JP2824811B2 - Method of forming low melting glass pattern - Google Patents

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 of a low-melting glass which is effectively used in the field of manufacturing electronic display devices and the like. And a method for forming a fine and sharp pattern.

[0002]

2. Description of the Related Art In the manufacture of electronic display devices and the like, for example, low melting glass is often used as a spacer between electrodes. As a method of forming a pattern of this low-melting glass, a method in which a low-melting glass is dispersed in an acrylic binder or a cellulose-based binder is screen-printed, or the low-melting glass is dispersed in an acrylic photosensitive agent, and screen printing is performed. Drying, exposure, development,
There is a firing method.

However, in the former method of directly obtaining a low-melting glass pattern by screen printing, it is difficult to obtain a desired thick-film low-melting glass pattern at one time. It was necessary to perform recoating, and the operation was complicated, and a fine pattern could not be obtained, and the formation of a pattern of about 100 μm was the limit. Also, if the screen mesh is made low to obtain a thick film, a certain thick film can be obtained,
There is a problem that the printed pattern is sagged and the pattern accuracy is reduced.

The latter method can form a finer pattern than the former method, but causes halation due to irregular reflection of the low-melting glass dispersed in the acrylic photosensitive agent, and particularly, a thick film. When a pattern is formed, development failure tends to occur, and this method has a problem that only a pattern having a thickness of about 8 μm at the maximum can be obtained, and a good pattern cannot be obtained.

Further, a method is also known in which a mask pattern having etching resistance is formed on a low melting point glass layer, and a portion which is not protected by the mask pattern is removed by etching. For the etching, chemical etching using hydrofluoric acid solution or cutting method using sand as an abrasive is performed, and such etching cannot form a pattern of low melting point glass excellent in pattern shape, Particularly, the substrate is likely to be damaged during etching, for example, when a low-melting glass pattern is formed on a substrate on which a transparent electrode pattern is formed, the transparent electrode pattern is likely to be adversely affected during etching, which is practical. Not a way.

[0006]

SUMMARY OF THE INVENTION The present inventor has sought to improve the above-mentioned drawbacks of the prior art and to form a fine and sharp pattern without damaging the substrate when cutting low-melting glass by the sandblasting method. As a result of intensive studies for the purpose of providing the above method, it has been found that the object can be achieved by providing a protective layer which has sandblast resistance and can be removed by baking on a substrate, and has accomplished the present invention.

[0007]

According to the present invention, there is provided (a) a step of forming a protective layer having a sandblast resistance and capable of being removed by firing on a substrate, and (b) forming a low melting point glass layer on the protective layer. Forming; (c) forming a mask pattern on the low-melting glass having sandblast resistance and capable of being removed by firing; (d) cutting a low-melting glass layer which is not protected by the mask pattern by sandblasting. And (e) baking and removing the protective layer and the mask pattern.

Hereinafter, the present invention will be described in detail. In the method of the present invention, as step (a), a protective layer having sandblast resistance and capable of being removed by firing is formed on the substrate. In this case, the substrate is not particularly limited, and any substrate can be used. Specific examples include a glass plate and a ceramic plate. The substrate used in the method of the present invention also includes a substrate on which a transparent electrode is patterned.

As the protective layer, any material may be used as long as it has sandblast resistance and has a property that it can be removed by firing.
Although not particularly limited, when a substrate on which a patterned transparent electrode is formed is used, a substrate having excellent coverage of the unevenness of the transparent electrode is preferable.
A preferable material for forming such a protective layer is a urethane acrylate having at least three urethane bonds in a molecule, particularly a urethane acrylate having at least three urethane bonds in a molecule and a light-emitting material. A photosensitive material obtained by blending with a polymerization initiator can be preferably used. In this case, the compounding amounts are as follows: 90 to 99.5% by weight of a urethane acrylate having at least three urethane bonds in the molecule;
-10% by weight.

By the way, as a method for forming the protective layer, for example, the material having the properties as the protective layer can be easily obtained by applying the above-mentioned material on a substrate by using a spinner or the like and drying it. When a photosensitive material containing a photopolymerization initiator is used, a stronger protective layer can be formed by irradiating with actinic light after coating and drying. The practical thickness of the protective layer is 5 to 15 μm.

In the step (b) of the present invention, a low melting point glass layer is formed on the protective layer. PbO—B ₂ O ₃ —SiO ₂ glass, Pb
_O-ZnO-B 2 O ₃ based glass, _{ZnO-B 2} O 3 -S
iO ₂ -based glass, PbO-Al ₂ O ₃ -SiO ₂ -based glass, and the like. These low-melting glass powders are dispersed in various binder solutions by a doctor blade method or a screen printing method. A low-melting glass layer is formed by coating on the protective layer and drying. The thickness of the low-melting glass layer is not particularly limited. However, when a thin line (for example, 100 μm or less) pattern is formed,
It is preferably not more than 00 μm.

