JP2000030531A - Formation of pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pattern formation method for easily forming an electrode pattern of a plasma display panel or the like at high precision. SOLUTION: A transfer layer 33 having at least an inorganic component containing conductive powder and glass frit, and further having an organic component containing a photosensitive resin composition removable at a baking process, is formed on a base film for use as a transfer sheet. In this case, the transfer layer 33 is transferred to a substrate and a photo mask M is laid for the transfer layer 33 under the formation of in-plane irregularities equal to or less than ±50 μm within the range of 50 to 500 μm. Furthermore, the transfer layer 33 is exposed to parallel beams via the photo mask M and then developed for patterning. Thereafter, the pattern is baked to form an electrode pattern.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a pattern forming method, and more particularly to a pattern forming method for forming an electrode pattern with high accuracy.

[0002]

2. Description of the Related Art In recent years, plasma display panels (P
It is required that the electrode pattern formation in DP) can be performed at a low manufacturing cost while maintaining a high level of layer thickness and pattern accuracy.

Conventionally, formation of an electrode pattern or the like in a PDP is performed by forming a film by a printing method such as screen printing or offset printing using a paste having desired characteristics.
It has been performed by a printing method of baking after drying or the like.

[0004]

However, the above-mentioned printing method is expected to simplify the process and reduce the manufacturing cost. However, in the screen printing method, the printing accuracy due to the elongation of the mesh material constituting the screen printing plate is reduced. There is a limit, and there is a problem that the formed pattern has meshes or blurs of the pattern, resulting in poor edge accuracy of the pattern. Further, in the offset printing method, as the number of printings increases, the pattern forming paste is not completely transferred to the substrate but remains on the blanket, and the layer thickness and the accuracy of the pattern are reduced. Therefore, it is necessary to replace the blanket at any time to prevent the blanket of the paste from remaining, and to maintain the accuracy of forming the electrode pattern. Therefore, there is a problem that the operation is extremely complicated.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to provide a pattern forming method for forming an electrode pattern of a plasma display panel or the like with high accuracy and ease.

[0006]

SUMMARY OF THE INVENTION In order to achieve the above object, the present invention comprises at least an inorganic component containing a conductive powder and a glass frit and an organic component containing a photosensitive resin composition that can be removed by firing. Using a transfer sheet provided with a transfer layer on a base film, the transfer layer is pressure-bonded on the substrate and superimposed, and then the base film is peeled off and the transfer layer is transferred onto the substrate, and the transfer layer 50-500μ
In the range of m, a photomask is provided with a gap having an in-plane variation of within ± 50 μm, the transfer layer is exposed to parallel light through the photomask, and then developed and patterned, and then baked. To form an electrode pattern.

Further, the present invention provides a transfer sheet provided on a base film having a transfer layer containing at least an inorganic component containing a conductive powder, a glass frit, and an organic component containing a photosensitive resin composition which can be removed by firing. Using, the transfer layer is pressed on the substrate and superimposed, and 50 to
A photomask is provided with a gap having an in-plane variation within ± 50 μm within a range of 500 μm, and the transfer layer is exposed to parallel light through the photomask. After transferring onto a substrate, developing and patterning, it was baked to form an electrode pattern.

In the present invention as described above, the gap provided between the transfer layer transferred onto the substrate and the photomask, or between the base film of the transfer sheet pressed onto the substrate and the photomask. Has a function of preventing contamination of the photomask and adhesion of dust, and since the light irradiated to the transfer layer through the photomask is parallel light, a high-precision which faithfully reproduces the opening pattern of the photomask. Can be performed on the transfer layer.

[0009]

Embodiments of the present invention will be described below with reference to the drawings. Description of Pattern Forming Method The pattern forming method of the present invention will be described with reference to an example of forming an electrode pattern of a plasma display panel (PDP).

First, before describing the pattern forming method of the present invention, an AC type PDP will be described.

FIG. 1 is a schematic structural view showing an AC type PDP, showing a state in which a front plate and a rear plate are separated.
In FIG. 1, a PDP 1 has a front plate 11 and a rear plate 21 arranged in parallel and opposed to each other.
A barrier 26 is formed on the front side of 1 so as to be erected,
The front plate 11 and the rear plate 21 are held at regular intervals by the barrier 26.

The front plate 11 has a front glass substrate 12, and on the back side of the front glass substrate 12, composite electrodes composed of a sustain electrode 13 which is a transparent electrode and a bus electrode 14 which is a metal electrode are formed in parallel with each other. A dielectric layer 15 is formed so as to cover this, and an MgO layer 16 is further formed thereon.
Are formed.

