JPH09245629A - Pattern forming material, thick film pattern forming method and plasma display panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make effective a crack and etching and form a high accurate thick film pattern, by applying a forming material of resin component and inorganic component of specific proportion. SOLUTION: A pattern forming material of a first layer 2 composed of 0.5 to 4wt.% resin component and an inorganic component is applied in an after drying condition on a substrate 1. Ratio of this resin component is effective for efficiency of cracking and etching work of the first layer 2. The inorganic component is mainly composed of a fire resisting filler non-softened at a 450 to 600 deg.C burning temperature and low boiling point glass powder fluidized to be secured. Next, a prescribed pattern is printed by a printing method on the first layer 2, to be dried with a solvent removed, a second layer 3 is formed. Here, the resin component after drying is 5 to 100wt.%. Next, the second layer 3 applies a resist mask, exposed first layer 2 is removed by etching, by burning at 500 to 600 deg.C, a layered structure pattern 4 of the first/second layers 2, 3 is formed. In this way, a high accurate thick film pattern can be formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pattern forming material, a thick film pattern forming method and a plasma display panel, and more particularly to high precision electrodes, resistors and the like in the manufacturing process of image display devices, thermal heads, integrated circuits and the like. TECHNICAL FIELD The present invention relates to a pattern forming material for forming a thick film pattern, a method for forming a highly accurate thick film pattern using this pattern forming material, and a plasma display panel having a highly accurate barrier.

[0002]

2. Description of the Related Art A plasma display panel (PDP) which is a gas discharge panel is provided with a pair of electrodes, which are regularly arranged, on two facing glass substrates, and Ne, He, Xe and the like are mainly disposed between them. The structure is filled with rare gas. Then, a voltage is applied between these electrodes, and a discharge is generated in minute cells around the electrodes, so that each cell emits light and display is performed.
In order to display information, cells arranged regularly are selectively (II) discharged by discharge. There are two types of PDP, a direct current type (DC type) in which the electrodes are exposed in the discharge space and an alternating current type (AC type) in which the electrodes are covered with an insulating layer. Both types are different in display function and driving method. Furthermore, it is further classified into a refresh drive system and a memory drive system.

In the DC type PDP and the AC type PDP, each cell is formed by holding two glass substrates facing each other by a barrier. Such a barrier is to maximize the display discharge space and obtain high-luminance light emission.
It is required to cut perpendicularly to the glass substrate and to have a narrow width and a sufficient height. Especially high-definition PD
In P, for example, the width is 30 to 5 with respect to the height of 100 μm.
A high aspect ratio barrier such as 0 μm is required.

Conventionally, in the PDP manufacturing process, a barrier having a predetermined pattern has been formed by screen printing. In the screen printing, the limit of the film thickness that can be formed by one printing is several tens of μm, so it is necessary to repeat printing and drying a large number of times, generally 10 times or more.
However, in general, the coating film formed by screen printing has a convex shape in which the peripheral portion is lowered, and when overprinting is performed many times as described above, the dripping of the coating liquid in the peripheral portion of the pattern is accumulated. There is a problem that the bottom surface has a wide cross-sectional shape. Therefore, it has been difficult to form a barrier having the required high aspect ratio by screen printing.

In order to solve such a problem, a barrier forming method using a subtractive method has been proposed (Electronic Material No. 11, P138 (1983)). In this barrier formation method, after forming a barrier formation layer, a subtractive resist pattern is formed on this layer by printing or photolithography, and the barrier formation layer exposed in the resist opening is removed to form a barrier. To form. As a method of removing the barrier forming layer, there is a so-called sand blast method in which a compressed gas mixed with fine particles is jetted at high speed to perform physical etching. By using this sandblast method, it is cut perpendicular to the substrate, and
The barrier forming layer can be processed into a desired shape having a narrow width and a sufficient height.

The method of forming a barrier (thick film pattern) using the above sandblasting method is generally performed as follows.

A barrier forming layer is provided on a glass substrate using a barrier forming material containing a glass component and a resin binder as main components. A resist mask is formed on this barrier forming layer by photolithography using a photosensitive material. The barrier forming layer exposed in the opening of is removed by sandblasting. The resist mask is removed by stripping with a stripping solution. The patterned barrier forming layer is baked to fuse the contained glass components to form a barrier. Form (thick film pattern)

[0008]

However, the barrier formation method using the sandblast method as described above has the following problems. (1) Since the resist mask is formed by using the photo process, the apparatus is expensive and the manufacturing cost is high. (2) In order to reduce the thermal deformation of the glass substrate, it is necessary to lower the firing temperature in the above step as much as possible. However, if the glass component in the barrier forming material is made to have a low softening temperature, the barrier forming layer will not contain alkali or alkali. Becomes unstable to water,
The glass component of the patterned barrier forming layer is damaged in the above resist mask peeling step, making it difficult to form a highly accurate pattern.

In order to solve the above-mentioned problem (2), it is conceivable to remove the resist mask by firing in the firing furnace in the above step, instead of a wet method using a stripping solution. However, in the conventionally used photoresist, the carbide remains and adheres on the glass substrate in such baking removal,
Good removal of the resist mask is difficult, and further, carbides generated during firing removal are deposited in the firing furnace and adhere to the substrate when the firing furnace is used in other steps, resulting in defective products. There was also a problem.

