JP2002352709A - Coating liquid for black stripe forming, the black stripe using the liquid and manufacturing method of the black stripe using the coating liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating liquid for black stripe forming, which is capable of producing black stripes, having high optical density(OD) values per unit film thickness, and obtaining a prescribed OD value having smaller thickness than that of previous coating liquid, and having both superior optical characteristics and reflectivity at low cost, and also provide a manufacturing method of black stripes, which is capable of producing black stripes in safety and at a low cost with a very easy process, using the coating liquid for black stripe forming. SOLUTION: This coating liquid for black stripe forming contains at least Mn compound, Cu compound, Fe compound, SiO2 and an organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating liquid for forming a black stripe, a black stripe using the same, and a method for producing the same, and more particularly, to a black stripe capable of forming a patterned black stripe on a substrate. The present invention relates to a coating liquid for formation, a patterned black stripe, and a method for producing the black stripe.

[0002]

2. Description of the Related Art At present, a plasma display panel (PDP) having good responsiveness and color reproducibility has attracted attention as a large-screen, high-quality image display device for high vision. One of the methods for improving the image quality of this PDP is to increase the bright room contrast. Therefore, in order to provide a gap between the discharge cells of the substrate on the front side of the PDP, a black stripe is formed between these discharge cells. The method is adopted. Since this gap is for preventing erroneous discharge, it basically does not contribute to light emission. For this reason,
This is to suppress the reflection of external light by filling the space between the discharge cells with black. It is generally said that the provision of the black stripe improves the bright room contrast by 20%.

As a characteristic required for a material for forming the black stripe, adhesion to glass is high. Low reflectivity. Low transmittance. High insulation. Excellent solvent resistance. Low reactivity with transparent electrodes and bath electrodes. And the like.

Therefore, in order to satisfy these characteristics, a black glass paste of a type in which a PbO—B ₂ O ₃ —SiO ₂ -based glass powder and a black pigment are mixed has conventionally been used. This black glass paste is classified into a printing type (resolution: about 70 to 100 μm) and a photosensitive type (resolution: about 30 to 50 μm), which are properly used in consideration of design rules. The printing type is patterned by screen printing, and the photosensitive type is patterned by photolithography, and finally fired at 550 to 600 ° C. to form black stripes having a film thickness of 3 to 7 μm.

[0005]

However, at present, the conventional black glass paste described above has a low optical density (OD) value per unit film thickness, and a black stripe is required to obtain a predetermined OD value. The film thickness must be increased. Also, in order for the black stripe to obtain a predetermined insulating property, a transparent dielectric film must be formed on the black stripe. However, when the thickness of the black stripe increases, the unevenness of the substrate surface increases. ,
There is a problem that it is difficult to form a transparent dielectric film with a uniform film thickness thereon.

Further, when the thickness of the black stripe is increased, the total film thickness including the transparent dielectric film is increased, so that the transmittance of the panel is reduced. Therefore, there is an increasing demand for a black stripe forming material that has a higher absorbance than before and can obtain a predetermined OD value with a thinner film thickness than before when forming a thin film.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problem, and has been made in view of the above circumstances.
D) For forming a black stripe which has a high value, a predetermined OD value can be obtained with a thinner film thickness than the conventional one, and a black stripe excellent in optical characteristics having low reflectivity can be formed at low cost. Coating solution, patterned black stripes formed using this coating solution for forming black stripes, black stripes that can be manufactured in a very simple process, at a safe and low cost It is to provide a manufacturing method of.

[0008]

In order to solve the above-mentioned problems, the present invention employs the following coating liquid for forming a black stripe, a black stripe using the same, and a method for producing the same. That is, the coating liquid for forming a black stripe according to claim 1 of the present invention comprises a Mn compound, a Cu compound,
It is characterized by containing at least an Fe compound, SiO ₂ and an organic solvent.