The back plate 21 includes a back glass substrate 22
The underlayer 2 is provided on the front side of the rear glass substrate 22.
3, address electrodes 24 are formed parallel to each other and located between the barriers 26 so as to be orthogonal to the composite electrode.
A dielectric layer 25 is formed so as to cover this, and a phosphor layer 27 is provided so as to cover the wall surface of the barrier 26 and the bottom surface of the cell.

In this AC type PDP, the front glass substrate 1
By applying a predetermined voltage from an AC power supply between the composite electrodes on the upper electrode 2 to form an electric field, discharge occurs in each cell as a display element defined by the front glass substrate 12, the rear glass substrate 22, and the barrier 26. Is performed. Then, the phosphor layer 27 is caused to emit light by the ultraviolet light generated by the discharge, and the light transmitted through the front glass substrate 12 is visually recognized by an observer.

In the AC type PDP shown in FIG. 1, the address electrodes 24 and the like are provided on the rear glass substrate 22 with the base layer 23 interposed therebetween, but the base layer 23 may not be formed. .

Next, the formation of the address electrodes 24 on the back plate 21 of the PDP according to the first embodiment of the pattern forming method of the present invention will be described.

FIG. 2 is a process chart for explaining the formation of an electrode pattern using the transfer sheet according to the present invention. still,
In this case, the transfer layer of the transfer sheet contains a negative photosensitive resin composition as a photosensitive resin composition that can be removed by baking.

In FIG. 2, first, the transfer layer 33 of the transfer sheet 31 for forming an electrode pattern is formed on the back glass substrate 22 provided with the base layer 23 (or directly on the back glass substrate 22 without providing the base layer 23). Side, the base film 32 is peeled off, and the transfer layer 33 is transferred (FIG. 2).
(A)). In this transfer step, when heating is necessary for transfer of the transfer layer 33, heating of the back glass substrate 22, heating with a pressure roll, or the like may be performed.

Next, a photomask M is provided with a gap between the transfer layer 33 and the transfer layer 33 is exposed through the photomask M (FIG. 2B). The gap between the photomask M and the transfer layer 33 is in the range of 50 to 500 μm, and the variation of the gap in the plane is within ± 50 μm. The gap between the photomask M and the transfer layer 33 is 50 μm
If it is less than 1, contamination of the photomask M is likely to occur,
If it exceeds 500 μm, the line width of the exposure pattern becomes large, and it becomes difficult to form a high-definition pattern. If the in-plane variation of the gap exceeds ± 50 μm, the line width of the exposed pattern varies, making it difficult to form the pattern with high accuracy.

In the present invention, parallel light is used for exposing the transfer layer 33. The light source of the parallel light can be appropriately selected from various conventionally known light sources.

Next, a pattern 33 'is formed on the underlayer 23 by developing the transfer layer 33 (FIG. 2).
(C)) Thereafter, baking is performed to remove the organic components of the pattern 33 ', thereby forming the address electrode pattern 24.
Is formed (FIG. 2D).

In the formation of such an address electrode pattern 24, as described above, the gap provided between the transfer layer 33 and the photomask M is within the range of 50 to 500 μm, and the in-plane variation is within ± 50 μm. In addition, since parallel light is used for exposure, high-precision exposure that faithfully reproduces the opening pattern of the photomask M can be performed on the transfer layer 33. Further, by setting the above gap, contamination due to the adhesion of the transfer layer 33 to the photomask M is prevented, and furthermore, dust is prevented from being adhered to the transfer layer 33. The pattern 24 can be formed.

Next, the formation of the address electrodes 24 on the back plate 21 of the PDP according to the second embodiment of the pattern forming method of the present invention will be described.

FIG. 3 is a process chart for explaining the formation of an electrode pattern using the transfer sheet according to the present invention. still,
In this case, the transfer layer of the transfer sheet contains a negative photosensitive resin composition as a photosensitive resin composition that can be removed by baking.

In FIG. 3, first, the transfer layer 33 of the transfer sheet 31 for forming an electrode pattern is formed on the back glass substrate 22 provided with the base layer 23 (or directly on the back glass substrate 22 without providing the base layer 23). Crimp the sides (Fig. 3
(A)). If heating is required in the pressing of the transfer layer 33, heating of the rear glass substrate 22, heating by a pressing roll, or the like may be performed.

Next, the base film 3 of the transfer sheet 31
A photomask M is arranged so as to provide a gap between the transfer layer 33 and the transfer layer 33 (FIG. 3B). The gap between the base film 32 and the photomask M is in the range of 50 to 500 μm, and
The variation of the gap in the plane is within ± 50 μm. If the gap between the base film 32 and the photomask M is less than 50 μm, contamination of the photomask M is likely to occur, and
If it exceeds 00 μm, the line width of the exposure pattern becomes large,
It becomes difficult to form a high-definition pattern. If the in-plane variation of the gap exceeds ± 50%, the line width of the exposure pattern varies, making it difficult to form the pattern with high accuracy.