In the step (c) of the method of the present invention, a mask pattern having sandblast resistance and capable of being removed by firing is formed on the low melting point glass layer. As a material for forming the mask pattern, for example, a photosensitive composition comprising a urethane acrylate having at least three urethane bonds in a molecule, an alkali-soluble cellulose having a carboxyl group, and a photopolymerization initiator is preferably used. In this case, the compounding amount of each component is 50 to 90% by weight of urethane acrylate, 5 to 50% by weight of alkali-soluble cellulose, and the photopolymerization initiator is 0.1 to 0.1% based on the total amount of urethane acrylate and alkali-soluble cellulose. 20% by weight. Examples of the alkali-soluble cellulose having a carboxyl group used as a material for forming the mask pattern include carboxymethyl cellulose, cellulose acetate phthalate, and the like, and a partial acetate of cellulose, a dicarboxylic acid or a tricarboxylic acid, such as succinic acid, What reacted adipic acid, trimellitic acid, etc. can also be used.

The urethane acrylate having at least three urethane bonds in a molecule used for the material for forming the protective layer and the mask pattern can be produced by a known method. For example, a condensate of an aliphatic compound having two carboxyl groups and an aliphatic compound having two hydroxyl groups, specifically, a carboxyl group or a hydroxyl group of a polyester obtained from adipic acid and 1,6-hexanediol and two condensates The isocyanate group of the reaction product obtained by reacting with an aliphatic compound having an isocyanate group, for example, hexamethylene diisocyanate,
-Hydroxyethyl acrylate can be obtained by reacting with an acrylic compound having a hydroxyl group at a terminal.

The photopolymerization initiator used for the material for forming the above-mentioned protective layer and mask pattern includes 9, 10
-Anthraquinone, 1-chloro-9,10-anthraquinone, benzophenone, 4-chlorobenzophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, 2-chlorothioxanthone, 2,4-diethylthioxanthone, and the like. These photopolymerization initiators may be used alone or in combination of two or more.

In addition to the above components, various additives such as a photopolymerization accelerator, a thermal polymerization inhibitor, a stabilizer, a pigment, a dye, and the like may be added to the material for forming the protective layer and the mask pattern, if necessary. It can be used in a range that does not impair the object of the present invention.

In the step (d) of the method of the present invention, the low melting point glass layer which is not protected by the mask pattern is cut by a sand blast method. In the sandblasting method, a conventionally known means is used, and the size, material, and the like of the abrasive are appropriately selected depending on the processing dimensions. According to the method of the present invention, since the protective layer having sandblast resistance is formed on the substrate, the substrate is not damaged by the abrasive even during sandblasting.

Step (e) of the method of the present invention is a step of finally forming a low-melting glass pattern and firing and removing the protective layer and the mask pattern. The firing temperature in this case is 450 to 800 ° C., preferably 500 to 7 ° C.
It is in the range of 50 ° C.

[0018]

According to the method for forming a low-melting glass pattern of the present invention, a protective layer having sand blast resistance and capable of being removed by baking is provided on a substrate. There is an effect that a fine and sharp pattern can be easily formed without causing damage.

[0019]

EXAMPLES Example 1 SR-6178, a polyurethane acrylate having five urethane bonds in the molecule (manufactured by Daicel Chemical Industries, Ltd.)
10 parts by weight of ethylene glycol monobutyl ether 5
After dissolution in 0 parts by weight, 2,4-diethylthioxanthone 5 parts by weight, p-dimethylaminobenzoic acid ethyl ester 5 parts by weight, N-nitrosophenylhydroxyamine aluminum salt 0.05 parts by weight, and methylhydroquinone 0.05 parts by weight The mixture was added and dissolved to prepare a photosensitive solution for forming a protective layer.

The prepared photosensitive liquid for forming a protective layer is applied on a glass plate using a spinner so that the film thickness after drying becomes 10 μm, and then dried by blowing air at 70 ° C. for 7 minutes. A protective layer was formed on the glass plate by exposing the entire surface to an irradiation amount of 20 mJ / cm ^{2 using} a high-pressure mercury lamp. Then After those dispersed in an acrylic binder solution PbO-ZnO-B ₂ O ₃ based glass powder on the protective layer by a screen printing method, a glass frit by repeating the drying - acrylic binder A low-melting glass layer having a thickness of 150 μm was formed.

Next, KC-71 which is an alkali-soluble cellulose having a carboxyl group (manufactured by Wako Pure Chemical Industries, Ltd.)
30 parts by weight and 70 parts by weight of SR-6138 (manufactured by Daicel Chemical Industries, Ltd.), a polyurethane acrylate having 5 urethane bonds in the molecule, were mixed with 100 parts by weight of ethylene glycol monobutyl ether and 10 parts by weight of methyl ethyl ketone 10
After dissolving in a mixed solvent consisting of 0 parts by weight, 5 parts by weight of 2.2-dimethoxy-2-phenylacetophenone, 5 parts by weight of 2,4-diethylthioxanthone, p-
Dimethylaminobenzoic acid ethyl ester 5 parts by weight, N-
Nitrosophenylhydroxylamine aluminum salt (0.05 parts by weight) and methylhydroquinone (0.05 parts by weight) were added and dissolved to prepare a photosensitive liquid for forming a mask pattern.