Further, in order to solve the above-mentioned problem (1), a barrier forming method has been disclosed in which a resist mask is formed by a printing method without using photolithography (JP-A-6-36683). . Although such a barrier formation method can certainly reduce the manufacturing cost, the resist mask material used cannot be peeled off well in the firing step. Therefore, it is necessary to remove the resist mask by a wet method, which causes the same problem as in the case of using photolithography.

The present invention has been made in view of the above circumstances, and includes a pattern forming material which has a function as a resist mask and does not require a wet-type stripping step.
An object of the present invention is to provide a thick film pattern forming method capable of forming a highly accurate thick film pattern such as an electrode and a resistor using this pattern forming material, and a plasma display panel having a highly accurate barrier. And

[0012]

In order to achieve such an object, the pattern forming material of the first invention contains at least a resin component, and the resin component is 5 to 5 in a dry state of the pattern forming material. It was contained so as to occupy 100% by weight, and was configured to volatilize or decompose by baking at 600 ° C. or less.

Further, the composition is such that it contains an inorganic powder having a softening temperature of 450 to 600 ° C., and the dynamic viscosity is in the range of 500 to 4000 poise.

In such a pattern forming material of the present invention, the resin component contained in the range of 5 to 100% by weight in a dried state exhibits appropriate flexibility and imparts etching resistance to the pattern forming material. And, this resin component is 60
Since it is volatilized or decomposed by baking at 0 ° C. or lower, it can be removed by baking in the baking step, and when inorganic powder is contained, fusion occurs at this time and becomes a part of the thick film pattern. Also, by setting the dynamic viscosity to 500 to 4000 poise, it becomes possible to form a fine pattern having a thickness of 3 μm or more.

The thick film pattern forming method of the second invention uses a first layer forming material containing at least a resin component and an inorganic component, wherein the resin component accounts for 0.5 to 4% by weight.
A first step of forming a layer on a substrate, and a second step of forming a second layer in a predetermined pattern on the first layer by using the pattern forming material as described above as a second layer forming material.
And a third step of forming a pattern having a laminated structure of the first layer and the second layer by removing the exposed first layer by an etching method using the second layer as a resist mask.
A fourth step of baking the pattern at a temperature of 0 to 600 ° C. to form a thick film pattern and fixing the thick film pattern to a substrate;
And a process.

The etching method in the third step is a sandblast method.

Further, the printing method of the second step is an intaglio offset printing method using an intermediate transfer medium, and further, at least the outermost surface of the intermediate transfer medium is a silicone resin whose main component is a dimethylsiloxane unit. And
A configuration in which the transfer rate of the second layer forming material is 100% when the second layer forming material is transferred onto the first layer to form the second layer, and is used for the intaglio offset printing method. The plate depth of the intaglio plate was 10 to 50 μm.

The printing method in the second step is a screen printing method.

Further, the thickness of the second layer after drying is 3 to.
The structure is such that it is 50 μm.

In such a thick film pattern forming method of the present invention, after the pattern having the laminated structure of the first layer and the second layer is formed in the third step, the conventional resist mask removing step is omitted and the baking step is performed. Directly move to the fourth step,
In the third step, the resin component is baked and removed from the second layer that has acted as a resist mask, and the inorganic component is fused to integrate the first layer and the second layer into a thick film pattern.

The plasma display panel of the third invention is constructed such that the barrier forming the display discharge space is formed by any of the thick film pattern forming methods described above.

In such a plasma display panel of the present invention, the barrier can be cut vertically to the glass substrate and can have a narrow width and a sufficient height.

[0023]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The preferred embodiments of the present invention will be described below.

The pattern forming material of the present invention contains at least a resin component, and the resin component is contained so as to account for 5 to 100% by weight in the pattern forming material in a dry state, and is 600 ° C. or less. It is one that is volatilized or decomposed by firing, for example, firing in the range of 300 to 600 ° C. The pattern forming material of the present invention further contains an inorganic powder having a softening temperature of 450 to 600 ° C.

The resin component constituting the pattern forming material of the present invention does not volatilize and decompose by baking at a low temperature of 600 ° C. or less as described above, and does not leave a carbide in the pattern material. Examples of such resin components include cellulose resins, polymethacrylic acid esters, poly-α-methylstyrene, polyvinyl alcohol, polybutene and the like. However, when a pattern forming material of the present invention is printed on a substrate using an intaglio offset printing method via an intermediate transfer medium described below, when a high molecular weight resin is used as a resin component, a low molecular weight resin is contained in the pattern forming material. It becomes necessary to contain a large amount of the above solvent, and the on-machine stability of the pattern forming material deteriorates,
Swelling of the intermediate transfer medium occurs, which is not preferable. Therefore, as the resin component, an oligomer that is liquid at room temperature is preferable, and when a low molecular weight resin is used, a resin having a molecular weight of 100 or more is preferable.

The above-mentioned resin component has a volatilization and decomposition temperature of 600.
If the temperature exceeds ℃, the firing temperature for removing the resin component becomes high, and for example, when forming a thick film pattern on a glass substrate used for a plasma display panel or the like, thermal deformation may occur in the glass substrate. It is not preferable. On the other hand, the lower limit of the volatilization and decomposition temperature of the resin component is not particularly limited. Volatilization and decomposition temperature lower limit of 30
It is preferable to set the temperature to about 0 ° C. Further, if the resin component in the dry pattern forming material is less than 5% by weight, the flexibility of the pattern forming material becomes insufficient, and good etching resistance cannot be obtained.

The inorganic powder that can be used in the pattern forming material of the present invention is mainly composed of an inorganic powder such as low softening temperature glass powder that flows and sticks to each other during firing. In addition to these inorganic powders, ceramic powders such as alumina and zirconia that do not soften during firing can also be used. The content of such inorganic powder in the pattern forming material is preferably in the range of 0 to 1900 parts by weight with respect to 100 parts by weight of the resin component. The amount of the inorganic powder having a softening temperature of 450 to 600 ° C. in all the inorganic components is preferably about 0 to 50% by weight. Such an inorganic powder causes fusion when the resin component volatilizes or decomposes by firing at 500 to 600 ° C., and the fused inorganic component exists in the pattern forming material after firing. However, the traces of the resin component and the carbides do not remain. If the softening temperature of the inorganic powder exceeds 600 ° C., it is necessary to increase the firing temperature. For example, when forming a thick film pattern on a glass substrate used for a plasma display panel or the like, the glass substrate is not thermally deformed. It is not desirable because it will occur. On the other hand, if the temperature is lower than 450 ° C, the inorganic component is fused before the resin component is completely decomposed and volatilized, so that voids are likely to occur, which is not preferable. Furthermore, in the production of the plasma display panel described later, about 45
Since the sealing is performed at 0 ° C., it is not preferable to use the inorganic powder having a low softening temperature.

The pattern forming material of the present invention as described above is
Mixing the above-mentioned resin component and inorganic powder in a solvent of low volatility,
It can be kneaded by a roll mill to obtain a paste-like coating solution, or can be kneaded by a ball mill or the like to obtain a slurry-like coating solution. Examples of the low volatility solvent used include triethylene glycol monobutyl ether, triethylene glycol, polyethylene glycol, polypropylene glycol, dioctyl phthalate, diisodecyl phthalate.

Next, the thick film pattern forming method of the present invention will be described with reference to the drawings. The thick film pattern referred to in the present invention refers to a film obtained by applying a coating material in which a powder of metal, ceramics, glass or the like is dispersed in a resin component and sintering it. Does not mean a large membrane.

FIG. 1 is a drawing for explaining the thick film pattern forming method of the present invention. In the thick film pattern forming method of the present invention, first, as a first step, as shown in FIG. 1 (A), a first layer 2 is formed on a substrate 1. This first layer 2
Is formed using a known coating means such as screen printing, blade coating, comma coating, reverse roll coating, spray coating, gun coating, extrusion coating, lip coating and the like using the first layer forming material. Alternatively, the first layer forming material may be applied onto the film by the applying means, and the applied film may be transferred onto the substrate 1 to form the first layer 2. By using such a transfer method, it is possible to form the first layer 2 in a pattern only on a necessary portion, and the film thickness accuracy and the surface smoothness are improved.
The thickness of the first layer 2 thus formed can be appropriately set according to the thickness of the target thick film pattern.

The first layer forming material contains a resin component and, if necessary, an inorganic component and the like, and the resin component occupies 0.5 to 4% by weight in a dried state. The resin component is 0.
If it is less than 5% by weight, the stability of the coating liquid of the first layer forming material is poor, and cracks occur in the first layer formed by drying after coating, which is not preferable. On the other hand, if the resin component exceeds 4% by weight, the efficiency of the etching process in the third step, which will be described later, deteriorates, which is not preferable.

The resin component used is one that does not cause carbides to remain in the pattern material by burning, decomposing or vaporizing by firing at low temperature. Examples of such a resin component include ethyl cellulose, methyl cellulose, nitrocellulose, cellulose acetate, cellulose propionate, cellulose butyrate, and other cellulose resins, methyl (meth) acrylate, ethyl (meth) acrylate, normal butyl (meth) acrylate. , Isobutyl (meth) acrylate, isopropyl (meth) acrylate, 2-ethylmethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, etc., or poly (meth) acrylic acid esters composed of these copolymers , Poly-α-methylstyrene, polyvinyl alcohol, polybutene and the like.

The inorganic components contained in the first layer forming material are mainly composed of a refractory filler that does not soften during firing and a low melting point glass powder that flows and adheres to each other during firing. .

The low-melting glass powder contains, for example, 50% by weight or more of PbO for a barrier of PDP, has the effect of preventing the phase separation of glass, adjusts the softening temperature, and has a thermal expansion coefficient of glass substrate. To match
Al ₂ O ₃ , B ₂ O ₃ , SiO ₂ , MgO, CaO, S
It is preferable to use a material containing rO, BaO, or the like.

The refractory filler is 500 to 600.
Materials that do not soften at a firing temperature of about ° C can be widely used, and examples of materials that can be obtained at low cost include ceramic powders such as alumina, magnesia, zirconia, calcia, cordierite, silica, and mullite.

The content of the low melting point glass powder in the inorganic component is preferably 30 to 70% by weight. When the content of the low melting point glass powder exceeds 70% by weight, the shape retention by firing is deteriorated, the debinding property is impaired, and the denseness is deteriorated, which is not preferable. If the content of the low-melting glass powder is less than 30% by weight, the gap between the refractory fillers cannot be sufficiently filled, the denseness is deteriorated and the mechanical strength after firing is lowered, and the panel is sealed in a PDP. Causes a chipping. The content of such an inorganic component in the first layer forming material is 0 to 2 with respect to 100 parts by weight of the resin component.
A range of 400 parts by weight is preferred.

In the first layer forming material for the barrier of the PDP, in order to reduce the reflection of external light of the PDP and raise the practical contrast, the barrier formed by containing a black pigment is made black. You can In this case, the black pigment used is Co-Cr-Fe, Co-Mn-Fe, Co.
-Fe-Mn-Al, Co-Ni-Cr-Fe, Co-
Ni-Mn-Cr-Fe, Co-Ni-Al-Cr-F
e, fire resistant black pigments such as Co-Mn-Al-Cr-Fe-Si are preferred. On the other hand, for the purpose of effectively guiding the light emission of the phosphor to the front surface of the panel, the barrier formed by containing a white pigment can be made white. In this case, the white pigment used is preferably a fire-resistant white pigment such as titania.

Further, in the material for forming the first layer, a plasticizer, a surface active agent, an antifoaming agent, an antioxidant and the like are used as additives, if necessary. Among them, as the plasticizer, phthalic acid esters, sebacic acid esters, phosphoric acid esters, adipic acid esters, glycolic acid esters,
Citrate esters and the like are generally used. If the addition rate of the plasticizer is too high, the flexibility of the resin component increases too much, and the etching rate by the sand blast method described later becomes slow. Therefore, the addition amount of the plasticizer is 1 / weight ratio to the resin component.
It is preferably 5 or less.

Further, the first layer forming material may contain a solvent which is a good solvent for the resin component used, for example, terpionate, butyl carbitol acetate and the like. The solvent is selected mainly by considering the volatility of the solvent and the solubility of the resin component used. When the solubility of the solvent in the resin component is low, the viscosity of the first layer forming material becomes high even if the solid content ratio is the same, and the suitability for coating is deteriorated, which is not preferable. Further, the content of the solvent is such that bubbles in the first layer forming material can be removed, the leveling is good, the smoothness of the coating film is good, and the dispersed particles in the first layer forming material are It can be set such that the sedimentation is slow and the composition is stable, and the energy and time required for drying can be reduced, and for example, about 25 to 50% by weight is preferable.

The above-mentioned first layer forming material can be obtained by dispersing and mixing a mixture of a resin component with necessary inorganic components, solvents and additives by a ball mill. in this case,
Inorganic components (low melting point glass powder and refractory filler) in a solution in which a resin component is dissolved in a solvent and additives are added as necessary.
After making a mixture by mixing, the mixture is dispersed and blended in a ball mill, but ceramic balls are used to avoid mixing of impurities, and more preferably, a ball mill whose inner wall is coated with ceramics or plastic is used. . Then, after dispersion and blending, defoaming is performed under reduced pressure using a vacuum stirrer.

Next, in the second step, the above-mentioned pattern forming material of the present invention is used as the second layer forming material, and a predetermined pattern is printed on the first layer 2 by a printing method and dried to remove the solvent. To form the second layer 3 (see FIG. 1).
(B)). After drying, the second layer has an appropriate flexibility because the resin component occupies 5 to 100% by weight as described above, and exhibits excellent etching resistance against etching by the sandblast method described later. . The thickness of such a second layer 3 is preferably about 3 to 50 μm. Second layer 3
If the thickness is less than 3 μm, sufficient etching resistance cannot be obtained, and if it exceeds 50 μm, the edge accuracy of the pattern is lowered and the uniformity of the film thickness is further deteriorated. Further, the width of the pattern of the second layer 3 can be appropriately set in the range of 30 to 300 μm according to the target thick film pattern.

Examples of the printing method for forming the second layer 3 include screen printing, intaglio printing, intaglio offset printing, lithographic offset printing, letterpress printing, letterpress offset printing and the like. 3-5
Intaglio offset printing and screen printing are particularly preferable as a method for stably forming the second layer having a film thickness of about 0 μm.

FIG. 2 is a diagram for explaining the formation of the second layer by intaglio offset printing via the intermediate transfer medium in the second step. In FIG. 2, first, the recess 11a of the flat plate-shaped intaglio 11 is filled with the second layer forming material 12 comprising the pattern forming material of the present invention using a doctor, and the intaglio 11 is covered with a blanket cylinder which is an intermediate transfer medium. 21 is rolled (FIG. 2 (A)). The blanket cylinder 21 is provided with a blanket 22 on its peripheral surface, and
The second layer forming material 12 is transferred from 1a onto the blanket 22. It is preferable that the intaglio 11 enhances the durability of the doctor blade and is excellent in the transferability of the second layer forming material 12 to the blanket 22, and for example, glass, metal, or a composite thereof can be used. Further, the doctor blade is required to have scraping property and durability, and SUS is preferable as a material. Next, the blanket cylinder 21 is rolled on the first layer 2 formed on the substrate 1 to transfer the second layer forming material 12 from the blanket 22 onto the first layer 2 to form the second layer 3. Transfer formation (Fig. 2)
(B)). In this case, at least the outermost surface of the blanket 22 is formed of a silicone resin containing a dimethylsiloxane unit as a main component, and the dynamic viscosity (1
By the 0H _z) in the range of 500～4000Poise, the metastasis rate of the second layer forming material 12 from the upper blanket 22 to the first layer 2 above it can be 100%. Further, the depth (plate depth) of the recess 11a of the intaglio 11 is 10 μm or more, preferably 10 to 50 μm, and the second layer forming material 1
2 dynamic viscosity of (10H _z) 500~4000poise
By setting the range of 3 to 50 μm as described above,
m second layer can be formed. Second layer forming material 1
When 2 Dynamic viscosity (10H _z) is less than 500Poise, metastasis rate of the second layer forming material 12 from the upper blanket 22 to the first layer 2 above is lowered, the blanket 22 from the intaglio 11 exceeds 4000poise Second layer forming material 1
It is not preferable because the transfer of No. 2 becomes worse and some scratches are left on the intaglio plate 11 during doctoring.

When the second layer 3 is formed by the screen printing method, the screen used is 100 to 50.
About 0 mesh is preferable.

Next, in a third step, the second layer 3 is used as a resist mask and the exposed first layer 2 is removed by an etching method to form a laminated structure of the first layer 2 and the second layer 3. A pattern is formed (FIG. 1C). As the etching method, a so-called sandblast method is preferable, in which a compressed gas mixed with fine particles is jetted at high speed to physically perform etching.

Then, as a fourth step, 500 to 600
The pattern composed of the first layer 2 and the second layer 3 is formed into a thick film pattern 4 by firing at a temperature of ℃ (FIG. 1D). In the fourth step, the resin component contained in the second layer 3 is volatilized or decomposed together with the resin component contained in the first layer 2 and removed without leaving any carbide. Also, the second
When the layer 3 contains inorganic powder, the second layer is formed by firing.
The inorganic powder contained in the layer 3 causes fusion, and also fuses with the inorganic component of the first layer 2 which also causes fusion. This allows
The second layer 3 acting as a resist mask in the above-mentioned third step can be removed without passing through a wet-type peeling step, and the formed thick film pattern layer 4 is fixed to the substrate 1 with sufficient strength. To be done.

Next, the plasma display panel of the present invention will be described.

FIG. 3 is a schematic configuration diagram showing an AC type plasma display panel (PDP) which is an embodiment of the plasma display panel of the present invention, and shows a state in which the front glass substrate and the rear glass substrate are separated from each other. is there. In FIG. 3, the PDP 31 has a front glass substrate 32 and a rear glass substrate 33 arranged in parallel to each other and facing each other, and a barrier 34 is provided on the front side of the rear glass substrate 33 so as to stand thereon. The barrier glass 34 holds the front glass substrate 32 and the rear glass substrate 33 at regular intervals. This barrier 34 normally has a height H of 30-
The width W is set to 300 μm and the width W is set to 30 to 300 μm, and the aspect ratio H / W is set to about 0.1 to 10.
Then, on the back side of the front glass substrate 32, a composite electrode including a sustain electrode 35 which is a transparent electrode and a bus electrode 36 which is a metal electrode is formed in parallel with each other, and a dielectric layer 37 is formed so as to cover the composite electrode. And a MgO layer 3 on top of it
8 are formed. Address electrodes 39 are formed on the front side of the rear glass substrate 33 so as to be orthogonal to the composite electrodes and between the barriers 34, and address electrodes 39 are formed in parallel with each other, and further cover the wall surface of the barrier 34 and the bottom surface of the cell. And a phosphor layer 40 is provided. In this AC type PDP, by applying a predetermined voltage from an AC power source between the composite electrodes on the front glass substrate 32 to form an electric field, the front glass substrate 32, the rear glass substrate 33, and the barrier 34 are partitioned. Discharge is performed in each cell as a display element. And
The phosphor layer 40 is caused to emit light by the ultraviolet rays generated by this discharge, and the observer visually recognizes this light transmitted through the front glass substrate 32.

The barrier 34 in the plasma display panel having such a structure is formed on the front glass substrate 32 by the above-described pattern forming method of the present invention. Therefore, the barrier 34 can have a high aspect ratio as described above, and a high brightness and high definition plasma display panel can be realized.

[0050]

Next, the present invention will be described in more detail with reference to examples. (Example 1) First, Ag was placed on a glass substrate having a thickness of 2 mm.
The electrode pattern was formed by firing using a thick film paste.

Next, as a first step, a barrier paste having the following composition as a first layer forming material is applied on a glass substrate having an electrode pattern formed thereon by a reverse roll coater, and is heated at 100 ° C. by a hot plate at 30 ° C. After drying for 1 minute, it was further dried at 170 ° C. for 20 minutes to form a first layer having an average film thickness of 150 μm (corresponding to FIG. 1A).

Composition of barrier paste : Glass frit (KF6274 manufactured by Iwaki Glass Co., Ltd.) 80 parts by weight Ethyl cellulose (Etocel STD100 manufactured by Dow Chemical Co.) 1 part by weight Butyl carbitol acetate 19 parts by weight The pattern forming materials having the following nine types (A to I) of compositions were prepared. The dynamic viscosity (1
It is shown in Table 1 0H _z) below.

Composition of pattern forming material A : Ethyl cellulose (N-22 manufactured by Hercules) (decomposition temperature 400 ° C.) 10 parts by weight Polyethylene glycol monomethacrylate (M40G manufactured by Shin-Nakamura Chemical Co., decomposition temperature 560 ° C.) 90 parts by weight-Glass frit (average particle diameter 4 μm, softening temperature 480 ° C.) (KF6274 manufactured by Iwaki Glass Co., Ltd.) 50 parts by weight Composition of pattern forming material B Maleated polybutene (MPB manufactured by NOF Corporation) ( Decomposition temperature 480 ° C.) 50 parts by weight Glass frit (average particle size 4 μm, softening temperature 480 ° C.) (KF6274 manufactured by Iwaki Glass Co., Ltd.) 50 parts by weight Composition of pattern forming material C Acrylic resin (decomposition temperature 550 ° C. ) (Polyflow No. 3 manufactured by Kyoeisha Yushi Co., Ltd.) 95 parts by weight ・ Glass frit (average particle size 4 m, a softening temperature of 480 ° C.) (Matsunami Glass Co., Ltd. MB-13) ... 5 parts by weight pattern forming material composition Polyethylene glycol monomethacrylate D (Shin-Nakamura Chemical Co., Ltd. M40G, decomposition temperature 560 ° C.) ... 80 Parts by weight Methacrylic resin (decomposition temperature 330 ° C.) (BR105 manufactured by Mitsubishi Rayon Co., Ltd.) 20 parts by weight Composition of pattern forming material E Triethylene glycol monobutyl ether 94 parts by weight β-methacryloyloxyethylene hydrogen phthalate ( Shin Nakamura Chemical Co., Ltd. CB-1, decomposition temperature 390 ° C.) 1 part by weight Methacrylic resin (decomposition temperature 330 ° C.) (Mitsubishi Rayon Co., Ltd. BR 105) 5 parts by weight Composition of pattern forming material F Ethylene glycol monobutyl ether… 94 parts by weight β-methacryloyloxyethyl Renhydrodiene phthalate (CB-1 manufactured by Shin Nakamura Chemical Co., Ltd., decomposition temperature 390 ° C.) 2 parts by weight Methacrylic resin (decomposition temperature 330 ° C.) (BR105 manufactured by Mitsubishi Rayon Co., Ltd.) 3.5 parts by weight pattern Composition of forming material G Polybutene (3N manufactured by NOF CORPORATION, decomposition temperature 450 ° C.) 50 parts by weight Glass frit (average particle size 4 μm, softening temperature 480 ° C.) (KF6274 manufactured by Iwaki Glass Co., Ltd.) 50 Parts by weight Composition of pattern forming material H Polybutene (200N manufactured by NOF CORPORATION, decomposition temperature 460 ° C.) 50 parts by weight Glass frit (average particle size 4 μm, softening temperature 480 ° C.) (KF6274 manufactured by Iwaki Glass Co., Ltd.) ) 50 parts by weight Composition of pattern forming material I Triethylene glycol monobutyl ether 40 parts by weight Ethyl cellulose ( Hercules N-200, decomposition temperature 400 ° C.) 10 parts by weight Glass frit (average particle size 4 μm, softening temperature 480 ° C.) (Iwaki Glass Co., Ltd. KF6274) 50 parts by weight Next, as a second step. , The pattern forming material (A to
Using I) as the second layer forming material, printing on the first layer by an intaglio offset printing machine and drying at 80 ° C. for 5 minutes,
A second layer was formed in a stripe pattern having a line width of 80 μm and a pitch of 220 μm (corresponding to FIG. 1B). The intaglio plate used here is a soda lime glass plate on which recesses having the depths shown in Table 1 below are formed by etching.
As the intermediate transfer medium, a blanket cylinder equipped with a blanket produced by casting a room temperature curing type silicone rubber on a polyester film was used. The thickness of the formed second layer and the content of the resin component are shown in Table 1 below.

Then, in the third step, the first layer is formed by the sandblast method under the following conditions using the second layer as a resist mask.
The unnecessary portion of the layer was removed by etching (corresponding to FIG. 1C). Table 1 below shows the etching amount of the first layer / the etching amount of the second layer (relative blast ratio) in this etching.

Etching conditions -Distance between nozzle and substrate surface: 8 cm-Abrasive material: Brown fused alumina # 1000-Spout pressure: 3 kg / cm ² -Etching time: 35 minutes Next, as the fourth step, the peak temperature was 560 ° C. And baking (peak temperature holding time 20 minutes) to remove the resin component of the second layer which has acted as a resist mask by baking.
The first layer and the second layer are integrated and a thick film pattern (barrier) is fixedly formed on a glass substrate (corresponding to FIG. 1D).
I got ~ 11.

The evaluation results of the thick film pattern (barrier) thus formed are shown in Table 1 below.

[0057]

[Table 1] As shown in Table 1, the decomposition temperature is 60 in the second layer.
0 ℃ next following 5 to 95% by weight resin component is in the range of (300 to 600 ° C.), the dynamic viscosity (10H _z) 50
The samples (1 to 2, 4 to 7) using the pattern forming material in the range of 0 to 4000 poise and the intaglio having the plate depth of 10 to 50 μm can be processed with a high relative blast ratio in the third step. Yes, and the average line width at the top is about 40μ.
It was possible to form a good thick film pattern (barrier) having a height of about 120 m and a height of about 120 μm and high surface smoothness. In addition, disconnection of the electrode pattern did not occur.

On the other hand, in Sample 3 using the intaglio plate having a plate depth of 8 μm, the thickness of the second layer was 2 μm, the relative blast ratio was as low as 90, and the thick film pattern (barrier) had large unevenness. became. Further, in the sample 8 using the pattern forming material F in which the resin component in the second layer is 3.5% by weight, the relative blast ratio is 90 and the action as the resist mask of the second layer is insufficient, resulting in a thick film. Pattern (barrier)
Became uneven.

[0059] On the other hand, dynamic viscosity (10H _z) is 500po
In Sample 9 using the pattern forming material G of less than ise (450 poise), although the relative blast ratio was large, unevenness was observed in the thick film pattern (barrier) and ink residue was generated on the blanket. Furthermore, the dynamic viscosity (10H
_z ) exceeds 4000 poise (6000 poise, 45
In samples 10 and 11 using the pattern forming materials H and I of (00 poise), scratches are left during the doctor ring in the intaglio, and scumming occurs during the formation of the second layer, resulting in a good thick film pattern (barrier). Could not be formed. Comparative Example 1 First, in the same manner as in the first step of Example 1,
An Ag electrode pattern was formed on a glass substrate having a thickness of 2.2 mm, and a first layer having an average film thickness of 150 μm was further formed.

Next, a pattern forming material having the following composition was prepared.

Composition of pattern forming material : Ethyl cellulose (N-10 manufactured by Hercules Co., decomposition temperature 390 ° C.) 26 parts by weight Toluene 52 parts by weight Ethanol 12 parts by weight Dibutyl phthalate 10 parts by weight Using the pattern forming material as the second layer forming material, printing on the first layer by an intaglio offset printing machine and drying at 80 ° C. for 5 minutes, line width 80 μm, pitch 22
An attempt was made to form the second layer in a stripe pattern of 0 μm. The intaglio plate used was a soda lime glass plate having 20 μm deep recesses formed by etching. As the intermediate transfer medium, a blanket cylinder equipped with a blanket produced by casting a room temperature curing type silicone rubber on a polyester film was used.

However, the solvent component of the pattern forming material was absorbed by the silicone rubber of the blanket, the pattern forming material was solidified on the blanket, and it was impossible to transfer and form the second layer. (Example 2) First, as the first step, as in the first step of Example 1, an Ag electrode pattern was formed on a glass substrate having a thickness of 2.2 mm, and the first film having an average film thickness of 150 μm was formed.
A layer was formed.

On the other hand, pattern forming materials having the following six types (I to VI) of compositions were prepared.

Composition of pattern forming material I : Ethyl cellulose (N-22 manufactured by Hercules, decomposition temperature 400 ° C.) 10 parts by weight Butyl carbitol acetate (volatilization temperature 170 ° C.) 40 parts by weight Glass frit (average particle size) 4 μm, softening temperature 480 ° C. (KF6274 manufactured by Iwaki Glass Co., Ltd.) 50 parts by weight Composition of pattern forming material II butyl carbitol acetate (volatilization temperature 170 ° C.) 20 parts by weight Methacrylic resin (decomposition temperature 330 ° C.) (BR105 manufactured by Mitsubishi Rayon Co., Ltd.) 10 parts by weight Glass frit (average particle size 4 μm, softening temperature 480 ° C.) KF6274 manufactured by Iwaki Glass Co., Ltd. 70 parts by weight Composition of pattern forming material III , ethyl cellulose (hercules) N-200 manufactured by the company, decomposition temperature 400 ° C) 10 parts by weight butyl Carbitol acetate (volatilization temperature 170 ° C.): 80 parts by weight Glass frit (average particle size: 4 μm, softening temperature: 480 ° C.) (Matsunami Glass Co., Ltd. MB-13): 10 parts by weight Composition of pattern forming material IV: Ethyl cellulose (N-200 manufactured by Hercules, decomposition temperature 400 ° C.) 7 parts by weight Butyl carbitol acetate (volatilization temperature 170 ° C.) 83 parts by weight Glass frit (average particle size 4 μm, softening temperature 480 ° C.) (Iwaki glass ( KF6274 manufactured by K.K.) 10 parts by weight Composition of pattern forming material V Ethyl cellulose (N-22 manufactured by Hercules, decomposition temperature 400 ° C) 4.2 parts by weight Butyl carbitol acetate (volatilization temperature 170 ° C) 15 8 parts by weight ・ Glass frit (average particle size 4 μm, softening temperature 480 ° C.) (K manufactured by Iwaki Glass Co., Ltd.) 6274) ... 80 parts by weight of the patterning material composition, ethylcellulose VI (Hercules Corp. N-22, decomposition temperature 400 ° C.) ... 3.4 parts by weight of butyl carbitol acetate (volatilization temperature 170 ° C.) ... 16.6 parts by weight Glass frit (average particle diameter 4 μm, softening temperature 480 ° C.) (KF6274 manufactured by Iwaki Glass Co., Ltd.) 80 parts by weight Next, as a second step, the above pattern forming material (I to
VI) was used as the second layer forming material, printed on the first layer by a screen printer and dried at 80 ° C. for 5 minutes to form the second layer in a stripe pattern having a line width of 80 μm and a pitch of 220 μm.

Then, as a third step, the third step of the first embodiment is performed.
Similar to the process, the unnecessary portion of the first layer was removed by etching by the sandblast method using the second layer as a resist mask.
In this etching, the etching amount of the first layer / second
The etching amount (relative blast ratio) of the layer is shown in Table 2 below.

Next, as the fourth step, the peak temperature 560
Baking at 20 ° C. (peak temperature holding time: 20 minutes) to remove the resin component of the second layer, which acted as a resist mask, to firmly form a thick film pattern (barrier) on the glass substrate. Obtained.

The evaluation results of the thick film pattern (barrier) thus formed are shown in Table 2 below.

