WO2006009051A1 - 感光性ペーストおよびディスプレイパネル用部材の製造方法 - Google Patents
感光性ペーストおよびディスプレイパネル用部材の製造方法 Download PDFInfo
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- WO2006009051A1 WO2006009051A1 PCT/JP2005/012983 JP2005012983W WO2006009051A1 WO 2006009051 A1 WO2006009051 A1 WO 2006009051A1 JP 2005012983 W JP2005012983 W JP 2005012983W WO 2006009051 A1 WO2006009051 A1 WO 2006009051A1
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- photosensitive
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- glass
- paste
- photosensitive paste
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0094—Shielding materials being light-transmitting, e.g. transparent, translucent
- H05K9/0096—Shielding materials being light-transmitting, e.g. transparent, translucent for television displays, e.g. plasma display panel
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/114—Initiator containing
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/127—Spectral sensitizer containing
Definitions
- the present invention relates to a photosensitive paste containing an inorganic powder having soft magnetism.
- An electromagnetic wave shielding plate is widely used as a front filter attached to a display, for example, in order to block electromagnetic waves leaking from a display camera.
- the electromagnetic wave shielding plate used as the front plate of the display is required not to lower the visibility of the display screen of the display.
- an electromagnetic wave shield plate for example, an electromagnetic wave shield plate in which an etching sheet etched in a metal foil cache shape is bonded to a transparent substrate is used.
- a surface treatment process such as chrome plating is required to blacken the mesh-like metal surface, which requires a complicated process.
- Japanese Patent Laid-Open No. 2002-271086 discloses intaglio offset printing on a geometric pattern using an ink containing black pigment and metal particles by intaglio offset printing on a glass substrate.
- a method for manufacturing an electromagnetic wave shielding plate by firing after performing the method has been proposed.
- the black pigment has a high resistance value
- when the black pigment is added in such an amount that sufficient blackness can be obtained the resistance value of the obtained conductive layer becomes high. Therefore, in order to ensure sufficient electromagnetic wave shielding properties, it is necessary to form a metal layer on the surface of the black conductive layer by wet plating, and there is a problem that the process becomes complicated.
- Patent Document 1 Japanese Patent Laid-Open No. 2002-271086
- An object of the present invention is to provide a photosensitive paste capable of producing a display panel member having sufficient visibility and electromagnetic wave shielding properties by a simple process.
- Means for solving the problem [0004] That is, the present invention is a paste having an inorganic powder and a photosensitive organic component, wherein the inorganic powder contains at least a soft magnetic powder (A) and a glass powder (B), A photosensitive paste having a mass ratio of A) to glass powder (B) in the range of 20Z80 to 70Z30.
- the present invention is a method for producing a member for a display panel, which includes a step of applying the above-mentioned photosensitive paste on a substrate and drying it.
- the present invention it is possible to provide a photosensitive paste capable of pattern cleaning with high definition and capable of forming a soft magnetic layer having high magnetic permeability.
- a display panel member having excellent visibility and electromagnetic shielding properties can be produced by a simple process.
- the photosensitive paste in the present invention is a photosensitive base composed of an inorganic powder and a photosensitive organic component.
- the photosensitive paste of the present invention preferably contains 5 to 50% by mass of the photosensitive organic component in the paste and 50 to 95% by mass of the inorganic powder in the paste.
- the inorganic powder includes at least a soft magnetic powder and a glass powder.
- the soft magnetic powder may be any material that exhibits the property of losing magnetization and returning to its original state when the external magnetic field is removed.
- Specific examples of the soft magnetic powder include powder made of iron, iron alloy, or ferrite.
- the soft magnetic powder is preferably an iron alloy powder or a ferrite powder from the viewpoint of having high magnetic permeability and low electrical conductivity. Ferrite powder is more preferable because of its high saturation magnetic flux density and low coercive force. As ferrite powder
- a ferrite composed of a ferrite represented by the general formula (a divalent metal selected from Zn) is particularly suitable.
- iron alloy powder include permalloy, supermalloy, permendule, amorphous, sendust, ferrite, Fe-Ni, Fe-Co, Fe-Zr, Fe-Mn, Fe-Si, Fe-Al Etc.
- the soft magnetic powder preferably has a center particle diameter in the range of 0.1 to 5 / ⁇ ⁇ . center A powder having a particle size of less than 0.1 ⁇ m is not preferable because it is difficult to disperse well in the photosensitive paste. A powder having a center particle diameter exceeding 5 / zm is not preferable because the flatness of the film after firing deteriorates the shape of the pattern. The central particle diameter is more preferably in the range of 0.5 to 4 m. Furthermore, the soft magnetic powder preferably has a maximum particle size of 10 m or less. If the maximum particle size of the soft magnetic powder exceeds 10 m, the flatness of the film after baking and the shape of the pattern deteriorate, which is not preferable. The maximum particle size is more preferably 8 / zm or less.
- the central particle size and the maximum particle size can be obtained from a volume reference distribution such as a Coulter counter method, a photon correlation method, and a laser one diffraction method.
- the soft temperature of the glass powder is preferably 800 ° C or lower.
- the softening temperature of the glass powder is preferably 350 ° C or higher. Glasses with soft temperatures below 350 ° C have poor chemical stability. On the other hand, if the softening temperature exceeds 800 ° C, the glass powder becomes soft in the firing process.
- the softening temperature of the glass powder is preferably 750 ° C. or less, more preferably 650 ° C. or less.
- the glass powder also has an amorphous glass strength. In the case of crystalline glass, cracks or the like may occur on the film surface after firing, and the insulation and electrical characteristics may be deteriorated immediately.
- borosilicate glass powder containing at least one element selected from the group power of bismuth oxide, zinc oxide, lead oxide and acid linker is preferably used.
- glass powder containing bismuth oxide or zinc oxide as a main component is preferable.
- the substrate may be warped by an ion exchange reaction with the substrate glass during firing, so the alkali metal content should be 10% by mass or less. It is preferable.
- the center particle diameter of the glass powder is preferably in the range of 0.1 to 5 m.
- a powder having a center particle diameter of less than 0.1 ⁇ m is not preferable because it is difficult to disperse well in the photosensitive paste.
- a powder having a center particle diameter exceeding 5 / zm is not preferable because the flatness of the film after baking and the pattern shape deteriorate.
- the central particle diameter is more preferably in the range of 0.5 to 4 / ⁇ ⁇ .
- the maximum particle size of the glass powder is preferably 10 m or less. If the maximum particle size of the glass powder exceeds 10 / zm, the film flatness and pattern Since the shape is bad, it is not preferable.
- the maximum particle size of the glass powder is more preferably 8 m or less.
- the average particle size and the maximum particle size of the glass powder can be determined in the same manner as the soft magnetic powder.
- the particle diameter of the soft magnetic powder and the particle diameter of the glass powder are approximately the same.
- the center particle diameter of the soft magnetic powder Z The value of the center particle diameter of the glass powder is preferably in the range of 0.1 to 5, more preferably in the range of 0.5 to 4. The same applies to the maximum particle size.
- the glass powder is also called a glass frit, and is added to facilitate sintering of the inorganic powder during firing. Since glass frit is a component for bridging, it is preferable to use a small amount. Usually, about 3 to 10% by mass in the inorganic powder is added. However, the inventors have found that the amount of the glass powder (B) in the photosensitive paste of the present invention is 30% by mass with respect to the total of the soft magnetic powder (A) and the glass powder (B). Less than preferred, I did not get the result!
- the soft magnetic powder used has high magnetic permeability and soft magnetic properties. It is necessary that the magnetic powder and the glass powder are sufficiently sintered to form a dense soft magnetic layer. This is because if the soft magnetic layer is not dense, the magnetic permeability inherent in the soft magnetic powder is not expressed.
- the firing temperature needs to be relatively high. Depending on the application, firing may not be possible at a high temperature. For example, when glass is used for the substrate, firing temperature is limited because firing at a high temperature adversely affects the glass substrate.
- the firing temperature is adjusted by adjusting the content of the glass powder (B) to 30% by mass or more with respect to the total of the soft magnetic powder (A) and the glass powder (B).
- Magnetic powder and glass powder can be sufficiently sintered even at relatively low temperatures, and the desired electrical characteristics can be obtained.
- the content of the glass powder (B) exceeds 80% by mass with respect to the total of the soft magnetic powder (A) and the glass powder (B)
- the photosensitive paste of the present invention may contain an inorganic powder other than the soft magnetic powder and glass powder.
- an inorganic powder other than the soft magnetic powder and glass powder.
- adding a black pigment can contribute to an improvement in contrast when used as a display front plate.
- a pigment made of an inorganic acid including an acid such as cobalt, nickel, copper, iron, manganese, chromium and ruthenium can be preferably used. It is also effective to use a spinel compound composed of oxides of three or more elements.
- a black pigment it is preferable to use a pigment having a center particle diameter of 0.01-1.5 m because a black layer having uniform and sufficient blackness can be formed. When the central particle diameter of the black pigment is less than 0.01 m, the black pigment is easily aggregated and the blackness tends to be non-uniform immediately.
- the blackness of the black pigment exceeds 1, the blackness tends to decrease. It is also preferable to use carbon as the black pigment. By using carbon particles having a center particle diameter of 1 ⁇ m or less, a black layer having excellent blackness can be formed. When the heating step of 400 ° C. or higher is used, it is preferable to use heat-resistant carbon. The amount of black pigment added depends on the type of black pigment, but in order to obtain sufficient blackness, a range of 0.1 to 10% by mass with respect to the entire inorganic powder is preferable.
- the photosensitive organic component in the photosensitive paste is usually at least one selected from a reactive monomer, a reactive oligomer and a reactive polymer, and if necessary, a binder polymer, a photopolymerization initiator, and a photoacid.
- the reactivity in reactive monomers, reactive oligomers and reactive polymers means that when irradiated with actinic rays. It means that the chemical structure changes through a reaction such as photocrosslinking, photopolymerization, photodepolymerization, and photomodification.
- a compound having an active carbon-carbon unsaturated double bond is preferably used.
- Monofunctional and polyfunctional compounds having a vinyl group, an aryl group, an acrylate group, a methacrylate group, an acrylamide group or the like as the functional group can be preferably used.
- Specific examples include 2- (2 ethoxyethoxy) ethyl acrylate, 1,3 butanediol diacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, cyclohexyl methacrylate, ethylene glycol.
- Examples include dimetatalylate, trimethylol-propyl pantrimethacrylate, trimethylolpropane tritalylate, and glycidyl metatalylate. Ethylene oxide adducts and propylene oxide adducts of these compounds can also be preferably used.
- the photosensitive oligomer and photosensitive polymer oligomers and polymers having an active carbon-carbon unsaturated double bond are preferably used. It is preferable that the photosensitive oligomer and the photosensitive polymer have a carboxyl group because the developability of the photosensitive paste coating film after the exposure can be improved. Oligomers and polymers having a carboxyl group include, for example, monomers containing a carboxyl group such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid or acid anhydrides thereof, and methacrylic acid esters. It can be obtained by copolymerizing monomers such as acrylic acid ester, styrene, acrylonitrile, butyl acetate, 2-hydroxy acrylate.
- monomers containing a carboxyl group such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid or
- an acrylic copolymer having a (meth) acrylic acid ester and (meth) acrylic acid as a copolymerization component is preferably used because of its low thermal decomposition temperature during firing.
- styrene Z methyl methacrylate Z methacrylic acid copolymer is preferably used.
- the acid value of the copolymer having a carboxyl group is preferably 50 to 150 mgKOHZg.
- the acid value exceeds 150, the allowable development width becomes narrow.
- the acid value is less than 50, the solubility of the unexposed portion of the photosensitive paste coating film in the developing solution is lowered, so that development cannot be performed unless the concentration of the developing solution is increased.
- the developer concentration is increased, the exposed portion of the photosensitive paste coating film is peeled off, making it difficult to obtain a high-definition pattern.
- a glycidyl group or an isocyanate group with respect to a mercapto group, amino group, hydroxyl group or carboxyl group in the oligomer or polymer is used.
- an ethylenically unsaturated compound having a carboxylic acid a method of reacting with a strong rubonic acid such as acrylic acid chloride, methacrylic acid chloride or aryl chloride, and maleic acid can be used.
- Examples of the ethylenically unsaturated compound having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allylicidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonate, and glycidyl isocrotonate.
- glycidyl methacrylate is preferably used.
- Examples of the ethylenically unsaturated compound having an isocyanate group include (meth) atalyloyl isocyanate, (meth) atalyloylethylisocyanate and the like.
- Ethylenically unsaturated compounds having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid chloride, or aryl chloride may be added to the mercapto group, amino group, hydroxyl group and carboxyl group in the oligomer or polymer. It is preferable to carry out ⁇ 1 molar equivalent reaction.
- Preferable U and addition amount of the photosensitive monomer, photosensitive oligomer and photosensitive polymer are 2 to 40% by mass, more preferably 5 to 30% by mass in the photosensitive paste.
- a Noinder polymer When a Noinder polymer is required, polymers such as polybutyl alcohol, polyvinyl butyral, methacrylic acid ester polymer, acrylic acid ester polymer, acrylic acid ester-methacrylic acid ester copolymer, butyl methacrylate
- rosin For example, rosin can be used.
- the photopolymerization initiator used in the present invention is used by selecting a compound power that generates radical species when irradiated with actinic rays. Further, by using a sensitizer together with a photopolymerization initiator, the sensitivity can be improved and the effective wavelength range for the reaction can be expanded. As the photopolymerization initiator and sensitizer, general photopolymerization initiators and sensitizers can be used. However, since the photosensitive paste of the present invention contains soft magnetic powder, the photosensitive paste is black. Therefore, the exposure light is absorbed, a large amount of exposure is required, and it is difficult to obtain sufficient sensitivity.
- the photopolymerization initiator and Z or sensitizer in the present invention those having an extinction coefficient of 1, OOO (lZmol'cm) or more at a wavelength of 365 nm can be particularly preferably used. More preferably, the extinction coefficient at a wavelength of 365 nm is not less than 2, 0 OO (lZmol'cm). High sensitivity is obtained by using a photopolymerization initiator and Z or sensitizer having an extinction coefficient of 1, O00 (l / mol-cm) or more at a wavelength of 365 nm. Since the tolerance is also improved, the process margin can be expanded.
- the upper limit of the extinction coefficient is not particularly limited, but is preferably 100 0, OOO (lZmol'cm) or less at a wavelength of 365 nm.
- the extinction coefficient can be measured as follows.
- Absorption coefficient Absorbance Z (Molar concentration X d) (where d represents cell length)
- the photopolymerization initiator is preferably added in a range of 0.05 to 10% by mass with respect to the photosensitive organic component, and is more preferable. Or 0.1 to 10% by mass. If the amount of the polymerization initiator is too small, the photosensitivity decreases, and if the amount of the photopolymerization initiator is too large, the residual ratio of the exposed area may be reduced during development.
- the addition amount is preferably 0.05 to 10% by mass, more preferably 0.1 to 10% by mass with respect to the photosensitive organic component. . If the amount of the sensitizer is too small, the effect of improving the photosensitivity is not exhibited, and if the amount of the sensitizer is too large, the residual ratio of the exposed portion may be reduced during development.
- the photosensitive paste contains a photopolymerization initiator having an extinction coefficient of 1,000 (lZmol ⁇ cm) or more at a wavelength of 365 nm and Z or a sensitizer, so that the sensitivity of the photosensitive paste is high.
- the photosensitive paste coating film is thick, the exposure light attenuates at the bottom, so that sufficient hardening is difficult to proceed. Therefore, in order to advance the curing of the photosensitive paste coating film to the bottom, it is necessary to increase the exposure amount. Therefore, if a compound having an absorption maximum in a wavelength region exceeding 400 nm is further added, light having a wavelength exceeding 400 nm is applied to the photosensitive paste. Since it is easy to permeate to the bottom of the cloth film, curing proceeds at the bottom of the coating film. Therefore, exposure can be performed with a small exposure amount.
- the photosensitive paste coating film since the curing can proceed to the bottom of the photosensitive paste coating film, the photosensitive paste coating film does not peel off the substrate force even if the development time is extended, and the process margin can be widened. Also, processing with a thick film is possible.
- a bis (alkylamino) benzophenone or thixanthone derivative as a sensitizer and use it in combination with a compound having an absorption maximum in a wavelength region exceeding 400 nm because a remarkable effect is obtained.
- the absorption maximum of these compounds is more preferably in the wavelength region exceeding 405 nm, and more preferably in the wavelength region exceeding 410 nm, since the above effect is higher.
- the main wavelengths of ultra-high pressure mercury lamps used for exposure are usually 365 nm, 405 nm and 436 nm. Therefore, when using such a light source, the absorption maximum of these compounds is preferably in the wavelength region of 500 nm or less. .
- Preferred correct ⁇ Ka ⁇ of compounds having an absorption maximum in a wavelength region beyond the 400nm is 0.1 to 10 weight 0/0 in the photosensitive paste. More preferably, it is 0.5 to 5% by mass.
- UV absorber it is also effective to add an ultraviolet absorber to the photosensitive paste of the present invention.
- soft magnetic powders and glass powders having different properties are used as inorganic powders, so that the pattern in which exposure light scattering is large can easily spread within the photosensitive paste coating film. There is a tendency.
- the UV absorber absorbs scattered light inside the photosensitive paste coating film and weakens the scattered light. This suppresses the spread of the pattern and provides a sharp pattern.
- UV absorbers include benzophenone compounds, cyanoacrylate compounds, salicylic acid compounds, benzotriazole compounds, and indole compounds. Examples thereof include a compound and an inorganic fine particle metal oxide.
- benzophenone compounds cyanoacrylate compounds, benzotriazole compounds, and indole compounds are particularly effective.
- Specific examples thereof include 2,4-dihydroxybenzophenone, 2hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.
- the addition amount of the ultraviolet absorber is preferably 0.001 to LO mass% in the photosensitive paste, more preferably 0.005 to 5 mass%.
- the amount added is 0.001 to less than 10% by mass, the absorbing ability of scattered light is low. If the addition amount exceeds 10% by mass, the exposure light transmittance is lowered, and the sensitivity of the photosensitive paste is lowered.
- an organic dye as an ultraviolet absorber.
- organic dyes in addition to the effect of absorbing scattered light inside the photosensitive paste, the photosensitive paste By being colored, there is an effect that visibility during development is improved. That is, it becomes easy to distinguish between the portion where the paste remains at the time of image formation and the portion where the paste is removed.
- the organic dye is not particularly limited, but those that do not remain in the insulating film after firing are preferred.
- anthraquinone dyes indigoid dyes, phthalocyanine dyes, carbo dyes, quinone imine dyes, methine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes Dyes, phthalimide dyes, perinone dyes, etc.
- a dye that absorbs light having a wavelength in the vicinity of the h-line and i-line for example, a basic dye such as basic blue, because the effects of the present invention are more easily exhibited.
- the addition amount of the organic dye is preferably 0.001 to 1% by mass.
- a polymerization inhibitor to the photosensitive paste of the present invention.
- the polymerization inhibitor captures radicals with a small exposure amount. Because the photoreaction proceeds rapidly at the point where the exposure dose is increased to the extent that it cannot be suppressed by the polymerization inhibitor!], It is possible to increase the contrast between the dissolution and insolubility of the photosensitive paste in the developer after exposure. I'll do it.
- polymerization inhibitor examples include hydroquinone, phenothiazine, p-t-butylcatechol, 2,5-dibutylhydroquinone, mono-tert-butylhydroquinone, 2,5-di-ta-amylhydroquinone, N-ph.
- examples include, but are not limited to, enilnaphthylamine, 2,6 di-tert-butyl-p-methylphenol, chloranil, p-methoxyphenol, pyrogallol and the like. In the present invention, one or more of these can be used.
- the addition amount of the polymerization inhibitor, good Mashiku than preferably is from 0.001 to 1% by weight member in the photosensitive paste is from 0.005 to 0.5 mass 0/0.
- the content is less than these ranges, the effect of improving the contrast in insoluble and insoluble in the developer is small. Exceeding this range is not preferable because the sensitivity of the photosensitive base does not decrease and the degree of polymerization of the photosensitive organic component does not increase.
- the pattern shape By controlling the ultraviolet absorber and the polymerization inhibitor, the pattern shape can be controlled.
- organic solvents include methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl Pyr alcohol, Tetrahydrofuran, Dimethyl sulfoxide, Gamma-butyral rataton, Bromobenzene, Black-mouthed benzene, Dibromobenzene, Dichlorobenzene, Bromobenzoic acid, Black-mouthed benzoic acid, Diethylene glycol monoethyl ether acetate, Diethylene glycolenomono Butinoleethenore, Diethyleneglycolenobutinoreethenoleacetate, 2-Methyl-2,4-Pentanediol, 3-Methyl-1,5-p
- an organic solvent mainly considering volatility and solubility of the photosensitive monomer, photosensitive oligomer and photosensitive polymer to be used.
- the solubility of photosensitive monomers, photosensitive oligomers and photosensitive polymers in organic solvents is low, and even if the solid content ratio is the same, the viscosity of the photosensitive paste tends to be high, and the coating properties tend to be poor. .
- a preferred content of the organic solvent is 5 to 50 mass% in the photosensitive paste, preferably a further 10 to 40 mass 0/0.
- the photosensitive paste of the present invention is prepared by preparing various components so as to have a predetermined composition, and then predispersing with a mixer such as a planetary mixer, and then dispersing and kneading means with a disperser such as a three-roller. To make a uniform dispersion.
- the photosensitive paste of the present invention can be suitably used for production of a display panel member.
- the display panel member refers to a member for a display panel having electromagnetic wave shielding properties. Typical examples include an electromagnetic wave shielding plate disposed on the front surface of the display panel, or an optical filter for a display panel incorporating the electromagnetic wave shielding plate.
- the photosensitive paste of the present invention can be used for an electromagnetic wave shield of a wireless communication device, a magnetic layer of a wiring board having a part of an inductor, and the like.
- a through hole portion is formed through an exposure step and a development step, and further baked to form a magnetic layer.
- the photosensitive paste of the present invention there are advantages such as high productivity, low cost, and peeling of the magnetic layer of a part of the inductor, thereby improving reliability.
- Examples of the layer configuration of the electromagnetic wave shielding plate include configurations of substrate Z black layer Z metal layer, substrate Z metal layer Z black layer, substrate Z black layer Z metal layer Z black layer, and the like. Also, using a substrate with a transparent conductive layer formed on the surface, the substrate Z transparent conductive layer Z black layer Z metal layer, substrate Z transparent conductive layer Z metal layer Z black layer, substrate Z transparent conductive layer Z black layer It is also preferable to adopt a configuration such as a Z metal layer Z a black layer. When the paste method is used to create the black layer and the metal layer, any layer configuration can be created by changing the type and order of the paste to be applied.
- the substrate used for the electromagnetic wave shielding plate can be used without particular limitation as long as it is transparent and can be disposed on the front surface of the display.
- glass substrates, resin substrates, films, and the like can be used.
- resin substrate a known transparent resin substrate such as an acrylic plate or a polycarbonate substrate having a thickness of 0.5 to 3 mm can be used.
- film a polyethylene terephthalate film or a polycarbonate film can be used.
- the thickness of the glass substrate is preferably about 0.7 to 5 mm, more preferably about 1.0 to 3.5 mm. If the thickness is less than 0.7 mm, the glass substrate is easily damaged during handling and use. If the thickness exceeds 5 mm, it becomes too heavy, which is not preferable.
- the glass substrate is tempered from the viewpoint of preventing damage during production and use. Is preferred. From the viewpoint of the tempering treatment, a glass substrate having a thickness of 1.5 mm or more is preferred.
- the glass substrate may be strengthened before or after the black layer and the metal layer are formed. That is, after a glass substrate is tempered, a black layer and a metal layer may be formed on the tempered glass, or after a black layer and a metal layer are formed on ordinary glass, the glass may be tempered.
- the glass strengthening process is a process for increasing the strength by giving a compressive strain to the glass surface, and can be divided into a heat strengthening process and a chemical strengthening process according to a method for giving the surface a compressive strain. Since glass breaks from the surface by tensile force, the strength can be increased if the surface is preliminarily compressed.
- the heat strengthening treatment is performed by heating the plate-like glass to the vicinity of its soft saddle point and then rapidly cooling the glass surface with an air jet to form a compressive stress layer on the glass surface.
- a group of air nozzle forces perpendicular to both sides of the glass substrate It is preferable to carry out by rapidly cooling by blowing an air jet.
- the glass substrate may be colored with metal ions, metal colloids, non-metal elements, and the like.
- the glass substrate can be colored by a known method. Coloring is often done to improve the visibility of the display.
- the resistance value of the substrate can be reduced and the electromagnetic wave shielding property can be improved while maintaining the light transmittance.
- the electromagnetic wave shielding property can be improved by using a glass substrate having a transparent conductive layer made of ITO or oxide tin oxide on the glass substrate surface.
- These transparent conductive layers can be formed on a substrate by a sputtering CVD (chemical 'vapor' deposition) method.
- ITO As a transparent conductive layer, ITO has the advantage that low resistance can be achieved compared with acid tin. However, when glass is used as the substrate, it is not necessary to use expensive indium. The cost is better. In addition, when silver is used as the metal layer, acid tin is also preferred for the advantage of suppressing the problem of yellowing due to the reaction between silver and Z glass when silver is formed on the glass substrate. (Metal layer)
- the electromagnetic wave shielding plate preferably has a surface resistance value of 1 ⁇ or less. More preferably, the surface resistance value is 0.1 ⁇ ′cm or less.
- the transparent conductive layer is formed thick in order to reduce the resistance value, the light transmittance decreases and the visibility of the display decreases, and a long vacuum process is required. There is a problem that remarkably decreases. Therefore, it is preferable to form a mesh or stripe metal layer on the substrate. By forming the metal layer in a mesh shape or a stripe shape, it is possible to transmit the mesh portion or stripe opening force light.
- the material of the metal layer it is preferable to use silver because the resistance value can be easily reduced.
- the metal layer may contain a metal such as nickel or aluminum.
- the silver content in the metal component is 50% by mass or more. When the silver content is less than 50%, the resistance value tends to increase.
- the line width of the mesh or stripe-shaped metal layer is 5 to 30 ⁇ m. If the line width force of the mesh or stripe is smaller than 5 ⁇ m, the pattern will be lost, and if the line width exceeds 30 m, the light transmittance will decrease.
- the thickness of the metal layer is preferably from 0.5 to 15 m, more preferably from 1 to 10 m. If it is thinner than 0.5 m, the resistance value of the metal layer increases and the electromagnetic wave shielding property is insufficient. On the other hand, if the metal layer is thicker than 15 m, the mesh and stripe formation process becomes complicated and the material cost increases. In addition, when the metal layer is thick, there is a problem that visibility is lowered due to reflection on the side of the pattern, and a transparent treatment process is required to prevent it.
- the PDP pixel pitch is preferably 1Z2 or less.
- a normal PDP has pixels of 0.7 to 1 mm square, it is preferable to form the mesh stripes with a pitch of 0.1 to 0.5 mm.
- Black layer Since the metal layer reflects light, there is a problem that the visibility of the display is lowered by the reflected light. Therefore, it is preferable to improve visibility by forming a black layer and suppressing reflection. Forming a black layer with the same stripe or mesh shape as the metal layer on top of the metal layer, that is, by forming the upper black layer, the reflection is suppressed, and the display visibility and electromagnetic wave shielding properties Can be achieved.
- the thickness of the black layer is influenced by the blackness of the black layer, but is preferably 0.5 to: LO / z m.
- the thickness of the black layer is preferably 0.5 m or more. In terms of material cost, the thickness of the black layer is preferably 10 ⁇ m or less.
- a black layer using the photosensitive soft magnetic paste of the present invention because the black layer itself has an electromagnetic wave shielding property, an electromagnetic wave shielding property is high, and an electromagnetic wave shielding plate can be formed.
- a method for producing a metal layer on a substrate a method of forming a metal layer by firing after forming a necessary pattern using a paste containing metal on the substrate can be exemplified.
- a pattern printing method such as offset printing or screen printing may be used.
- a preferred method is a photosensitive paste method.
- the photosensitive paste method is a method of forming a pattern by a photolithography method using a paste containing a photosensitive organic component and a metal powder.
- the photosensitive soft magnetic paste of the present invention is used to form a black layer by firing after forming a necessary pattern by a photolithography method.
- the method is preferably exemplified.
- the firing of the metal layer and the black layer can be performed at once.
- a photosensitive metal paste containing a metal powder and a photosensitive organic component is applied and dried to form a photosensitive metal paced coating film. Furthermore, the photosensitive of the present invention is further provided.
- the photosensitive soft magnetic paste is applied and dried to form a laminated coating film of a photosensitive metal paced coating film and a photosensitive soft magnetic paste coating film.
- the multilayer coating film is exposed to an actinic ray through a photomask corresponding to the mesh pattern and exposed to light, thereby forming a multilayer coating film in a mesh pattern. . Subsequently, when a glass substrate is used as the substrate, it is baked by heating to 400 to 700 ° C.
- the organic components in the multilayer coating film are burned off, and the inorganic powder adheres, forming a metal layer from the metal paced coating film and a black layer from the soft magnetic paced coating film.
- the firing temperature is less than 400 ° C.
- the organic matter in the metal layer and the black layer is not sufficiently reduced, so that the adhesion to the glass substrate is insufficient.
- the firing temperature exceeds 700 ° C, the glass substrate itself may be deformed.
- the residual amount of the organic matter in the metal layer and the black layer be 10% or less of the mass before firing, and further 5% or less. It is further preferable that The firing time may be adjusted so that the residual organic matter is reduced to the preferred range within the preferred temperature range.
- tempered glass is used as the glass substrate, it is necessary to set the firing conditions lower than the strain point of the glass so that the glass is not tempered. For this purpose, it is preferable to perform the firing at a temperature 30 ° C or more lower than the strain point of the glass, and further, the firing is performed at a temperature 50 ° C or more, particularly 100 ° C or more lower than the strain point of the glass. Is preferred.
- the glass substrate when ordinary glass is used as the glass substrate, a pattern of a photosensitive paste coating film is formed on the glass substrate, then fired at a temperature close to the soft point of the glass substrate, and then rapidly cooled.
- the glass substrate can be strengthened at the same time. Specifically, for example, after heating at 600 to 700 ° C. for about several tens of seconds to several tens of minutes, air is blown and rapidly cooled, thereby baking the photosensitive paste coating film and strengthening the glass substrate. Can be done simultaneously.
- the strengthening treatment conditions are appropriately determined depending on the required degree of strengthening, if the thickness of the glass substrate.
- an electromagnetic wave shielding plate in which a mesh-like metal layer and a black layer are formed on a glass substrate is obtained.
- An optical filter for display is created by providing an anti-reflection function and a transmittance control function to the electromagnetic wave shielding plate.
- a method of providing an antireflection function a low refractive index antireflection paint is applied to the processed substrate.