The prepared photosensitive liquid for forming a mask pattern is spin-coated on the above-mentioned low-melting glass layer so that the film thickness after drying becomes 10 μm, dried by blowing at 70 ° C. for 5 minutes, and then spin-dried again. After applying a photosensitive liquid for forming a mask pattern so as to have a thickness of 30 μm after drying using, and drying, the diameter for forming a via hole using an ultra-high pressure mercury lamp is 120 μm, 100 μm, 80 μm,
Exposure was performed at a dose of 35 mJ / cm ² through a positive mask.

Next, spray development is carried out using a 0.1% by weight aqueous sodium carbonate solution, washing with water, neutralization with dilute hydrochloric acid, washing with water,
By drying, a mask pattern faithful to the mask was formed on the low melting point glass layer.

Next, the low melting point glass layer exposed by using the mask pattern as a mask was sandblasted with an abrasive Alundum # 600 (manufactured by Fuji Seisakusho) at a blast pressure of 5 kg / cm ² and a blast time of 7 minutes. Diameter 120μm, 100μm, 8 faithful to mask on plate
A low melting glass layer having 0 μm holes was formed.

When the glass plate was cut at right angles to the pattern and observed with an electron microscope, there was no evidence of blast etching on the glass plate. In addition, the low melting point glass layer is fired by firing the glass plate at 550 ° C. for 5 hours, and the low melting point glass layer mask and the protective layer are fired and removed to form a sharp low melting point glass fired on the glass plate. A pattern was formed.

Example 2 SR-6138 which is a polyurethane acrylate having five urethane bonds in the molecule (manufactured by Daicel Chemical Industries, Ltd.)
10 parts by weight of ethylene glycol monoethyl ether 6
After dissolving in 0 parts by weight, 2 parts by weight of 2,4-diethylthioxanthone, 2 parts by weight of amyl p-dimethylaminobenzoate and 0.05 parts by weight of methylhydroquinone were added and dissolved. Was prepared

The prepared photosensitive liquid for forming a protective layer is applied on a glass plate using a spinner so as to have a thickness of 10 μm after drying, followed by drying by blowing at 70 ° C. for 5 minutes. The whole surface was exposed at an irradiation amount of 15 mJ / cm ² to form a protective layer on the glass plate.

Next, PbO—ZnO—B ₂ was formed on the protective layer.
After a thing in which the O ₃ -based glass powder was dispersed in an acrylic-based binder solution was printed by a screen printing method, and the drying was repeated, a low-melting glass layer having a thickness of 200 μm made of a glass frit-acrylic-based binder was formed.

Next, using the photosensitive liquid for forming a mask pattern used in Example 1, a low-melting glass layer was coated so as to have a thickness of 25 μm after drying, and dried at 70 ° C. for 10 minutes. 20 mJ / cm through a mask having a line and space of 100 μm using an ultra-high pressure mercury lamp
Exposure was performed at a dose of ² . Then, spray development is performed using an aqueous 0.1 wt% sodium carbonate solution, and the resultant is washed with water, neutralized with dilute hydrochloric acid, washed with water, and dried to obtain a 100 μm film faithful to a mask.
Was formed on the low melting point glass layer.

Next, using the mask pattern as a mask, the exposed low-melting glass layer is coated with an abrasive White Alundum # 40.
0 (manufactured by Fuji Manufacturing Co., Ltd.) and blast pressure 5 kg / c
When sand blasting was performed at m ² for 10 minutes, a low-melting glass layer faithful to the mask was formed on the glass plate.

When this glass plate was cut at right angles to the pattern and observed with an electron microscope, there was no evidence of blast etching on the glass plate. The low melting point glass layer is fired by firing the glass plate at 570 ° C. for 1 hour, and the sharp low melting point glass pattern fired on the glass plate is fired by removing the mask and protective layer of the low melting point glass layer. Was formed.

Claims (2)

(57) [Claims] (A) a step of forming a protective layer having sandblast resistance and capable of being removed by firing on a substrate; (b) a step of forming a low-melting glass layer on the protective layer; Forming a mask pattern on the low-melting glass layer having sandblast resistance and capable of being removed by firing; (d) cutting a low-melting glass layer not protected by the mask pattern by sandblasting; and (e) A) a method of forming a low-melting glass pattern comprising a step of baking and removing the protective layer and the mask pattern; 2. The method according to claim 1, wherein the protective layer is formed from a photosensitive material.