[0068]

[Table 2] As shown in Table 2, the resin component having a decomposition temperature or a volatilization temperature of 600 ° C. or less in the second layer is 5 to 9
3μ using a pattern forming material such as 5% by weight
Samples (1 to 3, 5) on which the second layer having a thickness of m or more is formed
In the third step, a high relative blast ratio can be processed, and the top line width average is about 40 μm, the height is about 120 μm, and a good thick film pattern (barrier) with high surface smoothness without chipping can be formed. It was possible. In addition, disconnection of the electrode pattern did not occur.

On the other hand, in sample 4, the thickness of the second layer was 2.5 μm, the relative blast ratio was as low as 88, and the thick film pattern (barrier) had large unevenness. Further, in the sample 6 using the pattern forming material VI in which the resin component in the second layer is 4% by weight, the relative blast ratio is 9
When 0, the action as the resist mask of the second layer was insufficient, and the thick film pattern (barrier) had large unevenness.

[0070]

As described above in detail, according to the first aspect of the present invention, the resin component which volatilizes or decomposes at 600 ° C. or lower is contained so as to account for 5 to 100% by weight in the dried state. Since the pattern forming material is made to contain an inorganic powder having a melting point of 450 to 600 ° C. as needed, the pattern forming material after drying exhibits good etching resistance due to the resin component and functions as a resist mask. And the resin component can be removed by baking in the baking step, and the inorganic powder is fused and remains in the baking removal.

In the thick film pattern forming method of the second invention,
Since the first layer forming material containing at least a resin component and an inorganic component and the above pattern forming material are used as the second layer forming material, a pattern having a laminated structure of the first layer and the second layer is formed in the third step. After that, in the fourth step, which is the baking step, the resin component is baked and removed from the second layer that has acted as the resist mask in the third step to form a thick film pattern, and the inorganic powder contained in the second layer is also melted. It is applied and integrated with the first layer. As a result, the step of removing the resist mask by a wet method can be omitted, so that the step is simplified and a material that is easy to etch and has low mechanical strength can be used as the first layer forming material.
It is possible to reduce time, material and energy in etching. Further, as the inorganic component used in the first layer forming material and the pattern forming material, a material that is unstable to alkali and water but has a low-temperature fusion property can be used. It becomes possible to lower the temperature (600 ° C. or lower, for example, 300 to 600 ° C.) as compared with the film pattern forming method, and therefore, the deformation of the substrate is prevented, and the deviation of the total pitch is extremely large for a large-area substrate. It is possible to form a small thick film pattern. Further, since the photo process is not necessary, the cost can be significantly reduced.

According to the third invention, the barrier forming the display discharge space is cut up perpendicularly to the glass substrate, and
Since the width is narrow and the height is sufficient, a plasma display panel with high brightness and high definition is possible.

[Brief description of drawings]

FIG. 1 is a view for explaining a thick film pattern forming method of the present invention.

FIG. 2 is a diagram illustrating formation of a second layer by intaglio offset printing via an intermediate transfer medium in a second step.

FIG. 3 is a schematic configuration diagram showing an embodiment of a plasma display panel of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... 1st layer 3 ... 2nd layer 4 ... Thick film pattern 11 ... Intaglio 21 ... Blanket cylinder (intermediate transfer medium) 22 ... Blanket 31 ... Plasma display panel 34 ... Barrier

Claims (11)

[Claims] 1. At least a resin component is contained, and the resin component is 5 to 100% by weight in a dry state of a pattern forming material.
The pattern forming material is characterized in that it is contained so as to occupy, and is volatilized or decomposed by baking at 600 ° C. or lower. 2. The pattern forming material according to claim 1, which contains an inorganic powder having a softening temperature of 450 to 600 ° C. 3. The pattern forming material according to claim 1 or 2, wherein the dynamic viscosity is in the range of 500 to 4000 poise. 4. A first step of forming, on a substrate, a first layer containing a resin component and an inorganic component, the first layer forming material containing 0.5 to 4% by weight of the resin component. A second step of forming the second layer in a predetermined pattern on the first layer by a printing method using the pattern forming material according to any one of claims 1 to 3 as a second layer forming material; The third step of removing the exposed first layer by a etching method using the layer as a resist mask and forming a pattern having a laminated structure of the first layer and the second layer, and baking at 500 to 600 ° C. A thick film pattern forming method, comprising: a thick film pattern, and a fourth step of fixing the thick film pattern to a substrate. 5. The method for forming a thick film pattern according to claim 4, wherein the etching method in the third step is a sandblast method. 6. The thick film pattern forming method according to claim 4, wherein the printing method in the second step is an intaglio offset printing method using an intermediate transfer medium. 7. The intermediate transfer medium is a silicone resin having at least the outermost surface as a main component of a dimethylsiloxane unit, and transfers the second layer forming material onto the first layer to form a second layer. The method for forming a thick film pattern according to claim 6, wherein the transition rate of the second layer forming material is 100%. 8. The thick film pattern forming method according to claim 6, wherein the intaglio plate used in the intaglio offset printing method has a plate depth of 10 to 50 μm. 9. The thick film pattern forming method according to claim 4, wherein the printing method in the second step is a screen printing method. 10. The thickness of the second layer after drying is 3 to 50.
The thick film pattern forming method according to any one of claims 4 to 9, wherein the thickness is μm. 11. A plasma display panel, wherein a barrier forming a display discharge space is formed by the method of forming a thick film pattern according to any one of claims 4 to 10.