JPH10188828A - Rib forming photosensitive insulating composition, structural body and forming method of rib - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide simplifying technique for an engineering process which can cope with improvement of accuracy and repeatability and generation of fineness and high resolution, in the case of forming a rib by a sand blast processing method. SOLUTION: A rib forming structural body 200 is formed in a structure laminating a support film 3/photosensitive insulating layer 6/bonding layer 5/protective film 4. The photosensitive insulating layer 6 is formed by a composition adding a photosensitive material to the conventional insulating material, by exposure, the photosensitive material is hardened, sand blast resistance is generated to appear. That is, the photosensitive insulating layer 6 hardened in a rib shape, displaying excellent sand blast resistance, can not be cut by a sand material, so that high accuracy and repeatability can be ensured, a fine rib of high resolution can be manufactured.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition, a structure, and a method for forming a rib for forming a glass substrate with a rib used for a plasma display or the like.

[0002]

2. Description of the Related Art One of manufacturing processes of a plasma display panel includes a rib forming process. The rib is a wall separating each discharge cell, and a sand blast method is being studied as a processing method. An example of a rib structure of a plasma display panel is as follows: rib width 50 μm, rib height 200 μm.
m and the aspect ratio are 4. Despite such a structurally unstable form, as a rib structure,
High accuracy and reproducibility are required.

A conventional rib manufacturing process by the sand blast method will be described with reference to FIGS. a: a step of uniformly forming an insulating layer 9 made of an insulating material for forming ribs on the glass substrate 1 with a predetermined thickness. b: A step of forming a photoresist layer 12 exhibiting sandblast resistance on the insulating layer 9 described above. c: a step of exposing the above-mentioned photoresist layer 12 by covering the photomask 2 with a predetermined pattern. d: Step of developing the above-described photoresist layer 12 to form a resist mask 13. e: a step of ejecting a sand material to remove the insulating layer 9 exposed from the resist mask 13. f: a step of removing the resist mask 13 remaining on the patterned insulating layer 9. g: baking the patterned insulating layer 9 to form the ribs 14
Process.

An insulating material for forming ribs of a plasma display is mainly composed of low melting point lead glass and alumina.
In addition, a mixed system in which an insulating inorganic material is added as necessary. For forming the insulating layer 9 by the sandblasting method, an insulating paste obtained by mixing the above-described insulating material, organic binder, and solvent is used. As a method for forming the insulating layer 9, a method in which an insulating paste is directly applied to a substrate by screen printing, roll coating, or the like and dried,
There is a method of attaching a green sheet-like insulating film formed from an insulating paste on a substrate.

[0005]

However, in the conventional sandblasting method, the rib 1 having a high aspect ratio is not used.
In the manufacturing process of No. 4, there are many defects in which the rib shape is damaged. Examples of the defect include breakage of the rib due to the impact of the sand material (FIG. 17A) and thinning of the rib due to the rebound of the sand material (FIG. 17B).

Further, the conventional sandblasting process requires a step of exposing the resist layer to light and then developing with a solvent, a step of removing the resist on the ribs after sandblasting, and the like, resulting in a problem that the working efficiency is low. Was.

On the other hand, as a measure for improving the luminous efficiency, which is a problem of the plasma display panel, the demand for the improvement of the aperture ratio of the discharge cell, that is, the demand for the finer rib width and the higher resolution is higher than before. And it was necessary to respond to these demands.

[0008]

SUMMARY OF THE INVENTION The present invention has been made for the purpose of improving the above-mentioned problems of the prior art, and is intended to improve the throughput and the cost when manufacturing a ribbed glass substrate used for a plasma display or the like. It aims to provide a manufacturing technology that can cope with reduction, improvement in accuracy and improvement in reproducibility.

The first invention is directed to a mixed composition of an insulating material and a material having a property of changing its properties upon irradiation with an electromagnetic wave such as ultraviolet rays or a particle beam such as β-ray, that is, a photosensitive material. A photosensitive insulating composition for forming a rib, wherein the sandblast resistance of a structure formed from the mixed composition is changed by the irradiation.

According to a second aspect of the present invention, there is provided a rib-forming structure, wherein the rib-forming photosensitive insulating composition according to the first aspect of the present invention is applied on a supporting film, dried and laminated.

A third aspect of the present invention is a rib forming structure, wherein a non-photosensitive insulating layer is laminated on the photosensitive insulating composition of the rib forming structure of the second aspect. .

A fourth invention is characterized in that it has a support film, a photosensitive resist layer laminated on the support film, and a non-photosensitive insulating layer laminated on the resist layer. It is a rib forming structure.

According to a fifth aspect of the present invention, the photosensitive resist layer is formed by applying and drying a photosensitive resist solution, and the non-photosensitive insulating layer is formed by applying and drying an insulating material paste. It is a rib forming structure of the fourth invention.

In a sixth aspect, a photosensitive resist layer comprises:
A selectively peelable photosensitive resist layer was formed in which the irradiated portion adhered to the support film and separated from the non-photosensitive insulating layer, and the non-irradiated portion adhered to the non-photosensitive insulating layer and separated from the support film. A rib forming structure according to the fourth or fifth aspect of the present invention.

In a seventh aspect, a photosensitive resist layer comprises:
A non-irradiated portion adheres to the support film and peels off from the non-photosensitive insulating layer, and an irradiated portion adheres to the non-photosensitive insulating layer and peels off from the support film. A rib forming structure according to the fourth or fifth aspect of the present invention.

An eighth invention provides a photosensitive resist layer comprising:
The structure for forming a rib according to the fourth or fifth aspect of the present invention, wherein a photosensitive resist layer whose sandblasting resistance of the irradiated portion is changed is formed.

According to a ninth aspect of the present invention, as a photosensitive resist layer,
The rib-forming structure according to any one of the fourth to eighth inventions, wherein a complete burning type photosensitive resist layer from which no residue is formed is formed.

A tenth invention is the rib-forming structure according to any one of the second to ninth inventions, wherein an adhesive layer is formed on an uppermost layer.

An eleventh aspect of the present invention is the rib-forming structure according to the tenth aspect of the present invention, wherein the adhesive layer has excellent sand blast resistance and is made of a complete combustion type adhesive that does not leave residue. It is.

The twelfth invention is characterized in that the protective film is releasably laminated on the adhesive layer.
It is a rib forming structure of the invention.

According to a thirteenth invention, a step of forming a photosensitive insulating layer on a substrate using the rib-forming photosensitive insulating composition of the first invention or the rib-forming structure of the second invention. And a step of coating the photosensitive insulating layer with a desired mask pattern and irradiating the photosensitive insulating layer with a resist mask, if necessary, after coating the resist mask as necessary. Is formed on a substrate.

[0022]

Embodiments of the present invention will be described below.

The photosensitive insulating composition for forming a rib according to the present invention comprises an insulating material and an electromagnetic wave such as ultraviolet rays, infrared rays, X-rays, etc.
The property of changing its properties when irradiated with a particle beam such as β-ray (electron beam) (in the present invention, these are referred to as radiation) (this property is called photosensitive from historical background. A composition having a property that changes its properties by irradiation with X-rays or particle beams is also referred to as photosensitive), and a structure formed from the mixed composition has a sand blast resistance, that is, a resistance to sand blast. A photosensitive insulating composition whose properties are changed by the irradiation.

Such a photosensitive insulating composition is prepared by adding a radiation-reactive material such as a radiation-polymerizable polymer, oligomer or monomer to a radiation-reactive material such as a radiation-polymerizable polymer, oligomer or monomer. It can be prepared by adding an initiator.

When the structure obtained by applying and drying the photosensitive insulating composition is irradiated with, for example, an ultraviolet ray, the irradiated portion, that is, the exposed portion is increased in the degree of curing by the photopolymerization reaction of the photosensitive material, for example, and the sandblast resistance is reduced. Will be expressed.

The material of the photosensitive insulating composition will be described. As the insulating material, PbO, SiO ₂ , MgO,
A low-melting-point lead glass powder composed of an inorganic substance such as Al ₂ O ₃ , ZnO, SnO ₂ and serving as a binder during the firing step;
A high-melting substance such as alumina serving as a skeleton of the rib structure is used.

The binder resin and the solvent are materials for converting the insulating material into a paste to give the rib-forming insulating layer a film forming ability, and do not react with the insulating material.
The material is not particularly limited as long as it is a material that burns and disappears in the firing step. For example, the following resins can be used. Cellulosic polymers such as nitrocellulose, acetylcellulose, ethylcellulose, carboxymethylcellulose, and methylcellulose; natural polymers such as natural rubber, polybutadiene rubber, chloroprene rubber, acrylic rubber, isoprene-based synthetic rubber, and cyclized rubber; polyethylene, polypropylene, and poly Synthetic polymers such as methyl acrylate, poly (methyl methacrylate), polystyrene, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate, polyester, polycarbonate, polyacrylonitrile, polyvinyl chloride, polyvinyl acetate, polyamide, and polyurethane. These resins are used alone, as a mixture or as a copolymer.

The solvent is preferably one that uniformly dissolves or disperses the above binder resin. For example, the following solvents can be used. Hydrocarbons such as triene, xylenetetralin and mineral spirit, alcohols such as methanol, ethanol, isopropanol and α-terpineol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone, methyl acetate, ethyl acetate and acetic acid Ethyl glycol glycol ethers such as butyl, ethyl acetate, etc., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, diethylene glycol monoe Ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol ether and diethylene glycol monobutyl ether acetate.

The radiation-polymerizable oligomer is not particularly limited, but acrylic oligomers such as ester acrylate, ether acrylate, epoxy acrylate and urethane acrylate are preferred in view of the reaction rate.

Examples of the radiation polymerizable monomer include (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl acrylate, benzyl acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxy Monofunctional monomers such as ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butoxyethyl acrylate, methoxyethylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol diacrylate , Pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, include impressionable ability monomers such as trimethylolethane tri (meth) acrylate.

Examples of the radiation polymerization initiator include acetophenone, 2,2'-diethoxyacetophenone, benzyldimethyl ketal, benzophenone, methyl o-benzoylbenzoate, benzoin, benzoin ethyl ether,
Benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, 2-hydroxy-2-methyl-propiophenone, 2-methylthioxanthone, 2-chlorothioxanthone and the like can be used.

In addition, dispersants such as isobitane fatty acid ester and benzene sulfonic acid, and plasticizers such as butyl cetearate, butyl benzyl phthalate, dibutyl phthalate and diisodecyl phthalate may be added as necessary. . As a method for preparing the paste of the photosensitive insulating composition, a mixing device such as a roll mill, a bead mill, and an automatic mortar is used.

In the rib-forming structure according to the present invention, the rib-forming photosensitive insulating composition is a film-shaped rib-forming structure laminated on a support film layer. As described above, by using the photosensitive insulating composition as a film-shaped photosensitive insulating layer, the thickness control of the rib-forming insulating layer is simplified.

The first embodiment of the rib forming structure according to the present invention will be specifically described with reference to FIG. 1 and the second embodiment thereof with reference to FIG. The rib forming structure 100 according to the first embodiment has a laminated structure of the support film 3 / photosensitive insulating layer 6 / protective film 4 from the lower layer. The same applies hereinafter.). On the other hand, the rib forming structure 200 of the second embodiment has a laminated structure of the support film 3, the photosensitive insulating layer 6, the adhesive layer 5, and the protective film 4. When a proper release agent is applied to the back surface of the support film 3 and the whole is wound up in a roll shape, it is not necessary to provide the protective film 4.

Then, the rib forming structures 100 and 20
No. 0 photosensitive insulating layer 6 is an insulating layer formed by applying and drying a paste of the rib-forming photosensitive insulating composition having the above-described configuration, and the exposed portion has a degree of curing by radiation polymerization reaction of the photosensitive material. In addition, excellent sandblast resistance is exhibited. Conversely, the unexposed portions are cut by a sand material during sandblasting.

As described above, the adhesive layer 5 of the rib forming structure 200 is provided between the photosensitive insulating layer 6 and the substrate,
It is a material that improves the adhesion between each other, and if it is a completely burning type adhesive or pressure-sensitive adhesive that does not burn off or leave organic carbides in the firing step, it is particularly limited, such as a solvent volatilization type, a chemical reaction type, and a heat melting type. Not done. For example, photo-curable acrylic adhesive, epoxy adhesive, natural rubber,
A styrene-butadiene-based or isoprene-based solvent-based pressure-sensitive adhesive, an acrylic-based solvent-based pressure-sensitive adhesive, a hot-melt-type pressure-sensitive adhesive such as a styrene-isoprene block copolymer or an ethylene-vinyl acetate thermoplastic elastomer can be used.

In addition, only the adhesive layer 5 which is in direct contact with the glass substrate 1 is protected by protecting the glass substrate 1 by adding a material having sand blast resistance, such as a plasticizer, to reduce the impact of the sand material during sand blast. can do.

The support film 3 and the protective film 4 are desirably smooth, flexible, solvent-resistant, heat-resistant, light-stable, and light-transmissive, such as polyethylene terephthalate. In addition to polyethylene terephthalate, polyethylene, polypropylene, triacetate, polystyrene, polyvinyl chloride, polycarbonate, polyurethane, polyimide and the like can be used. The thickness of the film is not particularly limited.
A thickness of about 100 μm is preferable.

A method of manufacturing the rib forming structures 100 and 200 will be described with reference to FIGS. First,
A paste made of the photosensitive insulating composition is uniformly applied on the support film 3, and the solvent component is sufficiently volatilized by a drying process to form a photosensitive insulating layer 6 for forming ribs. Next, in the rib forming structure 200, an adhesive is applied on the photosensitive insulating layer 6 to form the adhesive layer 5. Thereafter, the protective film 4 is pressed against both the rib-forming structures 100 and 200 to form the rib-forming structures 100 and 200.

As a method for applying the paste made of the photosensitive insulating composition to the support film 3, roll coating, curtain coating, gravure coating, screen printing, and the like can be used. These coating methods are appropriately used according to the material and the viscosity characteristics.

Next, an example of forming the ribs 14 on the glass substrate 1 using the rib forming structure 200 will be described with reference to the process chart of FIG. In this case, the photosensitive insulating layer 6 of the rib-forming structure 200 is formed to have a thickness through which irradiation light passes (to reach below).

First, while peeling off the protective film 4 of the rib forming structure 200, the adhesive layer 5 was formed using a laminator device.
Is pressed against the glass substrate 1 (FIG. 3A). Next, a photomask 2 having a predetermined pattern is brought into close contact with the support film 3 and irradiated with a predetermined exposure amount in a vacuum exposure apparatus (FIG. 3B). By repeating this process, the layers are stacked up to the required height of the rib structure (FIGS. 3C to 3E).

After completion of the lamination, sand blasting is performed with a sand material to cut the rib into a rib shape (FIG. 3F). At this time,
The exposed portion 7 of the photosensitive insulating layer 6 has an increased degree of hardening due to a radiation polymerization reaction, and therefore exhibits excellent sandblast resistance and is not cut with a sand material. In addition, if the adhesive layer 5 of the rib forming structure 200 used first has a resistance to sandblasting, the surface of the glass substrate 1 is protected. The surface is not damaged. Then, by firing in a firing furnace, the insulating ribs 14 can be formed (FIG. 3g).

The sand material is selected in such a manner that the hardness of the sand material is higher than the unexposed portion 8 of the photosensitive insulating layer 6 and
It is necessary to use a lower material. Sand materials include alumina, carborundum, glass beads, silicon carbide,
Hard plastic or the like can be used, and an appropriate sand material is appropriately selected. Further, the ejection strength of the sand material may be appropriately adjusted.

As described above, the rib forming structure 100
And 200, the photosensitive insulating layer 6 is a mixed composition of an insulating material and a photosensitive material. The photosensitive insulating layer 6 is formed on the glass substrate 1 and the exposed portions 7 are formed by using photolithography technology. Is cured into a rib shape and laminated to a desired height, followed by sandblasting.

That is, since the exposed portion 7 of the photosensitive insulating layer 6 cured into a rib shape exhibits excellent sand blast resistance, the rib strength at the time of rib production increases, and the rib shape produced by the conventional sand blast method is improved. Since high accuracy and reproducibility can be ensured, it is possible to manufacture a rib having a fine and high resolution.

The photosensitive insulating layer 6 can exhibit the above characteristics by adding a radiation-reactive material to the dry paste. As the radiation that induces the reaction, electromagnetic waves such as ultraviolet rays and infrared rays and particle beams such as β rays (electron beams) can be used, and it is necessary to select a reactive material according to the type of radiation.

In the rib forming step shown in FIG. 3, a paste made of a photosensitive insulating composition may be applied to the substrate instead of the rib forming structure 200 (Example 1). Also, the laminated rib forming structure 200
It is also possible to form a resist pattern by forming a photosensitive resist layer thereon and perform sandblasting.

Another example of forming the ribs 14 on the glass substrate 1 using the rib forming structure 200 will be described with reference to the process chart of FIG. Also in this case, the adhesive layer 5 has sandblast resistance. In this step, the thickness of the ribs of the photosensitive insulating layer 6 of the rib forming structure 200 is set in advance.

First, the adhesive layer 5 is pressed against the glass substrate 1 by using a laminator while peeling off the protective film 4. Next, a photomask 2 having a predetermined pattern is brought into close contact with the support film 3 and irradiated with a predetermined exposure amount in a vacuum exposure apparatus (FIG. 4A). After the exposure, the support film 3 is peeled off, sand blasting is performed with a sand material, and cut into a rib shape (FIG. 4B). At this time, the photosensitive insulating layer 6
The exposed portion 7 has increased hardness due to a radiation polymerization reaction or the like,
Since it exhibits excellent sandblast resistance and is not cut with a sand material, the photosensitive insulating layer 6 thereunder also remains.

Also in this case, the sand material needs to have a higher hardness than the unexposed portion 8 of the photosensitive insulating layer 6 and a lower hardness than the exposed portion 7 of the photosensitive insulating layer 6.

The depth of the exposed portion 7 is not particularly limited as long as it is within a range showing resistance to the sand material. However, since the scattering of radiation in the photosensitive insulating layer 6 causes a reduction in rib width accuracy, It is preferable that only the surface layer of the photosensitive insulating layer 6 be cured as much as possible. The depth of the exposure unit 7 is adjusted by conditions such as the type of radiation, intensity, and irradiation time. After that, since the exposed portion 7 is also an insulator derived from the photosensitive insulating layer 6, the conventional resist pattern peeling step is unnecessary,
Moving directly to the firing step, the ribs 14 can be formed by firing (FIG. 4c).

As described above, the conventional steps of applying a photosensitive resist solution and attaching a dry film resist are unnecessary when manufacturing a substrate with ribs, so that problems such as poor attachment can be avoided, and the manufacturing process is simple. Be transformed into Further, since no solvent is used for development, there is no penetration of the solvent into the rib layer. In addition, there is no need for a stripping step of an unexposed portion left after the conventional sandblasting step. Furthermore, as a bonding layer between the rib forming structure and the glass substrate, a substrate having sand blast resistance is used to maintain the uniformity of the substrate surface shape, and a complete combustion type is used for bonding during firing. The material can be completely demineralized.

The rib-forming structure 10 having no adhesive layer 5
In the case of manufacturing a substrate with ribs using No. 0, a hot-melt type adhesive or a thermoplastic resin is mixed in a photosensitive insulating paste and thermocompression-bonded.

A rib forming structure 300 according to a third embodiment of the present invention will be described with reference to FIG. The rib forming structure 300 has a laminated structure of a support film 3 / photosensitive insulating layer 6 / insulating layer 9 / adhesive layer 5 / protective film 4 from the lower layer. Also in this case, it is not necessary to provide the protective film 4 when an appropriate release agent is applied to the back surface of the support film 3 and the whole is wound into a roll.

The photosensitive insulating layer 6 is made of a mixture of an insulating material serving as a rib material and a photosensitive material, and has a performance equivalent to a conventionally known resist. That is, when exposed to radiation, the part is cured and develops excellent sand blast resistance. Conversely, the unexposed part is cut by sand blast, and the rib forming structure 200 is formed. The same material as the photosensitive insulating layer 6 is used.

On the other hand, the insulating layer 9 is made of a non-photosensitive insulating paste which has been conventionally used, and is made of glass frit,
A basic material is a high-melting substance such as alumina, a binder resin, a solvent, and an additive. The same as described above is used for the support film 3, the protective film 4, and the adhesive layer 5.

Next, a method of manufacturing the rib forming structure 300 will be described with reference to FIG. First, a photosensitive insulating paste that exhibits sandblast resistance by exposure is uniformly applied onto the support film 3, and the solvent component is sufficiently volatilized by a drying process to form the photosensitive insulating layer 6. An insulating paste made of a conventional composition having no photosensitive function is uniformly applied thereon, and a solvent component is volatilized by a drying process to form an insulating layer 9. After that, the adhesive layer 5 is applied on the insulating layer 9 and the protective film 4 is pressure-bonded to form the rib forming structure 300. The coating method of the insulating paste includes roll coating, curtain coating, gravure coating,
Screen printing or the like can be used. These coating methods are appropriately used according to the material and the viscosity characteristics.

Next, an example of forming the ribs 14 on the glass substrate 1 using the rib forming structure 300 will be described with reference to the process chart of FIG. First, while peeling off the protective film 4, the adhesive layer 5 was applied to the glass substrate 1 using a laminator device.
Crimp to Next, a mask 2 having a predetermined pattern is brought into close contact with the support film 3 and irradiated with a predetermined exposure amount in a vacuum exposure apparatus (FIG. 6A). After exposure, support film 3
Peel off and carry out sand blasting with sand material,
Cutting into a rib shape (FIG. 6b). At this time, the exposed portion 7 of the photosensitive insulating layer 6 has increased hardness due to the radiation curing reaction and exhibits excellent sand blast resistance, and is not cut with a sand material. The unexposed portions 8 that are not exposed and hardened but remain in a rib shape are cut by a sand material, so that the insulating layer 9 is also cut immediately below the unexposed portions 8. Also in this case, the adhesive layer 5 is made of a completely combustible material and has sandblast resistance.

The exposed portion 7 is usually exposed over the entire thickness of the photosensitive insulating layer 6. After that, since the exposed portion 7 is also an insulator derived from the photosensitive insulating layer 6, the conventional resist pattern peeling step is unnecessary, and the process can directly proceed to the firing step, and the rib 14 can be formed by firing. 6c).

The photosensitive insulating layer 6 of the rib forming structure 300 has characteristics of an insulating material and a photosensitive resist. This eliminates the need for a conventional photosensitive resist solution coating step or a dry film sticking step made of a photosensitive resist material, and can also avoid problems such as poor sticking. Also,
Since the development process is not required, there is no need to use a solvent,
There is no solvent penetration into the rib layer. In addition, there is no need to remove the unexposed portion of the dry film resist remaining on the rib tops as in the conventional sandblasting process. Furthermore,
As an adhesive layer between the rib forming structure and the glass substrate,
By using a material having sand blast resistance, the uniformity of the substrate surface shape can be maintained, and by using a complete combustion type, the adhesive material can be completely demineralized during firing.

When the photosensitive insulating layer 6 is exposed to light, the portion is decomposed to increase the elasticity. As a result, excellent sand blasting resistance is exhibited, and the unexposed brittle portion is cut by sand blasting. Figure 7 used
Next, the rib forming structure 400 according to the fourth embodiment of the present invention shown in FIG.

The rib forming structure 400 also has a laminated structure of a support film 3 / photosensitive insulating layer 6 / adhesive layer 5 / protective film 4 from the lower layer, and a radiation-reactive material is contained in the insulating paste. By adding it, the photosensitive resist function is added to the photosensitive insulating dry paste 6.

In this case, the adhesive layer 5 is also made of a complete combustion type material and has sandblast resistance. Further, as the support film 3 and the protective film 4, the same films as those of the rib forming structure 300 and the like can be used.

Next, an example of forming the ribs 14 on the glass substrate 1 by using the rib forming structure 400 will be described with reference to the process chart of FIG. First, while peeling off the protective film 4, the adhesive layer 5 was applied to the glass substrate 1 using a laminator device.
Crimp to Next, a photomask 2 having a predetermined pattern is brought into close contact with the support film 3 and irradiated with a predetermined exposure amount in a vacuum exposure apparatus (FIG. 8A). After the exposure, the support film 3 is peeled off, sand blasting is performed with a sand material, and cut into a rib shape (FIG. 8B). At this time, the unexposed portion 8 of the photosensitive insulating layer 6 is cut by a sand material because it is brittle, but the exposed portion 7 exhibits excellent sand blast resistance due to an increase in elasticity and is not cut by the sand material. And is formed in a rib shape together with the photosensitive insulating layer 6.

Also in this case, the sand material is not particularly limited as long as it has a higher hardness than the photosensitive insulating layer 6 and does not cut the exposed portion 7 of the photosensitive insulating layer 6. As the sand material, each of the above materials can be used.

The depth of the exposed portion 7 is not particularly limited as long as it is within the range of exhibiting resistance to the sand material. However, the scattering of the radiation in the photosensitive insulating layer 6 causes the rib width accuracy to decrease. Therefore, it is preferable that only the surface layer of the photosensitive insulating layer 6 is decomposed and elasticity is increased as much as possible. The depth of the exposure unit 7 is adjusted by conditions such as the type of radiation to be irradiated, the intensity, and the irradiation time. After that, since the exposed portion 7 is also an insulator derived from the photosensitive insulating layer 6, the conventional resist pattern peeling step is unnecessary, and the rib 14 can be formed by directly moving to the firing step ( FIG. 8c).