A black stripe forming coating solution according to a second aspect of the present invention is the black stripe forming coating solution according to the first aspect, wherein the Mn compound is an organic acid salt of Mn.
n, an organic acid salt of Mn, and a mixture of inorganic acid salts of Mn. The Cu compound is an organic acid salt of Cu, an inorganic acid salt of Cu, an organic acid salt of Cu, and an inorganic acid. A mixture of salts, wherein the Fe compound is
It is characterized by being one of an organic acid salt of Fe, an inorganic acid salt of Fe, and a mixture of an organic acid salt of Fe and an inorganic acid salt.

A third aspect of the present invention is the coating solution for forming a black stripe according to the first or second aspect, wherein the SiO ₂ is obtained by hydrolyzing an alkoxide of Si. And

According to a fourth aspect of the present invention, there is provided the coating liquid for forming a black stripe, wherein the organic solvent contains at least one kind of aprotic polar solvent. It is characterized by the following.

According to a fifth aspect of the present invention, in the coating solution for forming a black stripe according to any one of the first to fourth aspects, the Mn, C
The sum of the contents of u, Fe and Si is 1 to 20% by weight in terms of oxide based on the total weight of the coating solution.

[0013] The coating liquid for forming a black stripe according to claim 6 is the coating liquid for forming a black stripe according to any one of claims 1 to 5, wherein the content of the SiO ₂ is added to the total weight of the coating liquid. On the other hand, the content is 0.2 to 5% by weight.

According to a seventh aspect of the present invention, in the coating solution for forming a black stripe according to the fourth or fifth or sixth aspect, the content of the aprotic polar solvent is added to the total weight of the coating solution. It is characterized in that the content is 1 to 20% by weight.

The black stripe according to claim 8 is formed on a substrate on which a negative resist pattern has been formed in advance.
A patterned black stripe is formed by using the coating liquid for forming a black stripe according to any one of claims 1 to 7.

According to a ninth aspect of the present invention, there is provided a method for producing a black stripe, the method comprising forming a negative resist pattern on a substrate using a photosensitive resin, and then forming the negative resist pattern on the substrate. Apply and dry the liquid,
Then, it is characterized by firing at a temperature of 400 ° C. or more.

According to a tenth aspect of the present invention, there is provided a black stripe manufacturing method according to the ninth aspect, wherein the photosensitive resin is coated with the black stripe forming coating according to any one of the first to seventh aspects. It is characterized by having no compatibility or reactivity with a liquid and having liquid repellency.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the coating liquid for forming a black stripe of the present invention, a black stripe using the same, and a method of manufacturing the same will be described. The present embodiment is specifically described for better understanding of the spirit of the present invention, and does not limit the present invention unless otherwise specified.

[Coating Liquid for Black Stripe Formation] The coating liquid for black stripe formation of the present embodiment comprises a manganese (Mn) compound, a copper (Cu) compound, an iron (Fe) compound, silicon oxide (SiO ₂ ) and an organic solvent. At least. As SiO ₂ , those formed by hydrolyzing alkoxides of Si are preferably used.

Here, a manganese (Mn) compound, copper (C
The u) compound and the iron (Fe) compound are not particularly limited. For example, organic acid salts such as formate, acetate and citrate, and inorganic acid salts such as nitrate and chloride may be used. Can be. In particular, nitrates are soluble in organic solvents,
It is preferably used because of its excellent low-temperature thermal decomposability and the like. Examples of the Si alkoxide used as a raw material of SiO ₂ include general Si alkoxides, for example, tetramethoxysilane ((CH ₃ O) ₄ Si), tetraethoxysilane ((C ₂ H ₅ O) ₄ Si), tetra isopropoxide Bo silane _{((i-C 3 H 7} O) 4 Si) or the like is preferably used.

The organic butterfly is particularly limited.
But preferably contains an aprotic polar solvent
No. Examples of the aprotic polar solvent include, for example, 1-methyl
Ru-2-pyrrolidone (C_FourH₆NOCH_Three), Dimethylpho
Lumamide (HCON (CH_Three) _Two) Etc. are preferably used
You.

Here, a manganese (Mn) compound, copper (C
u) A compound and an iron (Fe) compound are each weighed to a predetermined amount, and mixed and stirred until completely dissolved in a solvent. Next, an alkoxide of Si is added, and the mixture is heated and stirred at 60 ° C. for 1 hour. In this heating and stirring process, a desired coating liquid for forming a black stripe is obtained by hydrolyzing the alkoxide of Si in the mixed solution to form a composite of SiO ₂ . As a supply source of water used at the time of this hydrolysis, when hydration water is contained in a manganese (Mn) compound, a copper (Cu) compound, and an iron (Fe) compound,
This water of hydration may be used, and when water of hydration is not contained, water may be added as needed.

In the above coating liquid for forming a black stripe, the total content of Mn, Cu, Fe and Si is 1 to 2 in terms of oxide with respect to the total weight of the coating liquid.
0% by weight, more preferably 9 to 13% by weight. Here, the reason for limiting the total of these contents as described above is that if the total of these contents is less than 1% by weight,
The obtained film thickness is too thin, and a predetermined OD value cannot be obtained. Conversely, if the total of these contents is more than 20% by weight, the film thickness becomes too thick, and cracks are easily generated. This is because a good film cannot be obtained.

The reason for adding SiO ₂ to the coating solution is to improve the film forming property and the film strength after firing. The content of the Si alkoxide to be added is SiO 2
_In terms of ₂ , it is 0.2 to 5% by weight, more preferably 1 to 3% by weight, based on the weight of the coating solution. Content is 0.2% by weight
If less, the film strength after firing becomes weak, and conversely, 5
If the content is more than 10% by weight, the film thickness becomes too large, cracks are easily generated, and a good film cannot be obtained.

The organic solvent used in the coating solution is not particularly limited as long as it can dissolve each metal salt and the alkoxide of Si. In consideration of coating properties, an alcohol such as 1-propanol or 2-propanol is used. Are preferably used. At least one kind of aprotic polar solvent is added to the organic solvent in order to increase the solubility of the metal salt in the solvent and prevent the film from becoming cloudy or the like which may occur during film formation.

As the aprotic polar solvent, 1-methyl-2-pyrrolidone, dimethylformamide and the like are preferably used. Among them, 1-methyl-2-pyrrolidone is particularly preferred. The content of the aprotic polar butterfly is 1 to 20% by weight, more preferably 8 to 14% by weight, based on the weight of the coating solution. If the content is less than 1% by weight, the effect of preventing white turbidity during film formation is small. Conversely, if the content is more than 20% by weight, repelling spots occur during film formation and a good coating film is obtained. It is not possible.

[Patterned Black Stripe and Manufacturing Method Thereof] The patterned black stripe is formed on a substrate on which a negative resist pattern has been previously formed by using a photosensitive resin. It is produced by applying and drying a coating liquid for use and baking. This method is an application of the lift-off method, in which a coating solution for forming a black stripe is embedded in a portion other than the resist pattern portion, dried, and baked, the resist pattern portion is decomposed and disappears, and a black stripe is formed there. Instead, a black stripe is formed only in the non-resist pattern portion in which the coating liquid is embedded.

As the photosensitive resin used here, a photopolymerizable acrylic resin, a photodegradable novolak resin, a photocrosslinkable water-soluble polymer, and the like can be used. It is necessary that the photosensitive resin has no compatibility or reactivity and exhibits liquid repellency. If these characteristics are not satisfied, the coating liquid for forming a black stripe remains on the resist pattern, and even after the resist disappears due to baking, a black stripe remains in that portion, and a good pattern cannot be obtained.

To apply this photosensitive resin on a substrate,
A known method can be adopted, and for example, a dip coating method, a spin coating method, a roll coating method and the like are suitably used. The resist pattern has a thickness of 1.0 to 1.0.
The thickness is set to 5.0 μm, preferably 2,0 to 3,0 μm. The reason is that the thickness of the resist pattern is 1.0
If the thickness is smaller than μm, the thickness of the obtained black stripe is too thin, and a required OD value cannot be obtained.
If the thickness is larger than 0 μm, the thickness of the obtained black stripe becomes too large, and cracks occur in the film after firing.

In the case of applying a coating liquid for forming a black stripe on the substrate on which the negative resist pattern is formed, a known method can be adopted, for example, a dip coating method, a spin coating method, a roll coating method and the like. Is preferably used. After applying this coating solution, 12
It may be dried at 0 ° C. for about 10 minutes. Then, in the atmosphere 4
At a temperature of at least 00 ° C, preferably at least 500 ° C,
By baking for about 60 minutes, a black stripe is formed only in the non-resist pattern portion in which the coating liquid is embedded.

According to the above-described method, a patterned black stripe can be produced safely and at low cost with very simple steps. Conventional black stripes have a thickness of 4 to 7 μm, but according to the present invention, black stripes having a required optical density (OD) value are formed even when the thickness is as thin as 0.5 to 1.0 μm. can do. Therefore, a transparent dielectric can be easily formed, the entire film thickness can be reduced, and the transmittance of the panel can be improved, which is suitable for improving the image quality of a PDP.

[0032]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1 [Coating Solution for Black Stripe Formation] Mn (NO ₃ ) _2.
6H ₂ O and _{18.0g, Cu (NO 3) 2} · 3H 2 O 8.
2 g and 6.1 g of Fe (NO ₃ ) ₃ .9H ₂ O were weighed, respectively, dissolved in 50.9 g of 1-propanol, and then 1-methyl-2-pyrrolidone was added to 11.0 g of 11.0 g.
g was added and stirred well for 30 minutes. After the stirring, 5.8 g of tetraethoxysilane was added, and the mixture was heated and stirred at 60 ° C. for 1 hour to hydrolyze the tetraethoxysilane to form SiO ₂ , and then cooled to obtain a mixture of Example 1.
Was obtained. This coating liquid for forming a black stripe did not produce a precipitate or the like even after being left for one month, had no change in viscosity, and was stable.

[Formation of Pattern] 50 g of stilbasol-modified polyvinyl alcohol (PVA) (LS400: manufactured by Toyo Gosei Co., Ltd.), 20 g of butyl cellosolve, 3 g of tetrahydrofurfuryl alcohol, 2 g of 1-propanol and 25 g of ion-exchanged water were weighed and mixed. Stir well for 1 hour. The obtained photocrosslinkable water-soluble polymer solution was applied on a soda lime glass substrate using a spin coater (400 rpm, 20 sec), and then dried at 70 ° C. for 15 minutes. Then, L / S = 3 on this dried film
A 0/30 μm photomask was placed, ultraviolet light was applied (i-line exposure amount: 40 mJ / cm ² ), and development was performed with water for 1 minute. After the development, a heat treatment was performed at 200 ° C. to further advance the crosslinking of the polymer.

[Application of Black Stripe Forming Coating Solution] On the substrate on which this negative resist pattern is formed,
The above-mentioned coating liquid for forming a black stripe was applied using a spin coater (1500 rpm, 20 sec), and then dried at 120 ° C. for 10 minutes. Since this negative resist pattern film has liquid repellency to the coating liquid for forming a black stripe, the coating liquid for forming a black stripe is selectively applied only on the glass substrate in a space portion (positive pattern formation). It had been.

Thereafter, it was baked at 500 ° C. for 1 hour in an electric furnace (atmosphere) to obtain a black stripe patterned to L / S = 30/30 μm. The film thickness of this black stripe was measured using a stylus-type film thickness measuring device (DIKTAK3030), and the optical density (OD) value, reflectance, and absorbance per unit film thickness were measured with a spectrophotometer (JASCO Corporation) )), The film thickness was 0.7 μm, the OD value was 2.6, the reflectance was 5.8%, and the absorbance per unit film thickness was 3.7 / μm. there were.

Example 2 [Coating Liquid for Black Stripe Formation] Mn (CH ₃ CO)
O) ₂ · 4H ₂ O and _{15.3g, Cu (CH 3 COO)} 2 ·
H ₂ O and 6.7 g, Fe a _{(NO 3) 3 · 9H 2} O 6.0
g, each of which was weighed and weighed 1-propanol.
After dissolving in 2 g, 11.0 g of 1-methyl-2-pyrrolidone was added and stirred well for 30 minutes. After stirring, 5.8 g of tetraethoxysilane was added, and the mixture was heated and stirred at 60 ° C. for 1 hour to hydrolyze the tetraethoxysilane to produce SiO ₂ , and then cooled to obtain the black of Example 2. A coating liquid for forming a stripe was obtained. This coating liquid for forming a black stripe did not produce a precipitate or the like even after being left for one month, and was stable with no change in viscosity.

[Formation of Pattern] A resist pattern was formed in the same manner as in Example 1. [Application of Black Stripe Forming Coating Solution] On the substrate on which the negative resist pattern was formed, the above black stripe forming coating solution was applied by a spin coater (1500 rpm).
m, 20 sec), and then dried at 120 ° C. for 10 minutes.

Thereafter, it was baked at 500 ° C. for 1 hour in an electric furnace (in the air atmosphere) to obtain a black stripe patterned to L / S = 30/30 μm. When this black stripe was evaluated by the same method as in Example 1, the film thickness was 0.9 μm, and the OD value was 3.2.
The reflectance is 5.2%, and the absorbance per unit film thickness is 3.6 /
μm.

(Example 3) [Coating solution for forming black stripe] Mn (COOH)
₂ · 2H ₂ O and _{11.3g, Cu (COOH) 2 ·} 4H 2 O
And 7.6 g of Fe (NO ₃ ) ₃ .9H ₂ O were weighed, and these were dissolved in 58.3 g of 1-propanol, and then 1-methyl-2-pyrrolidone 1
1.0 g was added and stirred well for 30 minutes. After the stirring, 5.8 g of tetraethoxysilane was added, and the mixture was heated and stirred at 60 ° C. for 1 hour to hydrolyze the tetraethoxysilane to form SiO ₂ , and then cooled,
A coating liquid for forming a black stripe of Example 3 was obtained. This coating liquid for forming a black stripe did not produce a precipitate or the like even after being left for one month, and was stable with no change in viscosity.

[Formation of Pattern] A resist pattern was formed in the same manner as in Example 1. [Application of Black Stripe Forming Coating Solution] On the substrate on which the negative resist pattern was formed, the above black stripe forming coating solution was applied by a spin coater (1500 rpm).
m, 20 sec), and then dried at 120 ° C. for 10 minutes.

Thereafter, it was baked at 500 ° C. for 1 hour in an electric furnace (in the atmosphere) to obtain a black stripe patterned to L / S = 30/30 μm. When this black stripe was evaluated by the same method as in Example 1, the film thickness was 0.8 μm, and the OD value was 2.9.
The reflectance is 5.5%, and the absorbance per unit film thickness is 3.6 /
μm.

Example 4 [Coating Liquid for Black Stripe Formation] Mn (NO ₃ ) _2.
6H ₂ O and _{18.0g, Cu (NO 3) 2} · 3H 2 O 8.
2 g and 6.1 g of Fe (NO ₃ ) ₃ .9H ₂ O were weighed and dissolved in 52.4 g of 1-propanol, and then 1-methyl-2-pyrrolidone was dissolved in 11.0 g.
g was added and stirred well for 30 minutes. After stirring, 4.3 g of tetramethoxysilane was added, and the mixture was heated and stirred at 60 ° C. for 1 hour to hydrolyze the tetramethoxysilane to form SiO ₂ , and then cooled, to thereby obtain Example 4.
Was obtained. This coating liquid for forming a black stripe did not produce a precipitate or the like even after being left for one month, had no change in viscosity, and was stable.

[Formation of Pattern] A resist pattern was formed in the same manner as in Example 1. [Application of Black Stripe Forming Coating Solution] On the substrate on which the negative resist pattern was formed, the above black stripe forming coating solution was applied by a spin coater (1500 rpm).
m, 20 sec), and then dried at 120 ° C. for 10 minutes.

Thereafter, it was baked at 500 ° C. for 1 hour in an electric furnace (in an air atmosphere) to obtain a black stripe patterned to L / S = 30/30 μm. When the black stripe was evaluated by the same method as in Example 1, the film thickness was 0.7 μm, and the OD value was 2.6.
The reflectance is 5.8%, and the absorbance per unit film thickness is 3.7 /
μm.

(Comparative Example 1) Screen printing (a screen mesh: 250, printing pressure: 2 kg / cm) of a photosensitive type black stripe forming paste (manufactured by DuPont) comprising a black pigment, a glass powder and a photosensitive resin. ² , clearance: 3mm, squeegee speed: 50mm / s
ec. ) Was applied on a glass substrate. Then 5
After performing leveling for 20 minutes, it was dried at 80 ° C. for 20 minutes. Thereafter, a photomask of L / S = 30/30 μm was disposed thereon, and ultraviolet rays were irradiated using a high-pressure mercury lamp. At this time, the exposure amount of the ultraviolet light was 300 mJ / cm ² .

Next, using a 2 wt% aqueous solution of Na ₂ CO ₃ for spray development (spray pressure: 2 kg / cm ² , 30
° C, 60 sec. ) To form a negative pattern.
Then, it baked at 550 degreeC for 30 minutes in air | atmosphere. The resolution of the obtained black stripe is L / S = 30/30.
μm. When the film thickness, the OD value, the reflectance, and the absorbance per unit film thickness were evaluated in the same manner as in Example 1, the film thickness was 4 μm, the OD value was 1.4, the reflectance was 7.0%, The absorbance per unit film thickness was 0.35 / μm. The thickness of the black stripe was 4 μm.
When it was thinner, a predetermined optical density (OD) value could not be obtained.

(Comparative Example 2) A black resist for forming a black stripe of a photosensitive type comprising a black pigment and a photosensitive resin (manufactured by Tokyo Ohka Co., Ltd.) was applied on a glass substrate by a spin coating method, and was then applied at 100 ° C. for 10 minutes. Dried. Thereafter, a photomask of L / S = 30/30 μm was disposed thereon, and ultraviolet rays were irradiated using a high-pressure mercury lamp. The exposure amount at this time was 300 mJ / cm ² .

Next, spray development (spray pressure: 2 kg / cm ² , 25%) using a 2 wt% aqueous solution of Na ₂ CO ₃
° C, 60 sec. ) To form a negative pattern.
Then, it baked at 600 degreeC for 30 minutes in air | atmosphere. The resolution of the obtained black stripe is L / S = 30/60.
μm. When the film thickness, OD value, reflectance and absorbance per unit film thickness were evaluated by the same method as in Example 1, the film thickness was 3 μm, the OD value was 3.2, and the reflectance was 6.0%. The absorbance per unit film thickness was 1.1 / μm. When the thickness of the black stripe was smaller than 3 μm, a predetermined optical density (OD) value could not be obtained.

(Comparative Example 3) A printing type black stripe forming paste (manufactured by Noritake Company Limited) comprising a black pigment, glass powder and resin was screen-printed (screen mesh: 250, mask pattern: L / S). = 100/100 μm, printing pressure: 2 kg / c
m ² , clearance: 3mm, squeegee speed: 30
mm / sec. ) Was applied on a glass substrate. Then, it is dried at 150 ° C. for 10 minutes, and then dried at 580 ° C. for 3 minutes.
Firing was performed in the air for 0 minutes.

The resolution of the obtained film is L / S = 100/1
It was 00 μm. When the film thickness, OD value, reflectance and absorbance per unit film thickness were evaluated by the same method as in Example 1, the film thickness was 7 μm, the OD value was 3.0, and the reflectance was 7.0%. The absorbance per unit film thickness was 0.4 / μm. The thickness of this black stripe was 7 μm.
When it was thinner, a predetermined optical density (OD) value could not be obtained.

[Evaluation of Black Stripe] Table 1 shows the film thickness, OD value, reflectance and absorbance per unit film thickness of the black stripes obtained in Examples 1 to 4 and Comparative Examples 1 to 3 above. It is a summary of the evaluation results.

[Table 1]

According to the results shown in Table 1, in Examples 1 to 4,
It was found that the film thickness could be easily reduced to 1 μm or less. In this case, the OD value, the reflectance, and the absorbance per unit film thickness show good characteristic values, and even when the film thickness is reduced to 1 μm or less, it is possible to easily obtain necessary and stable characteristics. I knew I could do it. On the other hand, in Comparative Examples 1 to 3, it was very difficult to reduce the film thickness to 1 μm or less. In addition, the OD value fluctuated greatly depending on the type of paste or the like used, and the reflectance and the absorbance per unit film thickness were inferior to those of Examples 1 to 4.

As described above, according to the coating liquid for forming a black stripe of the present embodiment, unlike the conventional pigment-mixed type, the precursor which is thermally decomposed into an oxide is based on the base. It is very easy to make the film thinner. Usually, the OD value of the black stripe is 1.4 to
Although 3.2 is required, according to the present embodiment, it is possible to obtain a necessary OD value in a thin film having a thickness of about 1/5 to 1/10 as compared with the conventional product. Also, the reflectance is lower than that of the conventional product.

In particular, when the black stripe obtained in the present embodiment is applied to a PDP, the transparent dielectric can be easily formed thereon by thinning the black stripe. Further, the thickness of the transparent dielectric can be reduced, and the transmittance of the panel can be improved.
Image quality can be improved.

[0056]

As described above, according to the coating liquid for forming a black stripe of the present invention, since it contains at least a Mn compound, a Cu compound, a Fe compound, SiO ₂ and an organic solvent, the film thickness can be reduced. It becomes very easy. Also, since the OD value per unit film thickness increases,
The required OD value can be obtained with a thinner film thickness than before. Further, since both the reflectance and the absorbance per unit film thickness are better than the conventional one, it is possible to realize a lower reflectivity than the conventional one.

The Mn compound may be any one of an organic acid salt of Mn, an inorganic acid salt of Mn, and a mixture of an organic acid salt of Mn and an inorganic acid salt.
, An inorganic acid salt of Cu, or a mixture of an organic acid salt of Cu and an inorganic acid salt of Cu, wherein the Fe compound is an organic acid salt of Fe, an inorganic acid salt of Fe, or an organic acid of Fe. When any one of a mixture of an acid salt and an inorganic acid salt is used, it is very easy to reduce the film thickness to 1 μm or less by using a precursor which is thermally decomposed to be an oxide. . Therefore, the OD value per unit film thickness can be made higher, and the required OD value can be obtained with a film thickness of about 1/5 to 1/10 of the conventional film thickness.

Further, when the SiO ₂ is obtained by hydrolyzing the alkoxide of Si, the film formability and the film strength after firing can be improved.

Further, when the organic solvent contains at least one kind of aprotic polar solvent, the solubility of the metal salt in the solvent can be increased, and problems such as cloudiness of the film during film formation can be prevented. Can be prevented.

According to the black stripe of the present invention, on a substrate on which a negative resist pattern has been formed in advance,
Since the patterned black stripe is formed by using the coating liquid for forming a black stripe of the present invention, a required OD value can be obtained with a smaller film thickness than before, and the reflectance and the unit thickness per unit film thickness can be obtained. Both have excellent absorbance. Therefore, if this patterned black stripe is applied to a PDP, a transparent dielectric can be easily formed thereon by thinning the black stripe. Further, since the thickness of the transparent dielectric can be reduced, the transmittance of the panel can be improved, which can contribute to the improvement of the image quality of the PDP.

According to the method for producing a black stripe of the present invention, a negative resist pattern is formed on a substrate using a photosensitive resin, then the coating liquid for forming a black stripe of the present invention is applied and dried, Since the baking is performed at a temperature of 400 ° C. or more, a patterned black stripe can be manufactured in a very simple process at a safe and low cost.

If the photosensitive resin has no compatibility or reactivity with the coating liquid for forming a black stripe of the present invention and has liquid repellency, the above-mentioned black stripe can be formed on a resist pattern. There is no possibility that the coating liquid for formation remains, and a black stripe having a good pattern can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01J 11/02 G02B 1/10 Z 5C040 F-term (Reference) 2H042 AA09 AA15 AA26 2H048 BA11 BA45 BA47 BA48 BB01 2K009 CC03 CC42 DD02 EE01 4G059 AA08 AB01 AB05 AC08 EA01 EA05 EB05 5C028 FF11 FF12 FF16 5C040 FA01 FA02 GH02 GH03 JA15 KA16 KA17 MA04 MA23 MA24 MA26

Claims (10)

[Claims] 1. A Mn compound, a Cu compound, an Fe compound,
A coating liquid for forming a black stripe, comprising at least SiO ₂ and an organic solvent. 2. The Mn compound is an organic acid salt of Mn, M
an inorganic acid salt of n, an organic acid salt of Mn and a mixture of inorganic acid salts, wherein the Cu compound is an organic acid salt of Cu, an inorganic acid salt of Cu,
Any one of a mixture of an organic acid salt and an inorganic acid salt of Cu;
A seed, wherein the Fe compound is an organic acid salt of Fe, an inorganic acid salt of Fe,
Any one of a mixture of an organic acid salt and an inorganic acid salt of Fe;
The coating liquid for forming a black stripe according to claim 1, which is a seed. 3. The SiO ₂ is obtained by hydrolyzing an alkoxide of Si.
The coating solution for forming a black stripe according to the above. 4. The coating liquid for forming a black stripe according to claim 1, wherein the organic solvent contains at least one kind of aprotic polar solvent. 5. The method according to claim 1, wherein the total content of said Mn, Cu, Fe and Si is 1 to 20% by weight in terms of oxide based on the total weight of said coating solution. 5. The coating liquid for forming a black stripe according to any one of 4. 6. The black stripe formation according to claim 1, wherein the content of the SiO ₂ is 0.2 to 5% by weight based on the total weight of the coating solution. Coating solution. 7. The content of the aprotic polar solvent is as follows:
The coating liquid for forming a black stripe according to claim 4, wherein the coating liquid is 1 to 20% by weight based on the total weight of the coating liquid. 8. A black stripe patterned using the coating liquid for forming a black stripe according to claim 1 is formed on a substrate on which a negative resist pattern has been previously formed. Black stripe characterized by becoming. 9. A negative resist pattern is formed on a substrate using a photosensitive resin, and then the coating liquid for forming a black stripe according to claim 1 is applied and dried. A method for producing a black stripe, characterized by firing at a temperature of at least ℃. 10. The photosensitive resin according to claim 1, wherein the photosensitive resin has no compatibility or reactivity with the coating liquid for forming a black stripe, and has liquid repellency. Item 10. The method for producing a black stripe according to Item 9.