for Preparing Green Sheet | |
| TWI819397B (en) | Conductive polymer dispersion and its manufacturing method, conductive polymer-containing liquid and its manufacturing method, conductive laminate and its manufacturing method, and capacitor and its manufacturing method | |
| KR100984489B1 (en) | Lead-free transparent dielectric composition used for the fabrication of a dry film for a plasma display panel | |
| JP2012072256A (en) | Epoxy modified polyvinyl acetal resin, ceramic slurry, and ceramic green sheet | |
| JP2009144078A (en) | Sheet for forming dielectric layer, sheet for forming dielectric layer/glass rib, method of manufacturing plasma display panel, and plasma display panel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |