JPH10148950A - Pattern formation method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for formation of patterns capable of forming the high-fineness patterns of electrodes, resistors, dielectric substances, etc., and forming the high-accuracy thick film patterns of barriers, etc. SOLUTION: A composite film 11 having at least a photosensitive resin layer 14 adjacent to a release film 13 is formed between a transfer base material sheet 12 and the release film 13 in a first stage. This photosensitive resin layer 14 is exposed via a prescribed photomask M in a second stage. The release film 13 is peeled, by which the photosensitive resin layer 14 is removed and exposed together with the release film 13 in the prescribed patterns in a third stag. A molding 1 to be patterned is press bonded to the photosensitive resin layer 14 remaining in the prescribed patterns on the composite sheet 11 and is backed after the release of the transfer base material 12, by which the patterns 4 are formed in a fourth stage.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a pattern, and more particularly, to a high-precision pattern of an electrode or a resistor in a manufacturing process of an image display device, a thermal head, an integrated circuit or the like, and a high-precision such as a barrier. The present invention relates to a pattern forming method for forming a thick film pattern.

[0002]

2. Description of the Related Art In recent years, fine patterns such as electrodes, resistors, and dielectrics have been formed in electronic devices such as integrated circuits and image display devices, or plasma display panels (PDs).
The formation of the barrier in P) is required to be able to be performed with higher accuracy and at a low manufacturing cost.

Conventionally, as a method of forming a pattern of an electrode or the like as described above, a method of etching a conductive thin film or the like formed by vapor deposition, sputtering, plating, printing, or the like by photolithography, forming a pattern having desired characteristics Printing method in which a predetermined pattern is formed by a printing method such as screen printing or offset printing using a paste for drying, and then dried and fired to form a pattern.

On the other hand, the barrier in the above PDP is cut perpendicularly to the glass substrate and is narrow and sufficiently high in order to make the display discharge space as large as possible and to emit light with high luminance. Is required. In particular, in a high-definition PDP, for example, a barrier having a high aspect ratio such that the thickness is about 100 μm for a width of 30 to 50 μm is required.

[0005]

However, in the pattern formation of electrodes and the like by the above-mentioned etching method, it is possible to form a pattern with high precision, but there is a problem that the manufacturing cost is increased due to the etching step. there were. Further, when electrodes and the like are formed on a large-area substrate such as a large-sized image display device, a large number of large-scale thin film forming devices, exposure devices, and etching devices are required, and this also increases the manufacturing cost. was there.

[0006] On the other hand, the printing method has no etching process, and the process is simpler than the above-mentioned etching method.
The production cost is expected to be reduced, but the screen printing method has a limitation in printing accuracy due to the elongation of the mesh material constituting the screen printing plate. There is a problem that the edge accuracy of the pattern is low. Also, in the offset printing method, as the number of printings increases, the pattern forming paste is not completely transferred to the substrate and remains on the blanket, and the pattern accuracy is reduced. However, there is a problem that the operation is complicated.

On the other hand, as a method of forming a thick film pattern having a high aspect ratio such as a barrier of a PDP, a barrier having a predetermined pattern is conventionally formed by a screen printing method. In the screen printing method, since the limit of the film thickness that can be formed by one printing is several tens μm, it is necessary to repeat printing and drying many times, generally ten times or more.
However, generally, the coating film formed by the screen printing method has a convex shape in which the peripheral portion is lowered, and when performing multiple overprinting as described above, dripping of the coating liquid in the pattern peripheral portion is accumulated. There is a problem that the bottom has a widened cross-sectional shape.

In order to solve this problem, a resist pattern is formed on the barrier forming layer by photolithography, and the barrier forming layer exposed at the opening of the resist pattern is removed to form a barrier. ing. However, since there are a wet development step and a washing step involved in the formation of the resist pattern, there is a problem that the operation is complicated, a material loss occurs, and a waste liquid treatment is required.

The present invention has been made in view of the above-described circumstances, and enables formation of high-definition patterns such as electrodes, resistors, and dielectrics, and formation of high-precision thick-film patterns such as barriers. It is an object to provide a simple pattern forming method.

[0010]

In order to achieve the above object, a first invention of a pattern forming method is to provide a photosensitive resin layer between a transfer base sheet and a release film adjacent to the release film. A first step of forming a composite sheet comprising at least: a second step of exposing the photosensitive resin layer through a predetermined photomask; and peeling the release film, whereby the photosensitive film is exposed together with the release film. A third step of removing and developing the conductive resin layer in a predetermined pattern, and pressing the pattern-formed body on the photosensitive resin layer remaining in the composite sheet in a predetermined pattern, and peeling the transfer base sheet. And a fourth step of forming a pattern by baking later.

A second invention of a pattern forming method includes a first step of laminating at least a photosensitive resin layer and a pattern forming layer on a transfer base sheet to form a composite sheet; A second step of exposing the photosensitive resin layer through a predetermined photomask on the pattern forming body so that the formation layer side faces, and peeling the transfer base sheet, thereby obtaining the transfer base sheet. And a third step of removing and developing the photosensitive resin layer in a predetermined pattern and performing a sandblasting process on the pattern formation layer using the photosensitive resin layer remaining in the predetermined pattern on the pattern formation layer as a mask. And baking to form a pattern.

[0013] A third invention of a pattern forming method is that a first photosensitive resin layer adjacent to the transfer base sheet and the first photosensitive resin layer are laminated between the transfer base sheet and the release film. A first step of forming a composite sheet including at least a patterned patterning layer and a second photosensitive resin layer adjacent to the release film, and the second photosensitive layer from the release film side via a predetermined photomask. A second step of exposing the photosensitive resin layer, a third step of removing the second photosensitive resin layer together with the release film in a predetermined pattern by peeling off the release film, and developing the composite sheet, A pattern forming body is pressed against the second photosensitive resin layer remaining in a predetermined pattern, and the first photosensitive resin layer is exposed from the transfer base material sheet side through a predetermined photomask. A step, by peeling off the transfer substrate sheet, the first with the transfer substrate sheet 1
A fifth step of removing and developing the photosensitive resin layer in a predetermined pattern, and subjecting the pattern formation layer to sandblasting using the first photosensitive resin layer remaining in the predetermined pattern on the pattern formation layer as a mask. And a sixth step of firing and forming a pattern.

According to the present invention as described above, the photosensitive resin layer of the composite sheet is exposed to light and the release film is peeled off to develop the photosensitive resin layer, or the photosensitive resin layer of the composite sheet overlaid on the pattern-formed body is exposed to light. The development is performed by peeling off the transfer base material sheet, or after the exposure and peeling development of the second photosensitive resin layer in the state of the composite sheet, the first photosensitive layer of the composite sheet superimposed on the pattern forming body is formed. The conductive resin layer is exposed and development is performed by peeling off the transfer base material sheet. After a desired pattern is formed by such dry peeling development, necessary sandblasting treatment is performed, and then the baking is performed so that the pattern layer is patterned. Formed on the compact.

[0014]

Embodiments of the present invention will be described below with reference to the drawings. The first invention (First Embodiment) FIG. 1 of the pattern forming method is a process diagram for explaining an embodiment of a pattern forming method of the first aspect of the invention.

(1) In FIG. 1, first, as a first step, a composite sheet 11 having a photosensitive resin layer 14 provided between a transfer base sheet 12 and a release film 13 is formed (FIG. 1 (A)). )). In the illustrated example, only the photosensitive resin layer 14 is provided between the transfer base sheet 12 and the release film 13, but another layer is transferred so that the photosensitive resin layer 14 is adjacent to the release film 13. It may be provided between the base sheet 12 and the release film 13.

The photosensitive resin layer 14 is formed on the transfer base sheet 12 by a known method such as direct gravure coating, gravure reverse coating, reverse roll coating, slide die coating, slit die coating, and comma coating. Can be formed by applying and drying the photosensitive resin composition by the application means described above, and overlaying and pressing the release film 13 on the applied film. Alternatively, the photosensitive resin composition may be applied on the release film 13 and dried, and the transfer base sheet 12 may be overlaid on the applied film and pressed. Further, the film prepared from the photosensitive resin composition is transferred to the transfer base sheet 12.
Alternatively, the photosensitive resin layer 14 may be formed by laminating on the release film 13.