In the present invention, parallel light is used for exposing the transfer layer 33. The light source of the parallel light can be appropriately selected from various conventionally known light sources.

Next, the base layer 32 is peeled off to transfer the exposed transfer layer 33, and then the transfer layer 33 is developed to form a pattern 33 'on the underlayer 23 (FIG. 3 ( C)). Thereafter, baking is performed to remove the organic components of the pattern 33 ', thereby forming the address electrode pattern 24 (FIG. 3D).

In the formation of the address electrode pattern 24, the gap provided between the base film 32 and the photomask M is within the range of 50 to 500 μm and the in-plane variation is within ± 50 μm as described above. In addition, since parallel light is used for exposure, high-precision exposure that faithfully reproduces the opening pattern of the photomask M can be performed on the transfer layer 33. Further, since the exposure is performed in a state where the base film is left without being peeled, the contamination due to the adhesion of the transfer layer 33 to the photomask M is prevented.
Thus, the address electrode pattern 24 can be formed with high precision without causing dust to adhere to the third electrode 3 and without causing a defect due to the dust. Description of Transfer Sheet Used in the Present Invention Next, the transfer sheet used in the pattern forming method of the present invention will be described.

FIG. 4 is a schematic sectional view showing an example of a transfer sheet that can be used in the present invention. In FIG. 4, a transfer sheet 31 is a transfer sheet for forming an electrode pattern including a base film 32, a transfer layer 33, and a protective film 34 provided on the transfer layer 33 so as to be peelable. The transfer layer 33 is provided releasably from the base film 32 and contains at least an inorganic component containing conductive powder and glass frit, and an organic component containing a photosensitive resin composition that can be removed by firing.

The transfer sheet 31 has a sheet shape.
Any of long shapes may be used, and in the case of a long shape, a roll shape wound around a core can be used. The core used is preferably a core formed of an ABS resin, a vinyl chloride resin, bakelite, or the like in order to prevent generation of dust and paper dust, and a paper tube impregnated with the resin.

Next, the structure of the transfer sheet 31 will be described. (Base Film) The base film 32 constituting the transfer sheet 31 is stable with respect to the ink composition when forming the transfer layer 33, has flexibility, and undergoes significant deformation due to tension or pressure. Use materials that do not occur. Further, when exposure is performed through the base film 32 as in the second embodiment of the pattern formation method described above, a material having transparency to light used for exposure is used.

As a material to be used, first, a resin film can be used. Specific examples of the resin film include a polyethylene film, an ethylene-vinyl acetate copolymer film, an ethylene-vinyl alcohol copolymer film, a polypropylene film, a polystyrene film, a polymethacrylate film, a polyvinyl chloride film, a polyvinyl alcohol film, and a polyvinyl film. Butyral film, nylon film, polyetherketone film, polyphenylene sulfide film, polysulfone film, polyethersulfone film, polytetrafluoroethylene-perfluoroalkylvinyl ether film, polyvinyl fluoride film, tetrafluoroethylene-ethylene film, tetrafluoroethylene -Hexafluoropropylene film, polychlorotrifluoroethylene Film, polyvinylidene fluoride film, polyethylene terephthalate film, 1,4-polycyclohexylene dimethylene terephthalate film, polyethylene naphthalate film, polyester film, cellulose triacetate film, polycarbonate film, polyurethane film, polyimide film, polyetherimide Films, films in which fillers are blended with these resin materials, and films using these resin materials
Axial stretching or biaxial stretching, a biaxially stretched film using these resin materials to increase the stretching ratio in the width direction from the flow direction, and using these resin materials to increase the stretching ratio in the flow direction from the width direction Biaxially stretched films, composites formed by laminating the same or different films of these films, and composites formed by co-extruding the same or different resins selected from the raw resin used for these films Films and the like can be mentioned. In addition, those obtained by treating the above resin film,
For example, silicon-treated polyethylene terephthalate, corona-treated polyethylene terephthalate, silicon-treated polypropylene, corona-treated polypropylene, or the like may be used.

When the base film 32 does not require light transmittance, a metal foil or a metal steel strip can be used. Specific examples of such metal foil and metal steel strip include copper foil, copper steel strip, aluminum foil, aluminum steel strip, and SU.
S430, SUS301, SUS304, SUS420
Examples include stainless steel strips such as J2 and SUS631, beryllium steel strips, and the like. Further, the above-mentioned metal foil or metal steel strip bonded to the above-mentioned resin film may be used.

When the exposure is performed through the base film 32 as in the second embodiment of the pattern forming method described above, highly accurate exposure is performed by absorbing the scattered light generated by the reflection on the transfer layer. For the base film 32
May contain an ultraviolet absorber or a coloring agent. As the ultraviolet absorber, a conventionally known ultraviolet absorber can be used, and examples thereof include a hydroxybenzophenone-based compound, a hydroxynaphthophenone-based compound, a phenylsalicylate-based compound, and a benzotriazole-based compound. As the colorant, conventionally known black pigments and black dyes can be used, and specifically, one or more of carbon black, aniline black, iron black and the like can be used. Base film 32
Can be set in the range of 5 to 50% by weight.

The thickness of the base film 32 as described above can be set in the range of 4 to 400 μm, preferably 10 to 150 μm. (Transfer Layer) The transfer layer 33 is a method in which an ink composition containing at least an inorganic component containing conductive powder and glass frit and an organic component containing a photosensitive resin composition that can be removed by baking is directly applied on the base film 32. It can be formed by applying and drying by a known application means such as a gravure coating method, a gravure reverse coating method, a reverse roll coating method, a slide die coating method, a slit die coating method, a comma coating method, and a slit reverse coating method. Inorganic component As the above glass frit, for example, a softening temperature of 3
50 to 650 ° C., and the coefficient of thermal expansion α ₃₀₀ is 60 × 10
^A glass frit having a temperature of ^{−7 to} 100 × 10 ⁻⁷ / ° C. can be used. Glass frit softening temperature 650 ℃
If the temperature exceeds the above, it is necessary to increase the firing temperature. For example, if the heat resistance of the pattern formation target is low, thermal deformation occurs in the firing step, which is not preferable. On the other hand, if the softening temperature of the glass frit is lower than 350 ° C., the glass frit is fused before the organic components are completely decomposed, volatilized and removed by baking, which is not preferable because voids are easily formed. Furthermore, the coefficient of thermal expansion α ₃₀₀ of the glass frit is 60 × 10
^{If it is} less than ^-7 / ° C or more than 100 × ^10-7 / ° C, the difference from the coefficient of thermal expansion of the pattern-formed body may become too large, causing distortion and the like, which is not preferable. The average particle size of such a glass frit is 0.1 to
A range of 10 μm is preferred. As such a glass frit, for example, a glass frit containing Bi ₂ O ₃ , ZnO or PbO as a main component can be used.

The transfer layer 33 is formed by adding an inorganic powder such as aluminum oxide, boron oxide, silica, titanium oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, or calcium carbonate as an inorganic component to 100 parts by weight of glass frit. On the other hand, it can be contained in a range of 30 parts by weight or less. Such an inorganic powder preferably has an average particle size in the range of 0.1 to 10 μm, and serves as an aggregate to prevent pattern casting during firing and to control the reflectance and the dielectric constant. Things.

In order to reduce the reflection of light in the transfer layer 33 at the time of exposure or to reduce the reflection of external light of the formed pattern, a fire-resistant black or white pigment is used as an inorganic component in the transfer layer 33. Can be contained. As the fire-resistant black pigment, Co-Cr-Fe, Co-Mn-F
e, Co-Fe-Mn-Al, Co-Ni-Cr-F
e, Co-Ni-Mn-Cr-Fe, Co-Ni-Al
-Cr-Fe, Co-Mn-Al-Cr-Fe-Si and the like. Examples of the fire-resistant white pigment include titanium oxide, aluminum oxide, silica, and calcium carbonate.

As the conductive powder to be contained in the transfer layer 33, one or more of Au powder, Ag powder, Cu powder, Ni powder, Al powder, Ag-Pd powder and the like can be used. Can be used. The shape of this conductive powder is spherical, plate-like,
It may be in various shapes such as a lump, a cone, a rod, etc., but a spherical conductive powder having no cohesive property and good dispersibility is preferable, and the average particle diameter is preferably in a range of 0.05 to 10 μm. The content ratio of the conductive powder and the above glass frit in the transfer layer 33 is such that the glass frit is 2 to 20 parts by weight, preferably 2 to 15 parts by weight with respect to 100 parts by weight of the conductive powder.
It can be in the range of parts by weight. The photosensitive resin composition that can be removed by baking contained in the organic component transfer layer 33 contains at least a polymer, a monomer, and an initiator, and is volatilized and decomposed by baking to form a carbide in the film after baking. It will not be left.