- a method of sticking a film having an antireflection function to the electromagnetic wave shielding plate can be passed through.
- optical filter with a rate control function can be created.
- an appropriate metal ion to the glass substrate itself, it is possible to impart near infrared absorption performance.
- an antifouling film or the like that prevents contaminants such as fingerprints from attaching to the surface.
- the optical filter thus obtained can be suitably used as a front filter for a display, for example, a front filter for a plasma display panel, etc.
- the metal layer and the black layer formed in a mesh shape were observed with a microscope, and the line width was measured and the shape was observed.
- the surface resistance was measured by the four-point needle method using the surface resistance measuring instrument “Loresda” manufactured by Mitsubishi Chemical Corporation, using the electromagnetic wave shielding plate obtained in each example.
- a square sample with a side of 100 mm was cut out from the electromagnetic wave shielding plate obtained in each example, and the electromagnetic wave shielding property was measured using an Anritsu EMI shield measuring device (MA8602B) compliant with the KEC (Kansai Electronics Industry Promotion Center) method. was measured.
- MA8602B Anritsu EMI shield measuring device
- the extinction coefficients of the photopolymerization initiator and sensitizer used for the photosensitive paste were determined by the following procedure.
- the absorbance in the wavelength region of 265 nm to 600 nm of the diluted solution of c b is measured in units of 0.5 nm using a Shimadzu UV-3101PC self-recording spectrophotometer (cell 10 mm).
- Absorption coefficient Absorbance Z (Molar concentration X d) (where d represents cell length)
- the particle size of the inorganic powder used in the photosensitive paste was measured by dispersing the sample lg in purified water with ultrasonic waves for 1.5 minutes using a microtrac particle size distribution analyzer HRA 9320-X100.
- the particle refractive index was changed depending on the type of inorganic powder, and the solvent refractive index was 1.33. The measurement was performed three times and the average value was obtained.
- a soda glass substrate manufactured by Nippon Sheet Glass Co., Ltd. having a size of 970 mm x 580 mm and a thickness of 3 mm, 3% by weight of glass powder, methylmethalate Z methacrylate copolymer (mass composition ratio 60Z40, mass average molecular weight 32000) 6 mass 0/0, dipentaerythritol hexa Atari rate 3 mass 0/0 to erythritol, 1 over Kishirufue hydroxy cyclohexane - ketone 1 wt 0/0, a g powder median particle diameter 2 m (Dowa Mining Co., Ltd.) 74 wt% , Organic solvent (diethylene glycol monobutyl ether Tellacetate) 13% by weight of photosensitive silver paste was applied to the entire surface using a Microtec screen printer and a 380 mesh screen plate, and 100 minutes at 100 ° C using a Tabai hot air dryer.
- Glass powders include acid bismuth (75% by mass), acid silicon (5% by mass), acid boron (10% by mass), acid zirconium (3% by mass), acid zinc ( A glass powder having a center particle size of 0.8 / ⁇ ⁇ and a maximum particle size of 7 m, obtained by pulverizing glass having a force of 3% by mass) and aluminum oxide (4% by mass) was used.
- the thickness of the photosensitive silver paste coating film after drying was 15 m.
- a photosensitive soft magnetic paste having the composition shown in Table 1 was applied over the entire surface of the photosensitive silver paste coating film using a Microtec screen printer and a 380 mesh screen. Then, it was dried at 100 ° C. for 30 minutes using a hot air dryer manufactured by Tabai. The thickness of the photosensitive soft magnetic paste coating film after drying was 13 m.
- the substrate thus obtained was irradiated with exposure light through a photomask having openings formed in a mesh shape with a line interval of 300 m and a line width of 20 m, and a photosensitive silver paced coating film and Photosensitive soft magnetic material The paste coating film was exposed simultaneously.
- the exposure machine used was a Dainippon Screen exposure machine (light source: 2kW ultra-high pressure mercury lamp).
- the photosensitive silver paced coating film and the photosensitive soft magnetic paste coating film are patterned in a mesh pattern by developing with a 0.5% 2-aminoethanol aqueous solution in a shower for 2 minutes. It was done. Thereafter, this glass substrate with a mesh pattern was fired at 700 ° C. for 5 minutes using a roller hearth firing furnace manufactured by Koyo Thermotech Co., Ltd., and then rapidly cooled by blowing air. By this treatment, the photosensitive silver base coating film and the photosensitive soft magnetic paste coating film are firmly adhered to the glass substrate as a metal layer and a black layer having a mesh pattern, and the base glass is It became tempered glass. In this way, an electromagnetic wave shielding plate was produced.
- Table 1 The materials used in Table 1 are as follows. In Table 1, the upper part is the material, and the lower part is the ratio (parts by mass).
- B Ni—Zn-based ferrite powder, trade name “BSN—714” (manufactured by Toda Kogyo Co., Ltd.), center particle size 2.7 m, maximum particle size 8. l ⁇ m
- G 2-Benzyl-2-dimethylamino 1- (4-morpholinophenyl) 1-butanone 1 (Molecular extinction coefficient at 365 nm wavelength: 7,800)
- H Bis (2, 4, 6-trimethylbenzoyl) mono-phosphine oxide (molecular extinction coefficient at a wavelength of 365 nm: 2, 300)
- Table 2 shows the results of using the photosensitive paste having the composition shown in Table 1.