The pressure bonding at the time of forming the composite sheet 11 may be heat pressing, in which case the heating temperature can be appropriately set according to the thermal properties of the photosensitive resin layer 14.

The photosensitive resin composition for forming the above-mentioned photosensitive resin layer 14 may be added to a known photosensitive resin composition in consideration of characteristics, actions, and the like required for a pattern to be formed. Those containing an appropriate agent can be used. As the above-mentioned photosensitive resin composition, a composition containing a polymer, a monomer, a polymerization initiator and the like can be used as described later. The thickness of the formed photosensitive resin layer 14 can be set in consideration of the thickness required for the pattern,
For example, it can be set in a range of about 2 to 200 μm.

In the description based on FIG. 1, the photosensitive resin layer 14 is cured by exposure and loses its tackiness.

The transfer substrate sheet 12 and the release film 13 used here need to be made of a material which has flexibility as described later and which does not cause significant deformation by tension or pressure. The transfer base sheet 12 can be selected in consideration of the characteristics of the release film 13 and the photosensitive resin layer 14. That is, a transfer base sheet 12 is used in which the adhesion of the transfer base sheet 12 to the photosensitive resin layer 14 is stronger than the adhesion between the release film 13 and the photosensitive resin layer 14. The thickness of such a transfer base sheet 12 can be set to 4 to 200 μm, preferably about 12 to 100 μm. Incidentally, the transfer substrate sheet 12,
A primer layer as described later may be formed on the release film 13 in order to adjust the adhesion between the release film 13 and the photosensitive resin layer 14.

The above-mentioned composite sheet 11 may be of a single-wafer type or may be of a long body. By forming the transfer base sheet 12 and the release film 13 into a long body, the composite sheet 11 can be wound and stored in a roll shape, and a required amount can be sent out as needed to be used for pattern formation.

(2) As a second step, the photosensitive resin layer 14 is exposed through a photomask M (FIG. 1).
(B)). This exposure may be either exposure from the transfer substrate sheet 12 side or exposure from the release film 13 side when both the transfer substrate sheet 12 and the release film 13 have optical transparency. The photomask M is provided with a predetermined light transmission pattern depending on whether the photosensitive resin layer 14 is a positive type or a negative type. The example shown is
The case where the photosensitive resin layer 14 is a negative type is shown.
The exposure amount of the photosensitive resin layer 14 is, for example, an exposure amount that completely cures the exposed portion of the photosensitive resin layer 14, or the curing of the exposed portion of the photosensitive resin layer 14 is stopped at an intermediate stage. Any of the above exposure amounts may be used.
It is necessary to set the exposure amount so that the peeling development in the step can be performed reliably. Exposure can be performed using a known exposure means such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, and a laser.

(3) As a third step, by peeling off the release film 13, the photosensitive resin layer 14 is removed in a predetermined pattern together with the release film 13 and developed (FIG. 1C). In the illustrated example, the exposed portion of the photosensitive resin layer 14 is peeled and removed together with the release film 13,
Unexposed portions of the photosensitive resin layer 14 form a residual pattern 14 '. Whether the entire unexposed portion of the photosensitive resin layer 14 remains on the transfer base sheet 12 as a residual pattern 14 ′ or whether a part of the photosensitive resin layer 14 in the thickness direction remains as a residual pattern 14 ′ depends on whether the release film 13 It is determined by the relationship between the adhesive force with the photosensitive resin layer 14 and the cohesive force of the photosensitive resin layer 14. Therefore, it is necessary to appropriately set the material of the release film 13, the constituent material of the photosensitive resin layer 14, the thickness of the photosensitive resin layer 14, and the like according to the thickness required for the residual pattern 14 '.

(4) As a fourth step, the composite sheet 1
The pattern-formed body 1 is pressure-bonded to the residual pattern 14 'on the first transfer base sheet 12 (FIG. 1 (D)). Next, the transfer base sheet 12 is peeled to transfer the residual pattern 14 ′ onto the pattern-formed body 1, and then fired to leave the residual pattern 1 ′.
By removing the resin component 4 ′, a pattern 4 is formed on the pattern forming target 1 (FIG. 1E).

In the present invention described above, in any of the first to fourth steps, there is no material loss in a coating step such as spin coating, and a wet development step and a cleaning step are not required. The use efficiency is high and the process is simple. First Invention of Pattern Forming Method (Second Embodiment) According to the first invention of the pattern forming method as described above, for example, an electrode pattern of a plasma display panel (PDP) can be formed.

Before explaining the formation of the electrode pattern of the PDP according to the first aspect of the pattern forming method, the AC
A type PDP will be described.

FIG. 2 is a schematic structural view showing an AC type PDP, in which a front plate and a back plate are separated.
In FIG. 2, the PDP 51 has a front plate 61 and a rear plate 71 arranged in parallel and opposed to each other, and a barrier 76 is formed on the front side of the rear plate 71 so as to stand upright. The front plate 61 and the back plate 71 are held at regular intervals by the barrier 76. The front plate 61 has a front glass substrate 62, and composite electrodes composed of a sustain electrode 63 which is a transparent electrode and a bus electrode 64 which is a metal electrode are formed on the rear side of the front glass substrate 62 in parallel with each other. And a dielectric layer 65 is formed over the
An O layer 66 is formed. The rear plate 71 has a rear glass substrate 72, and an address electrode 74 is disposed on the front side of the rear glass substrate 72 with a base layer 73 interposed between barriers 76 so as to be orthogonal to the composite electrode. Are formed in parallel with each other, a dielectric layer 75 is formed so as to cover them, and a phosphor layer 77 is provided so as to cover the wall surface of the barrier 76 and the bottom surface of the cell. In the AC type PDP, a predetermined voltage is applied from an AC power supply between the composite electrodes on the front glass substrate 62 to form an electric field, whereby the front glass substrate 62, the rear glass substrate 72, and the barrier 7 are formed.
Discharge is performed in each cell as a display element defined by the cells 6 and 6. Then, the phosphor layer 77 is caused to emit light by the ultraviolet light generated by the discharge, and the light transmitted through the front glass substrate 62 is visually recognized by the observer.

Next, the first invention of the pattern forming method will be described by taking as an example the formation of the address electrode 74 and the dielectric layer 75 on the back plate 71 of the PDP.

FIG. 3 is a process chart for explaining a second embodiment of the pattern forming method of the first invention.

(1) In FIG. 3, first, as a first step, a composite sheet in which a conductive photosensitive resin layer 14 and a dielectric layer 15 are provided between a transfer base sheet 12 and a release film 13 11 (FIG. 3A). In the composite sheet 11, the photosensitive resin layer 14 is adjacent to the release film 13, and the dielectric layer 15 is provided between the photosensitive resin layer 14 and the transfer base sheet 12. The conductive photosensitive resin layer 14 contains at least a conductive powder and a photosensitive resin composition as described later, and further has an adhesive property with a back glass substrate 72 (base layer 73) on which address electrodes are formed. It contains an inorganic powder if necessary for the purpose of improving the quality.

(2) As a second step, the photosensitive resin layer 14 is exposed through a photomask M (FIG. 3).
(B)). This exposure is performed from the release film 13 side because the dielectric layer 15 does not have light transmittance. The illustrated example shows a case where the photosensitive resin layer 14 is a negative type.

(3) As a third step, by peeling off the release film 13, the photosensitive resin layer 14 is removed in a predetermined pattern together with the release film 13 and developed (FIG. 3C). In the illustrated example, the exposed portions of the conductive photosensitive resin layer 14 are peeled and removed together with the release film 13, and the unexposed portions of the photosensitive resin layer 14 form a residual pattern 14 '.

(4) As the fourth step, the composite sheet 1
The back glass substrate 72 provided with the underlayer 73 is pressed against the remaining pattern 14 'of FIG. 1 (FIG. 3D). Next, the transfer base sheet 12 is peeled off to transfer the residual pattern 14 ′, which is a conductive photosensitive resin layer, and the dielectric layer 15 onto the base layer 73, and then baked to obtain a resin component of the residual pattern 14 ′. Is removed, thereby forming the address electrode pattern 74 and the dielectric layer 75 (FIG. 3E). Second Embodiment of Pattern Forming Method (First Embodiment) FIG. 4 is a process chart for explaining an embodiment of the pattern forming method of the second invention.

(1) In FIG. 4, first, as a first step, a composite sheet 21 provided by laminating a photosensitive resin layer 24 and a pattern forming layer 25 on a transfer base sheet 22 is formed (FIG. 4). (A)). In the illustrated example, the photosensitive resin layer 2
4, only the pattern forming layer 25 is provided, but another layer may be provided on the pattern forming layer 25.

The photosensitive resin layer 24 is formed on the transfer base sheet 22 by a known method such as a direct gravure coating method, a gravure reverse coating method, a reverse roll coating method, a slide die coating method, a slit die coating method, and a comma coating method. The photosensitive resin composition can be formed by applying and drying the photosensitive resin composition. Further, the photosensitive resin layer 24 may be formed by laminating a film made of the photosensitive resin composition on the transfer base sheet 22.

The pattern forming layer 25 can be formed by applying a desired material on the photosensitive resin layer 24 by the above-mentioned known coating means and drying it. It can be formed by laminating on the conductive resin layer 24.

The photosensitive resin composition for forming the above-mentioned photosensitive resin layer 24 may be added to a known photosensitive resin composition in consideration of the characteristics and functions required for the pattern to be formed. Those containing an appropriate agent can be used. As the above-mentioned photosensitive resin composition, a composition containing a polymer, a monomer, a polymerization initiator and the like can be used as described later. The thickness of the formed photosensitive resin layer 24 can be set in consideration of the thickness required for the pattern,
For example, it can be set in a range of about 5 to 100 μm. Further, the photosensitive resin layer 24 may contain the same inorganic powder as the pattern forming layer 25.

In the description based on FIG. 4, the photosensitive resin layer 24 is cured by exposure and loses its tackiness.

As will be described later, the pattern forming layer 25
The resin component contains an inorganic powder or the like appropriately selected according to the characteristics, action, and the like required for the pattern. The thickness of the pattern forming layer 25 can be set in consideration of the thickness required for the pattern.
It can be set in a range of about 300 μm.

The transfer base sheet 22 used here must be made of a material which has flexibility as described later and which does not cause significant deformation by tension or pressure. The transfer base sheet 22 can be selected in consideration of the characteristics of the photosensitive resin layer 24 and the pattern forming layer 25. That is, a transfer base sheet 22 is used in which the adhesion of the transfer base sheet 22 to the photosensitive resin layer 24 is weaker than the adhesion between the pattern forming layer 25 and the photosensitive resin layer 24. The thickness of such a transfer base sheet 22 is 4 to 200.
μm, preferably about 12 to 100 μm. Incidentally, a primer layer as described later may be formed on the transfer base material sheet 22 in order to adjust the adhesive strength with the photosensitive resin layer 24.

As in the case of the composite sheet 11 described above, the composite sheet 21 may be a single sheet type or a long body.

(2) As the second step, the composite sheet 2
The pattern formation target 1 is pressed against the first pattern formation layer 25, and the photosensitive resin layer 24 is exposed through a photomask M (FIG. 4B). In this exposure, when the transfer base sheet 22 has light transmittance, and when the pattern-formed body 1 and the pattern formation layer 25 have light transmittance, the exposure and transfer from the transfer base sheet 12 side are performed. Exposure from the pattern forming body 1 side may be used. The photomask M is provided with a predetermined light transmission pattern depending on whether the photosensitive resin layer 24 is a positive type or a negative type. The example shown is
The case where the photosensitive resin layer 24 is a negative type is shown.
The exposure amount of the photosensitive resin layer 24 is, for example, an exposure amount at which the exposed portion of the photosensitive resin layer 24 is completely cured, or the curing of the exposed portion of the photosensitive resin layer 24 is stopped at an intermediate stage. Any of the above exposure amounts may be used.
It is necessary to set the exposure amount so that the peeling development in the step can be performed reliably. Exposure can be performed using a known exposure means such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, and a laser.

(3) In the third step, the transfer base sheet 22 is peeled off,
At the same time, the photosensitive resin layer 24 is removed in a predetermined pattern and developed (FIG. 4C). In the illustrated example, the photosensitive resin layer 24
Of the exposed portions, the exposed portions are peeled and removed together with the transfer base sheet 22, and the unexposed portions of the photosensitive resin layer 24 correspond to the remaining pattern 2.
4 '. Note that the entire unexposed portion of the photosensitive resin layer 24 is left as a residual pattern 24 '.
It remains on the upper surface, or a part of the remaining pattern 24
Are left as the transfer base sheet 22 and the photosensitive resin layer 2
4 and the cohesive strength of the photosensitive resin layer 24. For this reason, the residual pattern 24 '
It is necessary to appropriately set the material of the transfer base sheet 22, the constituent material of the photosensitive resin layer 24, the layer thickness of the photosensitive resin layer 24, and the like according to the thickness required for the above.

(4) As a fourth step, the pattern forming layer 25 is subjected to sandblasting using the residual pattern 24 'as a mask. By this sandblasting, the portion of the pattern forming layer 25 covered with the residual pattern 24 'is protected by the elastic residual pattern 24' and is not ground, and only the exposed portion of the pattern forming layer 25 is selectively ground. Thus, a pattern corresponding to the residual pattern 24 'is formed (FIG. 4D). Sandblasting in this step can use a conventionally known processing method, and is not particularly limited. Next, the residual pattern 24 '
After peeling, the pattern 6 is formed on the pattern forming target 1 by removing the resin component of the pattern forming layer 25 by firing (FIG. 4E). As described above, when the photosensitive resin layer 24 contains the same inorganic powder as the pattern forming layer 25, the above-described residual pattern 24
It is not necessary to peel off the 'pattern, and the residual pattern 24' is integrated with the pattern forming layer 25 by baking to form the pattern 6.

In the present invention described above, in any of the first to fourth steps, there is no material loss in the coating step such as spin coating, and the wet development step and the cleaning step are not required. The use efficiency is high and the process is simple. Second Pattern Forming Method (Second Embodiment) According to the second pattern forming method described above, for example, a barrier pattern of a plasma display panel (PDP) as shown in FIG. 2 is formed. be able to.

Next, the back plate 71 of the PDP shown in FIG.
The second invention of the pattern forming method will be described by taking as an example the formation of the barrier 76 and the dielectric layer 75 in FIG.

FIG. 5 is a process chart for explaining a second embodiment of the pattern forming method of the second invention.

(1) In FIG. 5, first, as a first step, a photosensitive resin layer 24, a pattern forming layer 25 for forming a barrier, and a dielectric layer 26 are provided on a transfer base sheet 22. Forming composite sheet 21 (FIG. 5)
(A)). In this composite sheet 21, the pattern forming layer 2
5, a dielectric layer 26 is further provided.

(2) As the second step, the composite sheet 2
The underlayer 73 and the address electrode 7
4 is pressed, and the photosensitive resin layer 24 is exposed through a photomask M (FIG. 5).
(B)). This exposure is performed by the pattern forming layer 2 for forming a barrier.
Since No. 5 has no light transmittance, the transfer is performed from the transfer base sheet 22 side. The illustrated example shows a case where the photosensitive resin layer 24 is of a negative type.

(3) In the third step, the transfer base material sheet 22 is peeled off,
At the same time, the photosensitive resin layer 24 is removed in a predetermined pattern and developed (FIG. 5C). In the illustrated example, the photosensitive resin layer 24
Of the exposed portions, the exposed portions are peeled and removed together with the transfer base sheet 22, and the unexposed portions of the photosensitive resin layer 24 correspond to the remaining pattern 2.
4 '.

(4) As a fourth step, the pattern forming layer 25 is subjected to sandblasting using the residual pattern 24 'as a mask, and only the exposed portions of the pattern forming layer 25 are selectively ground (FIG. 5D). Then, after the residual pattern 24 'is peeled off, baking is performed to remove the resin component of the pattern forming layer 25, thereby forming the barrier pattern 76 and the dielectric layer 75 (FIG. 5).
(E)).

The photosensitive resin layer 24 is formed of the pattern forming layer 2
In the case of containing the same inorganic powder for forming a barrier as in No. 5, the above-described peeling of the residual pattern 24 'is unnecessary. Third Embodiment of Pattern Forming Method (First Embodiment) FIGS. 6 and 7 are process diagrams for explaining one embodiment of the pattern forming method of the third invention.

(1) In FIGS. 6 and 7, first,
As a first step, a composite sheet 31 including a first photosensitive resin layer 34, a pattern forming layer 35, and a second photosensitive resin layer 36 laminated between a transfer base sheet 32 and a release film 33 is provided. It is formed (FIG. 6A). In the example shown,
Although the second photosensitive resin layer 36 is provided adjacent to the pattern forming layer 35, another layer may be provided between the two layers.

The first photosensitive resin layer 34 is formed, for example, by direct gravure coating on the transfer base sheet 32,
The photosensitive resin composition can be formed by applying and drying the photosensitive resin composition by a known coating means such as a gravure reverse coating method, a reverse roll coating method, a slide die coating method, a slit die coating method, and a comma coating method. Further, the first photosensitive resin layer 34 may be formed by laminating a film made of the photosensitive resin composition on the transfer base sheet 32.

The pattern forming layer 35 can be formed by applying and drying a desired material on the first photosensitive resin layer 34 by the above-mentioned known coating means, or a film made of the desired material. Is laminated on the first photosensitive resin layer 34.

The second photosensitive resin layer 36 can be formed by applying and drying a photosensitive resin composition on the pattern forming layer 35, and laminating the release film 33 on the second photosensitive resin layer 36. The composite sheet 31 can be formed by pressure bonding. Further, a photosensitive resin composition is applied on the release film 33 and dried to form a second photosensitive resin layer 36, and the pattern forming layer 3 is formed on the second photosensitive resin layer 36.
The composite sheet 31 may be formed by stacking and pressing the transfer base sheet 32 on which the transfer sheet 5 is formed. Further, a film made of the photosensitive resin composition may be laminated on the release film 33 to form the second photosensitive resin layer 36. The first photosensitive resin layer 34 is formed by pattern formation as described later. The second photosensitive resin layer 36 is for forming a mask when sandblasting is performed on the layer 35, and the second photosensitive resin layer 36 is for forming a desired pattern.
The photosensitive resin composition constituting each photosensitive resin layer is prepared by appropriately adding a necessary additive to a known photosensitive resin composition in consideration of properties, actions, and the like required for a pattern to be formed. Can be used. As the above-mentioned photosensitive resin composition, a composition containing a polymer, a monomer, a polymerization initiator and the like can be used as described later. The thickness of the formed first photosensitive resin layer 34 and second photosensitive resin layer 36 is
The thickness can be set in consideration of the thickness required for the pattern. For example, the thickness can be set in a range of about 5 to 100 μm. Further, the first photosensitive resin layer 34 may contain the same inorganic powder as the pattern forming layer 35.

In the description based on FIGS. 6 and 7, the first photosensitive resin layer 34 and the second photosensitive resin layer 36 are cured by exposure and lose their tackiness.

As will be described later, the pattern forming layer 35
The resin component contains an inorganic powder or the like appropriately selected according to the characteristics, action, and the like required for the pattern. The thickness of the pattern forming layer 35 can be set in consideration of the thickness required for the pattern.
It can be set in a range of about 300 μm.

As will be described later, the transfer base sheet 32 and the release film 33 used here need to be made of a material having light transmittance and flexibility and not causing significant deformation by tension or pressure. is there. Transfer substrate sheet 32
Can be selected in consideration of the characteristics of the first photosensitive resin layer 34 and the pattern forming layer 35. That is, the adhesion of the transfer base sheet 32 to the first photosensitive resin layer 34 is
A transfer base sheet 32 that is weaker than the adhesion between the pattern forming layer 35 and the first photosensitive resin layer 34 is used.
The thickness of such a transfer base sheet 32 is 4 to 200 μm.
m, preferably about 12 to 100 μm. The release film 33 can be selected in consideration of the characteristics of the second photosensitive resin layer 36 and the pattern forming layer 35. That is, a release film 33 is used in which the adhesion of the release film 33 to the second photosensitive resin layer 36 is weaker than the adhesion between the pattern forming layer 35 and the second photosensitive resin layer 36. Such a release film 3
3 has a thickness of 4 to 200 μm, preferably 12 to 100 μm.
m can be set. The transfer base sheet 3
2. A primer layer, which will be described later, may be formed on the release film 33 in order to adjust the adhesive strength with the first photosensitive resin layer 34 and the adhesive strength with the second photosensitive resin layer 36.

As in the case of the composite sheet 11 described above, such a composite sheet 31 may be a single sheet type or a long body.

(2) In the second step, the second photosensitive resin layer 36 is exposed through the photomask M from the side of the light-transmitting release film 33 (FIG. 6B). The photomask M is provided with a predetermined light transmission pattern depending on whether the second photosensitive resin layer 36 is a positive type or a negative type. The illustrated example shows a case where the second photosensitive resin layer 36 is a negative type. The second photosensitive resin layer 36
The exposure amount is, for example, an exposure amount at which the exposed portion of the second photosensitive resin layer 36 is completely cured, or an exposure amount at which curing of the exposed portion of the second photosensitive resin layer 36 is stopped at an intermediate stage. The exposure amount may be any value, and it is necessary to set the exposure amount so that the peeling development in the third step described later can be reliably performed. Exposure can be performed using a known exposure means such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, and a laser.

(3) In the third step, the second photosensitive resin layer 36 is removed in a predetermined pattern together with the release film 33 by peeling off the release film 33 and developed (FIG. 6C). In the illustrated example, the exposed portions of the second photosensitive resin layer 36 are peeled and removed together with the release film 33, and the unexposed portions of the second photosensitive resin layer 36 form a residual pattern 36 '. The second photosensitive resin layer 36
Whether the entire unexposed portion remains on the pattern forming layer 35 as a residual pattern 36 'or a part of the unexposed portion in the thickness direction remains as a residual pattern 36' It is determined by the relationship between the adhesive force and the cohesive force of the second photosensitive resin layer 36. Therefore, depending on the thickness required for the residual pattern 36 ', the material of the release film 33, the constituent material of the second photosensitive resin layer 36,
It is necessary to appropriately set the thickness of the second photosensitive resin layer 36 and the like.

(4) As the fourth step, the composite sheet 3
The pattern forming body 1 is pressed against the remaining pattern 36 ′ of the first pattern forming layer 35, and the first photosensitive resin layer 34 is exposed from the transfer base sheet 32 side via the photomask M ′ (FIG. 6D )). The photomask M ′ is provided with a predetermined light transmission pattern depending on whether the first photosensitive resin layer 34 is a positive type or a negative type. The illustrated example shows a case where the first photosensitive resin layer 34 is a negative type.
The exposure amount of the first photosensitive resin layer 34 is, for example, an exposure amount at which the exposed portion of the first photosensitive resin layer 34 is completely cured, or the exposure amount of the first photosensitive resin layer 34 is cured. May be any of the exposure amounts that stop in the middle stage,
It is necessary to set an exposure amount so that peeling development in a fifth step described later can be reliably performed. Exposure can be performed using a known exposure means such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, and a laser.

(5) In the fifth step, the transfer base material sheet 32 is peeled off,
At the same time, the first photosensitive resin layer 34 is removed in a predetermined pattern and developed (FIG. 7A). In the illustrated example, the exposed portions of the first photosensitive resin layer 34 are peeled and removed together with the transfer base sheet 32, and the unexposed portions of the first photosensitive resin layer 34 form a residual pattern 34 '. It should be noted that whether the entire unexposed portion of the first photosensitive resin layer 34 remains on the pattern forming layer 35 as a residual pattern 34 'or whether a part of the first photosensitive resin layer 34 in the thickness direction remains as a residual pattern 34' is determined. 32
It is determined by the relationship between the adhesion between the first photosensitive resin layer 34 and the first photosensitive resin layer 34 and the cohesive force of the first photosensitive resin layer 34. Therefore, the material of the transfer substrate sheet 32 and the first photosensitive resin layer
, The thickness of the first photosensitive resin layer 34 and the like need to be appropriately set.

(6) As a sixth step, the pattern forming layer 35 is subjected to sandblasting using the residual pattern 34 'as a mask. Due to this sandblasting, the portion covered with the residual pattern 34 'of the pattern forming layer 35 is protected by the elastic residual pattern 34' and is not ground, and only the exposed portion of the pattern forming layer 35 is selectively ground. Thus, a pattern corresponding to the residual pattern 34 'is formed (FIG. 7B). Sandblasting in this step can use a conventionally known processing method, and is not particularly limited. Next, the residual pattern 34 '
After removing, the resin component of the pattern forming layer 35 and the resin component of the residual pattern 36 'are removed to form the pattern 4 and the pattern 6 on the pattern formation target 1 (FIG. 7C). ). As described above, when the first photosensitive resin layer 34 contains the same inorganic powder as the pattern forming layer 35, the peeling of the residual pattern 34 'is unnecessary, and the residual pattern 34 is not necessary. ′ Are integrated with the pattern forming layer 35 by firing to form the pattern 6
To form

In the present invention described above, in any of the first to sixth steps, there is no material loss in the application step such as spin coating, and the wet development step and the cleaning step are unnecessary, and The use efficiency is high and the process is simple. Third Invention of Pattern Forming Method (Second Embodiment) According to the third invention of the pattern forming method as described above, for example, an address electrode pattern and a barrier of a plasma display panel (PDP) as shown in FIG. A pattern can be formed.

Next, the back plate 71 of the PDP shown in FIG.
The third invention of the pattern forming method will be described by taking as an example the formation of the address electrode 74, the barrier 76, and the dielectric layer 75 in FIG.

FIGS. 8 and 9 are process charts for explaining a second embodiment of the pattern forming method of the third invention.

(1) In FIGS. 8 and 9, first,
As a first step, a first photosensitive resin layer 34, a pattern forming layer 35, a dielectric layer 37, and a conductive second photosensitive resin layer 3 are provided between the transfer base sheet 32 and the release film 33.
8 to form a composite sheet 31 provided by stacking
(A)). In this composite sheet 31, the pattern forming layer 3
A dielectric layer 37 is provided between the first photosensitive resin layer 5 and the second photosensitive resin layer 36. The conductive second photosensitive resin layer 36 contains at least a conductive powder and a photosensitive resin composition as described later, and further includes a back glass substrate 72 (base layer 73) on which address electrodes are formed. It contains an inorganic powder, if necessary, for the purpose of improving the adhesion.

(2) As a second step, the second photosensitive resin layer 36 is exposed through a photomask M (FIG. 8).
(B)). This exposure is performed from the release film 33 side.
The illustrated example shows a case where the second photosensitive resin layer 36 is a negative type.

(3) In the third step, the second photosensitive resin layer 36 is removed in a predetermined pattern together with the release film 33 by peeling off the release film 33 and developed (FIG. 8C). In the illustrated example, the exposed portion of the conductive second photosensitive resin layer 36 is peeled and removed together with the release film 33, and the unexposed portion of the second photosensitive resin layer 36 forms a residual pattern 36 '.

(4) As the fourth step, the composite sheet 3
The rear glass substrate 72 provided with the underlayer 73 is pressed against the first residual pattern 36 ', and the first photosensitive resin layer 34 is exposed from the transfer substrate sheet 32 side through the photomask M' (FIG. 8 ( D)). The illustrated example shows the first photosensitive resin layer 3
4 shows the case where the negative type is used.

(5) In the fifth step, the transfer base material sheet 32 is peeled off,
At the same time, the first photosensitive resin layer 34 is removed in a predetermined pattern and developed (FIG. 9A). In the illustrated example, the exposed portions of the first photosensitive resin layer 34 are peeled and removed together with the transfer base sheet 32, and the unexposed portions of the first photosensitive resin layer 34 form a residual pattern 34 '.

(6) As a sixth step, the pattern forming layer 35 is subjected to sandblasting using the residual pattern 34 'as a mask, and only the exposed portions of the pattern forming layer 35 are selectively ground (FIG. 9B). Next, after the residual pattern 34 'is peeled off, baking is performed to remove the resin component of the pattern forming layer 35 and the resin component of the residual pattern 36', whereby the barrier pattern 76 and the address electrode pattern 7 are removed.
4 and a dielectric layer 75 (FIG. 9)
(C)).

When the first photosensitive resin layer 34 contains the same inorganic powder for forming a barrier as the pattern forming layer 35, the above-described removal of the residual pattern 34 'is unnecessary.

Next, the materials used in the present invention will be described in detail. Transfer Base Sheet First, the transfer base sheets 12, 22 and 3 used in the present invention.
2 will be described.

The transfer base sheets 12, 22, 32 must be made of a material which has flexibility and does not cause significant deformation by tension or pressure. It is necessary to use a material through which light for exposing the photosensitive resin layer 34 is transmitted.

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 polymethacrylic acid film, a polyvinyl chloride film, a polyvinyl alcohol film, and a 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, polyvinylidenefluor De film, polyethylene terephthalate film, polyethylene naphthalate film, a polyester film, a cellulose triacetate film, polycarbonate film,
Polyurethane films, polyimide films, polyetherimide films, films in which fillers are blended with these resin materials, uniaxially or biaxially stretched films using these resin materials, and flow directions using these resin materials A biaxially stretched film with a higher stretching ratio in the width direction, a biaxially stretched film with a higher stretching ratio in the flow direction than the width direction using these resin materials, and a film of the same or different type among these films Examples thereof include a combined film and a composite film formed by co-extruding the same or different resins selected from the raw material resins used for these films.

Further, as the transfer base material sheets 12, 22, 32, metal foils or metal steel strips can be used. Specific examples of such metal foil and metal steel strip include copper foil, copper steel strip, aluminum foil, aluminum steel strip, SUS430, SU
S301, SUS304, SUS420J2 and SU
Examples include a stainless steel strip such as S631 and a beryllium steel strip. Among these, a stainless steel strip, particularly preferably a SUS430 stainless steel strip, can be used in that the coefficient of thermal expansion is close to that of a glass substrate for a color filter.

Further, the transfer base material sheets 12, 22, 32
As the material used for the above, a material in which the above-described metal foil or metal steel strip is bonded to the above-described resin film can also be used. Release Sheet Next, the release sheets 13 and 33 used in the present invention will be described. The release sheets 13 and 33 need to be made of a material that has flexibility and does not cause significant deformation by tension or pressure.
3 needs to use a material through which light for exposing the second photosensitive resin layer 36 is transmitted.

Specific examples of the release films 13 and 33 include a polyethylene film, an ethylene-vinyl acetate copolymer film, an ethylene-vinyl alcohol copolymer film, a polypropylene film, a polystyrene film, a polymethacrylic acid film, and a 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, Li vinylidene fluoride film, polyethylene terephthalate film, polyethylene naphthalate film, a polyester film, a cellulose triacetate film, polycarbonate film,
Polyurethane films, polyimide films, polyetherimide films, films in which fillers are blended with these resin materials, uniaxially or biaxially stretched films using these resin materials, and flow directions using these resin materials A biaxially stretched film with a higher stretching ratio in the width direction, a biaxially stretched film with a higher stretching ratio in the flow direction than the width direction using these resin materials, and a film of the same or different type among these films Examples thereof include a combined film and a composite film formed by co-extruding the same or different resins selected from the raw material resins used for these films. Among these films, it is particularly preferable to use a biaxially stretched polyester film. In the first invention of the method for forming a primer layer pattern, the adhesive strength between the transfer base sheet 12 and the photosensitive resin layer 14 and the release film 1
In the second invention of the adjustment of the adhesion between the photosensitive resin layer 14 and the photosensitive resin layer 14 and the pattern formation method, the adjustment of the adhesion between the transfer base sheet 22 and the photosensitive resin layer 24 and the third method of the pattern formation method In the invention, the transfer base sheet 32 and the first
Adhesion between the photosensitive resin layer 34 and the release film 33
A primer layer may be provided in order to adjust the adhesive force with the photosensitive resin layer 36. Also, by providing such a primer layer, the surface of the transfer base material sheet or the release film may be provided with the photosensitive resin layer. Even if it does not have the required surface smoothness to form, the primer layer material is precisely coated to be extremely smooth, so that the required surface smoothness is transferred to the transfer substrate sheet or release film. Can also be given.

Materials that can be used for such a primer layer include an ethylene-vinyl acetate copolymer,
Ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polystyrene, acrylonitrile-styrene copolymer, ABS resin, polymethacrylic acid resin, ethylene methacrylic acid resin, polyvinyl chloride resin, chlorinated vinyl chloride resin, polyvinyl alcohol, Cellulose acetate propionate, cellulose acetate butyrate, nylon 6, nylon 66, nylon 12, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl acetal, polyether ether ketone, polyether sulfone, polyphenylene sulfide, polyarylate, polyvinyl butyral ,
Epoxy resin, phenoxy resin, polyimide resin, polyamide imide resin, polyamic acid resin, polyether imide resin, phenol resin, urea resin, polyvinyl formal, polyvinyl pyrrolidone, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose , Carboxymethylethylcellulose, ethylhydroxyethylcellulose, bisphenol A type epoxy resin, orthocresol novolak type epoxy resin,
Melamine resins and the like can be mentioned.

The primer layer may be formed by crosslinking the above resin with a crosslinking agent such as an isocyanate crosslinking agent or a chelating crosslinking agent. The crosslinking agent can be appropriately selected according to the reactive functional group of the resin to be crosslinked, and can be arbitrarily selected from known ones. As an example of a crosslinking agent,
Isophorone diisocyanate, xylylene diisocyanate, xylylene diisocyanate hydrogenated product, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, tetramethyl xylylene diisocyanate, an adduct obtained by adding the diisocyanate to trimethylolpropane, a biuret of the diisocyanate , A dimer of the above-mentioned diisocyanate, a crosslinking agent having an epoxy group, an aziridine group or an oxazoline group, aluminum, zinc, titanium,
Chelating agents having a metal atom such as zirconium can be mentioned.

When the primer layer is crosslinked as described above, a known catalyst can be added according to the crosslinking agent to be blended. For example, when isocyanate is used as a crosslinking agent, di-n-butyltin dilaurate, di-n-octyltin dilaurate, tetramethylbutanediamine,
N, N, N ', N'-tetramethyl-1,3-butanediamine, 1,4-diaza-bicyclo [2,2,2] octane and the like can be used.

In order to form the primer layer on the transfer substrate sheet or the release film, one side of the transfer substrate sheet or the release film may be provided with a cross-linking agent, a cross-linking reaction promoting catalyst, etc. The necessary additives are dissolved in an appropriate organic solvent or water, or dissolved in a mixed solvent of organic solvent and water, or a dispersion dispersed in an organic solvent or water, for example, gravure direct Coating, drying can be performed by means such as a coating method, a gravure reverse coating method, a reverse roll coating method, a slide die coating method, and a slit die coating method. When the slide die coating method is used, the primer layer and the photosensitive resin layer can be simultaneously applied and dried.

The thickness of the primer layer to be formed is 0.05 to
It can be set within a range of 5 μm, preferably 0.1 to 2 μm. When the thickness of the primer layer is less than 0.05 μm, the film strength required for the primer layer cannot be obtained. On the other hand, if it exceeds 5 μm, there is a problem that it becomes difficult to enhance the uniformity of the surface of the coating film.

Even when the primer layer is provided on the transfer substrate sheet or the release film, the composite sheets 11 and
The formation of 1, 31 is not particularly limited.

Also, the primer layer has a releasing action,
The releasability between the transfer substrate sheet and the photosensitive resin layer (residual pattern) or between the release film and the photosensitive resin layer (residual pattern) may be improved. In this case, polyethylene wax, amide wax, Teflon powder, silicone wax, carnauba wax, wax such as paraffin wax, fluorine resin, melamine resin, polyolefin resin, ionizing radiation curable polyfunctional acrylate resin, polyester resin, epoxy Resins, and further, amino-modified, epoxy-modified, OH-modified, COOH-modified, catalyst-curable, photocurable, and thermosetting silicone oils, silicone resins, and the like can be used. Photosensitive resin composition Next, in the present invention, the photosensitive resin layers 14, 24, 34,
The photosensitive resin composition for forming 36 will be described.

The photosensitive resin composition contains at least a polymer, a monomer and an initiator, and does not volatilize or decompose by firing to leave carbide in the pattern.

As the polymer, methyl acrylate,
Methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, sec-butyl acrylate, sec-
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, N-vinyl-2-pyrrolidone, acrylic acid, methacrylic acid, dimer of acrylic acid (for example,
M-5600 manufactured by Toa Gosei Chemical Co., Ltd.), polymers or copolymers composed of one or more of itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof, and cellulose derivatives such as ethyl cellulose. No.

Further, there may be mentioned, for example, polymers obtained by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the above-mentioned copolymer, but it is not limited thereto.

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, triethylene glycol diacrylate, polyoxypropyl trimethylolpropane 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 those obtained by changing the above acrylate to methacrylate, γ-methacryloxypropyltrimethoxysilane,
1-vinyl-2-pyrrolidone and the like. In the present invention, the above-mentioned reactive monomers 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, naphthalene sulfonyl chloride, quinoline sulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzothiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide,
Examples include a combination of a photoreducing dye such as tribromophenyl sulfone, benzoin peroxide, eosin, and methylene blue with a reducing agent such as ascorbic acid and triethanolamine. In the present invention, these photopolymerization initiators are
Species or two or more can be used.

Further, a sensitizer, a polymerization terminator, a chain transfer agent, a leveling agent,
A dispersant, a plasticizer, a stabilizer, an antifoaming agent, a thickener, a suspending agent, a release agent and the like can be contained as required.

Examples of the plasticizer include normal alkyl phthalates such as dimethyl phthalate, dibutyl phthalate and di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate and ethyl phthalyl ethyl glycolate. Phthalic acid esters such as butylphthalylbutyl glycolate, tri-2-ethylhexyl trimellitate, tri-n-alkyl trimellitate,
Trimellitate esters such as triisononyl trimellitate and 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, acetyl tributyl citrate and the like Aliphatic dibasic acid esters, glycol derivatives such as polyethylene glycol benzoate, triethylene glycol di- (2-ethylhexoate) and polyglycol ether; glycerin derivatives such as glycerol triacetate and glycerol diacetyl monolaurate; sebacine Acid, adipic acid,
Polyester based on azelaic acid, phthalic acid, etc., low molecular weight polyether having a molecular weight of 300 to 3000, low molecular weight poly-α-styrene, low molecular weight polystyrene, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate Orthophosphates such as tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylendiphenyl phosphate, 2-ethylhexyl diphenyl phosphate, methyl acetyl ricinolate, etc. Ricinoleic acid esters, poly-1,3-butanediol adipate, polyester / epoxidized esters such as epoxidized soybean oil, glycerin tria Tate, mention may be made of acetic acid esters such as 2-ethylhexyl acetate.

The dispersant and the anti-settling agent are intended to improve the dispersibility and anti-settling property of the inorganic powder described later, and include, for example, phosphate ester type, silicone type, castor oil ester type, Various surfactants and the like can be mentioned, examples of the defoaming 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 acids Type, fatty acid ester type, castor oil type, wax type, compound type and the like. Examples of the leveling agent include fluorine type, silicone type and various surfactants, which can be added in appropriate amounts.

Examples of the solvent used together with the photosensitive resin composition for forming the photosensitive resin layer include alcohols such as methanol, ethanol, n-propanel, i-propanol, ethylene glycol, propylene glycol, and the like. Or terpenes such as β-terpineol, acetone, methyl ethyl ketone, ketones such as cyclohexanone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, Ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Glycol ethers such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether, ethyl acetate, butyl acetate,
Cellosolve acetate, ethyl cellosolve acetate,
Acetates such as butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like can be mentioned. Inorganic powder Next, in the present invention, the photosensitive resin layers 14, 24, 34,
The inorganic powder to be added as needed is described in 36.

As the inorganic powder, for example, a softening temperature of 4
00 to 650 ° C., and the thermal expansion coefficient 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, when the heat resistance of the pattern formation target 1 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 400 ° C., the glass frit is fused before the resin component of the photosensitive resin layer is completely decomposed and volatilized. Furthermore, the coefficient of thermal expansion α ₃₀₀ of the glass frit is 60 × 10 ⁻⁷
/ ° C or more than 100 × 10 ^-7 / ° C,
In some cases, the difference from the coefficient of thermal expansion of the pattern-formed body becomes too large, resulting in distortion or the like, which is not preferable. The average particle size of such a glass frit is 0.1-5.
The range of μm is preferred.

Further, inorganic powders such as aluminum oxide, boron oxide, silica, titanium oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, and calcium carbonate can be used as the inorganic powder. Such an inorganic powder has an average particle size of 0.1 to 20 μm.
The range of m is preferable, and as an aggregate, it functions to prevent pattern casting during firing.

Further, in the second embodiment of the second invention of the pattern forming method and the second embodiment of the third invention of the pattern forming method, the photosensitive resin layer 24, the first photosensitive resin layer 3
4 for pattern forming layer 25 and pattern forming layer 3 respectively.
In the case where the barrier pattern 76 is formed by baking and integrating the same inorganic powder as in Example 5, the inorganic powder is used as an inorganic powder in order to reduce external light reflection of the PDP and to improve practical contrast. Black pigment may be contained in the photosensitive resin layer 24 and the first photosensitive resin layer 34. As the fire-resistant black pigment used, Co-Cr-
Fe, Co-Mn-Fe, Co-Fe-Mn-Al, C
o-Ni-Cr-Fe, Co-Ni-Mn-Cr-F
e, Co-Ni-Al-Cr-Fe, Co-Mn-Al
—Cr—Fe—Si and the like. The conductive photosensitive resin layer used in the second embodiment of the first invention of the conductive powder pattern forming method and the second embodiment of the third invention of the pattern forming method is the above-mentioned photosensitive resin composition. Can be formed using a material containing conductive powder. As the conductive powder, one or more of Au powder, Ag powder, Cu powder, Ni powder, Al powder, Ag-Pd powder and the like can be used. The shape of the conductive powder may be various shapes such as a sphere, a plate, a lump, a cone, and a rod, but a spherical conductive powder having no agglomeration and good dispersibility is preferable, and the average Particle size is 0.05-10μ
The range of m is preferred. The average particle size of the conductive powder is 0.05
If it is less than μm, the structural viscosity (thixotropic property) of the photosensitive conductive paste is undesirably large. On the other hand, if the average particle size of the conductive powder exceeds 10 μm, the light transmittance becomes low and the photosensitivity is hindered, which is not preferable. Such conductive powder is added to the conductive photosensitive resin layer in an amount of 40 to 95%.
It can be contained in the range of weight%. In the second embodiment of the second invention of the barrier-forming material pattern forming method and the second embodiment of the third invention of the pattern-forming method, the pattern forming layers 25 and 35 are subjected to sandblasting to form P
A DP barrier is formed. In this case, the pattern forming layer 2
5, 35 can be composed of at least an inorganic component having a glass frit and a brittle resin.

As the glass frit, the glass frit mentioned as an example of the above-mentioned inorganic powder can be used.

As the inorganic component, in addition to the glass frit, various inorganic powders mentioned as examples of the above-mentioned inorganic powder can be used.
It is preferable to use 0 to 30 parts by weight with respect to parts by weight.

Further, as an inorganic component, an inorganic pigment can be used in order to reduce external light reflection of the PDP and to improve a practical contrast. When the barrier pattern to be formed is dark, C.I.
o-Cr-Fe, Co-Mn-Fe, Co-Fe-Mn
-Al, Co-Ni-Cr-Fe, Co-Ni-Mn-
Cr-Fe, Co-Ni-Al-Cr-Fe, Co-M
n-Al-Cr-Fe-Si or the like can be used. Further, as the fire-resistant white pigment, titanium oxide, aluminum oxide, silica, calcium carbonate and the like can be used. Dielectric Layer The dielectric layer can be composed of at least an inorganic component having a glass frit and a thermoplastic resin.

As the glass frit, the glass frit mentioned as an example of the above-mentioned inorganic powder can be used.

As the inorganic component, in addition to the glass frit, various inorganic powders mentioned as examples of the above-mentioned inorganic powder,
In addition, the above-mentioned inorganic pigments that can be used as the barrier-forming material can be used. These inorganic pigments are preferably used in a proportion of 0 to 30 parts by weight based on 100 parts by weight of the glass frit.

[0106]

Next, the present invention will be described in more detail with reference to examples. Example 1 First, a coating solution A having the following composition for forming a conductive photosensitive resin layer and a coating solution B having the following composition for forming a dielectric layer were prepared.

Composition of coating solution A : Silver powder (spherical, average particle size: 1 μm): 70 parts by weight Glass frit: 5 parts by weight (main components: Bi ₂ O ₃ , SiO ₂ , B ₂ O ₃ (alkali-free) (Softening point = 550 ° C, coefficient of thermal expansion α ₃₀₀ = 80 × 10 ^-7 / ° C) ・ Polymethyl methacrylate ... 15 parts by weight ・ Polyoxyethylated trimethylolpropane triacrylate ... 15 parts by weight ・ Photopolymerization initiator (Ciba-Geigy) Irgacure 907) 5 parts by weight Composition of coating solution B Glass frit 70 parts by weight (main component: Bi ₂ O ₃ , ZnO ₂ , B ₂ O ₃ (non-alkali) average particle size = 3 μm) ・ TiO ₂ ... 3 parts by weight · Al ₂ O ₃ ... 7 parts by weight (softening point of the inorganic component mixture = 570 ℃, Tg = 485 ℃ thermal expansion coefficient ^{_{α 300 = 80 × 10 -7 /}} ℃) · n- butyl methacrylate / Hid Xylethylhexyl methacrylate copolymer (8/2) 10 weight parts benzyl butyl phthalate 7 weight parts propylene glycol monomethyl ether 20 weight parts Next, a 25 μm thick polyethylene terephthalate film was prepared as a transfer base sheet. On the transfer base sheet, the coating liquid B is applied by a comma coating method and dried to form a dielectric layer having a thickness of 20 μm.
The coating liquid A is applied on a release film (polyethylene terephthalate film) having a thickness of 12 μm by a slit reverse coating method and dried to form a conductive photosensitive resin layer having a thickness of 15 μm. A composite sheet was prepared by laminating the dielectric layer surfaces. The formed conductive photosensitive resin layer is cured by exposure and loses adhesiveness. (The above is the first step) Next, the photosensitive resin layer was exposed from the release film side through a photomask corresponding to the address electrode pattern of the plasma display panel (PDP). For this exposure, an ultra-high pressure mercury lamp was used, and the exposure amount was 30 mJ / cm ² .
(The above, the second step) Next, by peeling off the release film, the exposed portion of the photosensitive resin layer is removed together with the release film and developed, and the residual pattern composed of the unexposed portion of the photosensitive resin layer is removed. It was formed on a dielectric layer. (The above, the third step) Next, a glass substrate was overlaid on the remaining pattern of the composite sheet, and pressed with a hot roll. Next, the transfer substrate sheet is peeled off to transfer the residual pattern, which is a conductive photosensitive resin layer, and the dielectric layer onto the glass substrate, and then baked at 570 ° C. for 10 minutes to form the address electrode pattern. Formed. The formed address electrode had a line width of 50 μm and a high definition. (Example 2) First, a coating solution C having the following composition for forming a photosensitive resin layer and a coating solution D having the following composition for forming a pattern forming layer were prepared.

Composition of coating solution C : Glass frit MB-010A: 65 parts by weight (manufactured by Matsunami Glass Industry Co., Ltd.) α-alumina RA-40 (manufactured by Iwatani Chemical Industry Co., Ltd.): 10 parts by weight Side black # 9510 10 parts by weight (manufactured by Dainichi Seika Industry Co., Ltd.) Photosensitive resin (the following composition) 30 parts by weight Methyl methacrylate / methacrylic acid copolymer 100 parts by weight (acid value = 100 mg KOH / g) Polyoxyethylated trimethylolpropane triacrylate: 70 parts by weight Photopolymerization initiator (Irgacure 907 manufactured by Ciba-Geigy Co., Ltd.): 10 parts by weight Composition of coating solution D Glass frit MB-008: 65 parts by weight (Matsunami Glass Industry) Ltd.), alpha-alumina RA-40 (manufactured by Iwatani chemical industry Co., Ltd.) ... 10 parts by weight TiO ₂ ... 10 parts by weight ethylene Cellulose 4 parts by weight Bis (2-ethylhexyl) phthalate 4 parts by weight Dimethyl phthalate 8.5 parts by weight Propylene glycol monomethyl ether 5 parts by weight Isopropyl alcohol 20 parts by weight A 75 μm-thick polyethylene terephthalate film is prepared as a sheet, the above-mentioned coating solution C is applied on this transfer base sheet by a comma coating method, and dried to form a 40 μm-thick photosensitive resin layer. The above coating solution D is applied thereon by a comma coating method and dried to form a pattern forming layer having a thickness of 180 μm. Further, the coating solution B of Example 1 is applied on the pattern forming layer by a comma coating method and dried. Thus, a dielectric layer having a thickness of 20 μm was formed to obtain a composite sheet. The formed photosensitive resin layer is cured by exposure and loses adhesiveness. (The above is the first step) Next, a glass substrate was overlaid on the dielectric layer of the composite sheet, and pressed by a hot roll. Next, the photosensitive resin layer was exposed from the transfer substrate sheet side via a photomask corresponding to the barrier pattern of the PDP. For this exposure, an ultra-high pressure mercury lamp was used, and the exposure amount was 40 mJ / cm ² . (The above, the second step) Next, by exfoliating the transfer base sheet, the exposed portions of the photosensitive resin layer are removed and developed together with the transfer base sheet, and the transfer is made up of the unexposed portions of the photosensitive resin layer. A residual pattern was formed on the pattern forming layer. (The above, the third step) Next, the pattern forming layer was subjected to sandblasting using the residual pattern as a mask, and then baked at 570 ° C. for 10 minutes to form a barrier pattern. The formed barrier pattern had a width of 50 μm and a height of 120 μm, and had a high aspect ratio and high definition. Example 3 A 75 μm-thick polyethylene terephthalate film was prepared as a transfer base sheet, and the coating solution C of Example 2 was applied on this transfer base sheet by a comma coating method and dried to obtain a 40 μm-thick first photosensitive film. A conductive resin layer was formed, and the coating solution D of Example 2 was applied on the first photosensitive resin layer by a comma coating method and dried to form a pattern forming layer having a thickness of 180 μm. Next, the coating solution B of Example 1 is applied on the pattern forming layer by a comma coating method and dried to form a dielectric layer having a thickness of 20 μm, and the coating solution A of Example 1 is comma-coated on the dielectric layer. A 15 μm-thick conductive second photosensitive resin layer is formed by applying and drying by a method, and a 25 μm-thick release film (polyethylene terephthalate film) is further laminated on the second photosensitive resin layer to prepare a composite sheet. did. The formed first photosensitive resin layer and the conductive second
The photosensitive resin layer is cured by exposure and loses its tackiness. (The above is the first step) Next, the second photosensitive resin layer was exposed from the release film side through a photomask corresponding to the address electrode pattern of the PDP. For this exposure, an ultra-high pressure mercury lamp was used, and the exposure amount was 40 mJ / cm ² . (The above, the second step) Next, by peeling off the release film, the exposed portion of the second photosensitive resin layer is removed together with this release film and developed, and the unexposed portion of the second photosensitive resin layer is developed. A residual pattern was formed on the dielectric layer. (The above, the third step) Next, a glass substrate was overlaid on the remaining pattern of the composite sheet, and pressed with a hot roll. Next, the first photosensitive resin layer was exposed from the transfer substrate sheet side via a photomask corresponding to the barrier pattern of the PDP. For this exposure, an ultra-high pressure mercury lamp was used, and the exposure amount was 100 mJ / cm ² . (The above is the fourth step) Next, by exfoliating the transfer base sheet, the exposed portions of the first photosensitive resin layer are removed and developed together with the transfer base sheet, and the transfer is performed. A residual pattern consisting of the exposed portions was formed on the pattern forming layer. (that's all,
Fifth Step) Next, the pattern forming layer was subjected to sandblasting using the residual pattern as a mask, and then baked at 570 ° C. for 10 minutes to form an address electrode pattern and a barrier pattern. The formed address electrode has a line width of 50.
The barrier pattern had a width of 50 μm and a height of 120 μm, and had a high aspect ratio and a high definition.

[0109]

As described above in detail, according to the present invention, the photosensitive resin layer is exposed to light in the composite sheet, and the release film is peeled off, thereby developing the composite sheet. The photosensitive resin layer is exposed and developed by peeling off the transfer base material sheet,
Alternatively, after the second photosensitive resin layer is exposed and peeled and developed in the state of the composite sheet, the first photosensitive resin layer of the composite sheet superimposed on the pattern forming body is exposed and the transfer base sheet is peeled off. Since the development is performed by the method, a wet development step and a washing step are not required in forming a desired pattern, so that the steps are simplified, and the pattern to be formed can be a high-definition pattern. Since the necessary sandblasting treatment is performed on the pattern forming layer using the pattern of the photosensitive resin layer formed by such dry peeling development as a mask, it is possible to form a high aspect pattern having a small width and a sufficient height.

[Brief description of the drawings]

FIG. 1 is a process chart for explaining a first embodiment of a first invention of a pattern forming method.

FIG. 2 is a schematic configuration diagram illustrating an example of a plasma display panel.

FIG. 3 is a process chart for explaining a second embodiment of the first invention of the pattern forming method.

FIG. 4 is a process chart for explaining the first embodiment of the second invention of the pattern forming method.

FIG. 5 is a process chart for explaining a second embodiment of the second invention of the pattern forming method.

FIG. 6 is a process chart for explaining a first embodiment of the third invention of the pattern forming method.

FIG. 7 is a process chart for explaining the first embodiment of the third invention of the pattern forming method.

FIG. 8 is a process chart for explaining a second embodiment of the third invention of the pattern forming method.

FIG. 9 is a process chart for explaining a second embodiment of the third invention of the pattern forming method.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Pattern forming body 4, 6 ... Pattern 11, 21, 31 ... Composite sheet 12, 22, 32 ... Transfer base material sheet 13, 33 ... Release film 14, 24 ... Photosensitive resin layer 34 ... 1st photosensitive resin Layer 36: Second photosensitive resin layer 25, 35 ... Pattern forming layer M, M '... Photomask

Claims (3)

[Claims] A first step of forming a composite sheet including at least a photosensitive resin layer adjacent to the release film between a transfer base sheet and a release film; A second step of exposing the resin layer, a third step of removing and developing the photosensitive resin layer together with the release film in a predetermined pattern by peeling the release film, and a predetermined pattern on the composite sheet. A fourth step of forming a pattern by pressing the pattern-formed body to the remaining photosensitive resin layer in step (1), peeling off the transfer base sheet, and then firing the pattern. . 2. A first step of laminating at least a photosensitive resin layer and a pattern forming layer on a transfer base sheet to form a composite sheet, and patterning the composite sheet so that the pattern forming layer side faces the composite sheet. A second step of exposing the photosensitive resin layer through a predetermined photomask, exposing the photosensitive resin layer together with the transfer base sheet by peeling the transfer base sheet; A third step of removing and developing with a pattern, forming a pattern by performing sandblasting on the pattern forming layer using the photosensitive resin layer remaining in a predetermined pattern on the pattern forming layer as a mask, and then firing the pattern; A pattern forming method, comprising: 3. A first photosensitive resin layer adjacent to the transfer substrate sheet between the transfer substrate sheet and the release film; a pattern forming layer laminated on the first photosensitive resin layer; A first step of forming a composite sheet including at least a second photosensitive resin layer adjacent to a release film; and a second step of exposing the second photosensitive resin layer from the release film side via a predetermined photomask. And a third step of removing and developing the second photosensitive resin layer together with the release film in a predetermined pattern by peeling the release film; and the third step remaining in the composite sheet in a predetermined pattern. A fourth step of pressing the pattern-formed body to the second photosensitive resin layer and exposing the first photosensitive resin layer from the transfer base sheet side via a predetermined photomask; A fifth step of removing and developing the first photosensitive resin layer together with the transfer base sheet in a predetermined pattern by peeling, the first photosensitive resin layer remaining in a predetermined pattern on the pattern forming layer; A sixth step of forming a pattern by subjecting the pattern formation layer to sandblasting using a resin layer as a mask and then firing the pattern formation layer to form a pattern.