As the polymer, methyl acrylate,
Methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-
Butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, te
rt-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, styrene, α
-Methylstyrene, one or more of N-vinyl-2-pyrrolidone, acrylic acid, methacrylic acid, dimer of acrylic acid (for example, M-5600 manufactured by Toagosei Co., Ltd.), 2-methacryloyloxyethyl succinate 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl phthalate, 2-acryloyloxyethyl phthalate,
2-methacryloyloxyethyl hexahydrophthalate, 2-acryloyloxyethyl hexahydrophthalate, itaconic acid, crotonic acid, maleic acid, fumaric acid,
Examples thereof include vinyl acetic acid, polymers or copolymers of one or more of these acid anhydrides, and carboxyl group-containing cellulose derivatives.

Examples of the copolymer include a polymer obtained by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the above copolymer, but the present invention is not limited thereto.

The molecular weight of the above polymer is from 5,000 to
300,000, preferably 30,000 to 150,0
00 range. Further, other polymers such as a methacrylate polymer, a polyvinyl alcohol derivative, an N-methyl-2-pyrrolidone polymer, a cellulose derivative, and a styrene polymer can be mixed with the above-mentioned polymer.

As the reactive monomer constituting the photosensitive resin composition, a compound having at least one polymerizable carbon-carbon unsaturated bond can be used. Specifically, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl Acrylate, isobonyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate,
Phenoxyethyl acrylate, stearyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,3
-Propanediol acrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate,
Tripropylene glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetra Acrylate, propylene oxide-modified pentaerythritol triacrylate, propylene oxide-modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanetriol triacrylate , 2,2,4-trimethyl-1,3
-Pentanediol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate,
Pentaerythritol hexaacrylate, and the above acrylate changed to methacrylate, γ-
Methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, and the like. The reactive monomers described above can be used as one kind or a mixture of two or more kinds, or as a mixture with other compounds.

Examples of the photopolymerization initiator constituting the photosensitive resin composition include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone,
α-amino acetophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenylketone, dibenzylketone, fluorenone, 2,2-diethoxyacetophonone, 2,2-dimethoxy-2-phenylacetophenone, -Hydroxy-2-methylpropiophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-
Chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethylketal, benzylmethoxyethylacetal, benzoinmethylether, benzoinbutylether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloranthraquinone, anthrone, benzantrone , Dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6
-Bis (p-azidobenzylidene) cyclohexane,
2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadione-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxy Carbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Michler's ketone, 2-methyl-
[4- (methylthio) phenyl] -2-morpholino-
1-propane, 2-benzyl-2-dimethylamino-1
-(4-morpholinophenyl) -butanone-1, naphthalenesulfonyl chloride, quinoline sulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine,
Examples include a combination of a photoreducing dye such as camphorquinone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide, eosin, and methylene blue with a reducing agent such as ascorbic acid and triethanolamine. One or more agents can be used.

The transfer layer 33 of such a photosensitive resin composition
Can be set in the range of 3 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the above-mentioned inorganic component. When the content of the photosensitive resin composition is 3
When the amount is less than the weight part, the shape retention of the transfer layer 33 is low,
In particular, there is a problem in the storability and handleability in a roll state, and when cutting (slitting) the transfer sheet 31 into a desired shape, inorganic components are generated as dust, which may hinder pattern formation. is there. On the other hand, if the content of the photosensitive resin composition exceeds 50 parts by weight, the organic components cannot be completely removed by firing, and carbides remain in the film after firing, which is not preferable because the quality deteriorates.

Further, in the above-mentioned photosensitive resin composition, a sensitizer, a polymerization terminator, a chain transfer agent, a leveling agent, a dispersant, a transferability-imparting agent, a stabilizer, a defoaming agent, A tackifier, a suspending agent, a release agent and the like can be contained as required.

The transferability-imparting agent is added for the purpose of improving the transferability and the fluidity of the ink composition. Examples thereof include dimethyl phthalate, dibutyl phthalate and di-n.
Normal alkyl phthalates such as octyl phthalate, phthalic acid esters such as di-2-ethylhexyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl glycolate and butyl phthalyl butyl glycolate; tri-2 -Ethylhexyl trimellitate, tri-
trimellitate such as n-alkyl trimellitate, triisononyl trimellitate, triisodecyl trimellitate, dimethyl adipate, dibutyl adipate, di-2-ethylhexyl adipate, diisodecyl adipate, dibutyl diglycol adipate, di- 2
-Ethylhexyl acetate, dimethyl sebacate, dibutyl sebacate, di-2-ethylhexyl sebacate, di-2-ethylhexyl malate, acetyl-tri- (2-ethylhexyl) citrate, acetyl-tri-n-butyl citrate, Aliphatic dibasic acid esters such as acetyl tributyl citrate, polyethylene glycol benzoate, triethylene glycol di- (2
-Ethylhexoate), glycol derivatives such as polyglycol ether, glycerin derivatives such as glycerol triacetate and glycerol diacetyl monolaurate, polyesters composed of sebacic acid, adipic acid, azelaic acid, phthalic acid, etc., having a molecular weight of 300 to 3,000. Low molecular weight polyether, the same low molecular weight poly-α-styrene, the same low molecular weight polystyrene, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate,
Orthophosphates such as tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xyenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, ricinoleates such as methyl acetyl ricinoleate, poly-1,3
-Polyester / epoxidized esters such as butanediol adipate and epoxidized soybean oil; and acetates such as glycerin triacetate and 2-ethylhexyl acetate.

The dispersant and the anti-settling agent are intended to improve the dispersibility and anti-settling property of the inorganic powder, and include, for example, a phosphate ester type, a silicone type, a castor oil ester type and various types. Surfactants and the like, examples of the antifoaming agent include silicone-based, acrylic-based, various surfactants and the like, and examples of the release agent include silicone-based, fluorine oil-based, paraffin-based, and fatty acid-based , Fatty acid ester type, castor oil type, wax type, compound type and the like, and as the leveling agent, for example, fluorine type, silicone type, various surfactants and the like,
Each can be added in an appropriate amount.

Examples of the solvent used together with the photosensitive resin composition for forming the transfer layer 33 include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol, α- and β-. Terpene such as terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone and 4-heptanone, and aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene , Cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene Glycol ethers such as ethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate,
Ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-hexyl acetate
Acetates such as ethoxyethyl acetate and 3-methoxybutyl acetate, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, ethyl 3-ethoxypropionate, methyl benzoate, N, N-dimethylacetamide, N, N-dimethylformamide and the like Is mentioned. (Protective Film) The protective film 34 can be made of a material that is flexible and does not significantly deform under tension or pressure. Specifically, polyethylene film, ethylene-vinyl acetate copolymer film, ethylene-vinyl alcohol copolymer film, polypropylene film,
Polystyrene film, polymethacrylic acid film, polyvinyl chloride film, polyvinyl alcohol film, polyvinyl butyral film, nylon film, polyetheretherketone film, polysulfone film, polyethersulfone film, polytetrafluoroethylene-perfluoroalkylvinylether film, Polyvinyl fluoride film,
Tetrafluoroethylene-ethylene film, tetrafluoroethylene-hexafluoropropylene film,
Polychlorotrifluoroethylene film, polyvinylidene fluoride film, polyethylene terephthalate film, polyethylene naphthalate film, polyester film, cellulose triacetate film, polycarbonate film, polyurethane film, polyimide film, polyetherimide film, filler for these resin materials , A film obtained by uniaxially or biaxially stretching a film using these resin materials, a biaxially stretched film obtained by using these resin materials to increase the draw ratio in the width direction from the flow direction, and these resins Biaxially stretched film having a higher stretching ratio in the flow direction than in the width direction using a material, a film obtained by laminating the same or different films among these films, and used for these films It can be mentioned composite films created by co-extruding the same or different resin selected from the fee resin. Among these films, it is particularly preferable to use a biaxially stretched polyester film. Further, those obtained by treating the above resin film, for example, silicon-treated polyethylene terephthalate, corona-treated polyethylene terephthalate, melamine-treated polyethylene terephthalate, corona-treated polyethylene, corona-treated polypropylene, silicon-treated polypropylene, and the like may be used.

The thickness of the protective film 34 as described above is
It can be set in the range of 4 to 400 μm, preferably 6 to 150 μm.

When the above-described transfer sheet 31 is used in the pattern forming method of the present invention, an electrode pattern can be formed by the same operation as in FIGS. 2 and 3 after the protective film 34 is peeled off.

The transfer sheet used in the pattern forming method of the present invention may not have a protective film on the transfer layer.

[0053]

Next, the present invention will be described in more detail with reference to examples. Example 1 First, a photosensitive resin composition having the following composition was prepared as an ink composition.

Composition of photosensitive resin composition: silver powder (spherical, average particle size: 1 μm): 96 parts by weight; glass frit: 4 parts by weight (main components: Bi ₂ O ₃ , SiO ₂ , B ₂ O ₃ (none) N-butyl methacrylate / 2-hydroxypropyl methacrylate / methacrylic acid copolymer (glycidyl methacrylate addition) (molecular weight = 80,000, acid value = 110 mg KOH / g) 13 parts by weight pentaerythritol Tri / tetraacrylate 11 parts by weight Photopolymerization initiator (Irgacure 369 manufactured by Ciba Geigy) 1 part by weight 3-methoxybutyl acetate 20 parts by weight Next, a polyethylene terephthalate film (T by Toray Industries, Inc.) was used as a base film. -60), and the above ink composition was sprayed on the base film. Coating and drying (100 ° C., 2 minutes) by coating to a thickness 17
A transfer layer having a thickness of μm was formed.