- Examples 1 to 9 exposure was possible with sufficiently practical sensitivity, and the line width and shape of the metal layer and the black layer were good.
- Example 10 a large amount of exposure was required, and the shapes of the metal layer and the black layer were slightly poor, but pattern formation was possible.
- Examples 11 to 13 the metal layer and the black layer were slightly inferior in shape, but pattern formation was possible.
- Table 2 shows the evaluation results of the obtained electromagnetic wave shielding plate.
- a functional film manufactured by Sumitomo Osaka Cement Co., Ltd. having an antireflection function, a color correction function, and a neon cut function is bonded to the electromagnetic wave shield plate produced in Examples 1 to 12 and a front filter. It was created. The visibility was evaluated based on the haze feeling of the screen.
- the size 970 mm X 580 mm on a polyester film, formed have use intaglio offset printing method, a carbon black with a 1 mass 0/0 silver paste containing, pitch 300 ⁇ ⁇ , a mesh pattern having a line width of 20 m And heated to 150 ° C. Subsequently, a copper plating layer was formed on the mesh-like silver paste pattern by electrolytic plating so as to have a thickness of 3 ⁇ m. Thus, the electromagnetic wave shielding film which has a mesh-like pattern on the polyester film was created.
- the obtained electromagnetic wave shielding film was bonded to a glass substrate, and a functional film having an antireflection function, a color correction function, and a neon cut function (manufactured by Sumitomo Osaka Cement Co., Ltd.) was pasted to create a front filter.
- a functional film having an antireflection function, a color correction function, and a neon cut function manufactured by Sumitomo Osaka Cement Co., Ltd.
- a dry film resist was laminated.
- the dry film resist was exposed through a photomask in which openings were formed in a mesh shape with a pitch of 300 ⁇ m and a line width of 20 ⁇ m.
- an electromagnetic wave shielding film having a mesh pattern on the polyester film was prepared through each step of development, etching, and resist stripping.
- the obtained electromagnetic wave shielding film was bonded to a glass substrate, and a functional film (manufactured by Sumitomo Osaka Cement Co., Ltd.) having an antireflection function, a color correction function and a neon cut function was bonded to the front surface filter. It was created. When the visibility was evaluated by the haze feeling of the screen, the haze feeling was strong and the visibility was poor.
- An electromagnetic wave shielding plate was prepared in the same manner as in Example 1 except that the composition of the photosensitive soft magnetic paste was changed as shown in Table 1. After firing, the metal layer and the black layer were peeled off from the glass substrate.
- An electromagnetic wave shielding plate and a front filter were prepared in the same manner as in Example 1 except that the composition of the photosensitive soft magnetic paste was changed as shown in Table 1.
- the composition of the photosensitive soft magnetic paste was changed as shown in Table 1.
- the photosensitive paste of the present invention it is possible to provide a photosensitive paste capable of producing an electromagnetic wave shield plate with excellent visibility by a simple process.
- the photosensitive paste of the present invention is used not only for an electromagnetic wave shielding plate of a display but also for an electromagnetic wave shielding of a wireless communication device, a magnetic layer of a wiring board having a part of an inductor, etc. Can do.
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- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Materials For Photolithography (AREA)
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- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Gas-Filled Discharge Tubes (AREA)
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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US11/658,006 US7776507B2 (en) | 2004-07-22 | 2005-07-14 | Photosensitive paste and manufacturing method of member for display panel |
KR1020077001418A KR101190921B1 (ko) | 2004-07-22 | 2005-07-14 | 감광성 페이스트 및 디스플레이 패널용 부재의 제조 방법 |
JP2006529105A JP4760709B2 (ja) | 2004-07-22 | 2005-07-14 | 感光性ペーストおよびディスプレイパネル用部材の製造方法 |
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JP2004-214586 | 2004-07-22 | ||
JP2004214586 | 2004-07-22 |
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WO2006009051A1 true WO2006009051A1 (ja) | 2006-01-26 |
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PCT/JP2005/012983 WO2006009051A1 (ja) | 2004-07-22 | 2005-07-14 | 感光性ペーストおよびディスプレイパネル用部材の製造方法 |
Country Status (6)
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US (1) | US7776507B2 (ja) |
JP (1) | JP4760709B2 (ja) |
KR (1) | KR101190921B1 (ja) |
CN (1) | CN100573323C (ja) |
TW (1) | TWI368477B (ja) |
WO (1) | WO2006009051A1 (ja) |
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JP7202783B2 (ja) | 2018-03-28 | 2023-01-12 | 太陽インキ製造株式会社 | 感光性樹脂積層体、ドライフィルム、硬化物、電子部品、および、電子部品の製造方法 |
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Also Published As
Publication number | Publication date |
---|---|
TW200610484A (en) | 2006-03-16 |
CN1989454A (zh) | 2007-06-27 |
TWI368477B (en) | 2012-07-11 |
US20090035452A1 (en) | 2009-02-05 |
JP4760709B2 (ja) | 2011-08-31 |
KR101190921B1 (ko) | 2012-10-12 |
KR20070033439A (ko) | 2007-03-26 |
JPWO2006009051A1 (ja) | 2008-05-01 |
CN100573323C (zh) | 2009-12-23 |
US7776507B2 (en) | 2010-08-17 |
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