Next, a silicon-treated polyethylene terephthalate film (SP-PET-03-25-C manufactured by Tosello Co., Ltd.) was laminated on the transfer layer as a protective film to form an electrode pattern as shown in FIG. Transfer sheet A was prepared.

Further, a photosensitive resin composition having the following composition not containing silver powder as a conductive powder was prepared, and using this, a transfer sheet B was prepared in the same manner as above.

Composition of photosensitive resin composition : Glass frit: 58 parts by weight (main component: Bi ₂ O ₃ , SiO ₂ , B ₂ O ₃ (non-alkali), softening point = 500 ° C.) n-butyl methacrylate / 2 -Hydroxypropyl methacrylate / methacrylic acid copolymer (glycidyl methacrylate addition) (molecular weight = 80,000, acid value = 110 mgKOH / g) ... 13 parts by weight-Pentaerythritol tri / tetraacrylate ... 11 parts by weight-Photopolymerization initiator (Ciba-geigi) Irgacure 369) 1 part by weight 3-methoxybutyl acetate 20 parts by weight Next, each of the transfer sheets was slit into a predetermined width, the protective film was peeled off, and the glass substrate was heated to 60 ° C. The base film was peeled off by pressing with a hot roll at 50 ° C., and the transfer layer was transferred to a glass substrate.

Then, after cooling to room temperature, irradiation with ultraviolet collimated light or ultraviolet scattered light (light source: ultra-high pressure mercury lamp) is performed (400 mJ) through a negative pattern mask (opening line width 150 μm) of the electrodes of the plasma display panel.
/ Cm ² ) to expose the transfer layer. The used transfer sheet, the gap between the transfer layer and the negative pattern mask at the time of exposure and the variation in the gap in the mask surface, and the used ultraviolet light were set as shown in Table 1 below.

Thereafter, the transfer layer was developed using a 0.5% aqueous sodium carbonate solution to obtain a predetermined pattern. Next, the glass substrate was fired at 600 ° C. to form patterns (samples 1 to 12). The line width of each formed pattern was measured and is shown in Table 1 below.

[0060]

[Table 1] As shown in Table 1, the transfer sheet A for forming an electrode pattern was used, and the gap provided between the transfer layer and the negative pattern mask was in the range of 50 to 500 μm, and the in-plane variation was within ± 50 μm. And, the electrode pattern (sample 1 to sample 4) formed using ultraviolet collimated light for exposure is
It was confirmed that the line width had high accuracy.

On the other hand, the electrode pattern (sample 5) formed with the gap between the transfer layer and the negative pattern mask being 30 μm has a high line width, but the transfer layer material adheres to the negative pattern mask. Contamination has occurred.

The electrode pattern (sample 6) formed with a gap between the transfer layer and the negative pattern mask of 600 μm and the electrode pattern (sample 8) formed using ultraviolet scattered light for exposure are both line widths. And the accuracy was low. Further, the electrode pattern (sample 7) formed under the condition that the variation in the gap between the transfer layer and the negative pattern mask exceeded ± 50 μm had large variation in line width and low precision.

On the other hand, using a transfer sheet B in which the transfer layer does not contain conductive powder (silver powder), the electrode pattern sample 2,
The patterns (samples 9 to 11) formed under the same conditions as 6, 7, and 8 were all as accurate as the above-mentioned electrode patterns (samples 1 to 4). For this reason, in the transfer layer containing the conductive powder, the irradiation light is easily reflected and scattered, and it is difficult to perform high-precision pattern exposure. It was confirmed that particularly excellent effects were exhibited in pattern formation using a transfer sheet provided with a transfer layer containing. Example 2 First, a photosensitive resin composition having the following composition was prepared as an ink composition.

Composition of photosensitive resin composition: silver powder (spherical, average particle size: 1 μm): 96 parts by weight; glass frit: 4 parts by weight (main components: Bi ₂ O ₃ , SiO ₂ , B ₂ O ₃ (none) N-butyl methacrylate / 2-hydroxypropyl methacrylate / methacrylic acid copolymer (glycidyl methacrylate addition) (molecular weight = 80,000, acid value = 110 mg KOH / g) 13 parts by weight pentaerythritol Tri / tetraacrylate 11 parts by weight Photopolymerization initiator (Irgacure 369 manufactured by Ciba Geigy) 1 part by weight 3-methoxybutyl acetate 24 parts by weight Ultraviolet absorber 12 parts by weight Next, the above ink composition And transfer for forming an electrode pattern as shown in FIG. 4 in the same manner as in the transfer sheet A of Example 1. It was produced over door.

Next, the transfer sheet was slit into a predetermined width, the protective film was peeled off, and the transfer sheet was pressed on a glass substrate heated to 60 ° C. with a hot roll at 50 ° C.

Then, after cooling to room temperature, irradiation with ultraviolet collimated light or ultraviolet scattered light (light source: ultrahigh pressure mercury lamp) is performed through a negative pattern mask (opening line width 150 μm) of the electrodes of the plasma display panel (200 mJ).
/ Cm ² ) to expose the transfer layer. Variations in the gap between the base film and the negative pattern mask and the gap in the mask surface during exposure, and the used ultraviolet light were set as shown in Table 2 below.

Next, the base layer was peeled off, and the transfer layer was transferred to a glass substrate. Thereafter, the transfer layer was developed using a 0.5% aqueous sodium carbonate solution to obtain a predetermined pattern. Next, the glass substrate was fired at 600 ° C. to form electrode patterns (samples 1 to 7). The line width of each formed pattern was measured and is shown in Table 2 below.

[0068]

[Table 2] As shown in Table 2, the gap provided between the base film and the negative pattern mask has an in-plane variation within ± 50 μm within a range of 50 to 500 μm, and uses ultraviolet parallel light for exposure. It was confirmed that the formed electrode patterns (samples 1 to 4) had high line widths and high accuracy.

On the other hand, the electrode pattern (Sample 5) formed with the gap between the base film and the negative pattern mask being 600 μm and the electrode pattern (Sample 7) formed by using ultraviolet scattered light for exposure are both shown. The line width is also thick and the accuracy is low, and the variation in the gap between the base film and the negative pattern mask is ± 5.
Electrode pattern formed under conditions exceeding 0 μm (Sample 6)
Has large line width variations and low accuracy.

[0070]

As described above in detail, according to the present invention, a gap provided between a transfer layer transferred on a substrate and a photomask, or a base film of a transfer sheet pressed on a substrate. The gap provided between the photomask and the photomask is in the range of 50 to 500 μm, the in-plane variation of the gap is within ± 50 μm, and parallel light is used for exposure. The exposure can be performed with high accuracy by faithfully reproducing the transfer layer, and the appropriate gap setting can prevent contamination of the photomask and adhesion of dust. A fine electrode pattern can be formed with high accuracy.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram illustrating an example of a plasma display panel.

FIG. 2 is a process chart for explaining an example of forming an electrode pattern by the pattern forming method of the present invention.

FIG. 3 is a process chart for explaining another example of forming an electrode pattern by the pattern forming method of the present invention.

FIG. 4 is a schematic sectional view showing an example of a transfer sheet that can be used in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Plasma display panel 11 ... Front plate 21 ... Back plate 24 ... Address electrode pattern 31 ... Transfer sheet 32 ... Base film 33 ... Transfer layer 34 ... Protective film M ... Photomask

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshi Kagami 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo Dai Nippon Printing Co., Ltd. F-term (reference) 5C027 AA01 5C040 FA01 GA03 GB14 GC18 GC19 JA15 JA19 JA21 KA01 KA09 KA16 KB03 KB17 KB24 MA22 MA24 5G301 DA03 DA36 DA37 DA38 DA42 DD01

Claims (2)

[Claims] 1. A transfer sheet comprising a base film having a transfer layer containing at least a conductive powder, an inorganic component containing a glass frit, and an organic component containing a photosensitive resin composition that can be removed by firing. The transfer layer is pressed onto the substrate and superimposed, then the base film is peeled off and the transfer layer is transferred onto the substrate, and a gap having an in-plane variation within ± 50 μm within a range of 50 to 500 μm with respect to the transfer layer. A pattern formation characterized by providing a photomask, exposing the transfer layer with parallel light through the photomask, developing and patterning, and then firing to form an electrode pattern Method. 2. A transfer sheet comprising a base film having a transfer layer containing at least an inorganic component containing a conductive powder and a glass frit and an organic component containing a photosensitive resin composition that can be removed by firing. A transfer layer is pressed on a substrate and superimposed, and a photomask is provided with a gap of ± 50 μm within a range of 50 to 500 μm in a plane within a range of 50 to 500 μm, and a parallel light is transmitted through the photomask. And exposing the transfer layer to a substrate, peeling the base film, transferring the transfer layer onto a substrate, developing and patterning, and baking to form an electrode pattern.