Next, the material of the rib forming structure 400 will be described. As a photosensitive insulating paste for forming the photosensitive insulating layer 6, an insulating material and a photosensitive material that exhibits the function of the photosensitive resist are required.

As the insulating material, the low melting point lead glass powder or alumina used for the photosensitive insulating layer 6 of the rib forming structures 100, 200, 300 is used.

On the other hand, the photosensitive resist function used here is an exposure-portion decomposition type (positive type). Therefore, the photosensitive material used as the positive resist is o-naphthoquinonediazidesulfonic acid ester-novolak resin,
Photo-modified molding of diazomeldrum acid-novolak resin system, diazodimedone-polyvinylphenol system, o-nitrobenzylcarboxylic acid ester and acrylic acid-methacrylic acid copolymer system, polymethyl methacrylate compound, polymethyl isopropenyl ketone And methacrylic acid and 3-methacryloxyimino-2-butanone copolymer, methacrylic acid and indanone copolymer, and photodegradation polymerization type such as polyglutarimide and polyolefin sulfone.

The photosensitive material of the photosensitive insulating layer 6 may be formed by using the above-described photosensitive substance alone, or may be used by mixing with a binder resin. Examples of the binder resin include natural polymers such as cellulose, alginic acid, and gums, polystyrene, polyvinyl alcohol, polyvinyl butyral, (meth) acrylic, vinyl chloride, vinyl acetate copolymer, and polyamide. A single or mixed system of synthetic polymers such as polyurethane and polyurethane can be used.

The solvent is preferably one that uniformly dissolves or disperses the above-mentioned binder and ink components. For example, aliphatic hydrocarbons, aromatic hydrocarbons, alcohols,
Ketones, esters, glycol ethers, glycol esters and the like can be mentioned. As additives, dispersants such as isopitane fatty acid ester and benzenesulfonic acid, butyl cetearate, butyl benzyl phthalate,
Plasticizers such as dibutyl phthalate and diisodecyl phthalate, other wetting agents, antifoaming agents and the like may be added as necessary.

The photosensitive insulating layer 6 of the rib forming structure 400 of the present invention also has the properties of an insulating material and a photosensitive resist. Therefore, the conventional process of applying a photosensitive resist solution or the process of attaching a dry film made of a photosensitive resist material is not required at the time of rib formation, and problems such as poor adhesion can be avoided. Further, since the developing step is unnecessary, there is no need to use a solvent, and there is no penetration of the solvent into the rib layer.

Further, there is no need to remove the unexposed portion of the dry film left on the top of the rib as in the conventional sandblasting process. Furthermore, as the adhesive layer between the rib forming structure and the glass substrate, a substrate having sand blast resistance is used to maintain the uniformity of the substrate surface shape, and
By using the complete combustion type, the adhesive material can be completely demineralized during firing.

A rib forming structure 500 according to a fifth embodiment of the present invention will be described with reference to FIG. The rib forming structure 500 has a laminated structure of a support film 3 / photosensitive resist layer 10 / insulating layer 9 / adhesive layer 5 / protective film 4 from the lower layer.

The photosensitive resist layer 10 of the rib forming structure 500 can be formed by using the photosensitive material of the photosensitive insulating layer 6 of the rib forming structure 400.
It can be developed by sandblasting and can be formed into a complete combustion type. That is, the exposed portion 7 which has been irradiated with the radiation is decomposed and increased in elasticity to form a resist mask exhibiting excellent sandblast resistance.
Is cut by sandblasting, and then the lower insulating layer 9 is also cut. The insulating layer 9 is completely burned out by the burning process or does not leave organic carbide.

In the rib forming structure 500,
The conventional steps of applying a photosensitive resist solution and attaching a dry film are not required, so that the manufacturing process can be simplified, the resist mask developing and stripping steps can be eliminated, and the solvent can be eliminated.

A method for manufacturing the rib forming structure 500 will be described with reference to FIG. First, a photosensitive resist solution is uniformly applied on the support film 3, and a solvent component is sufficiently volatilized by a drying process to form a photosensitive resist layer 10 for forming ribs. Next, an insulating paste is uniformly applied on the photosensitive resist layer 10, and a drying process is performed.
And Thereafter, the adhesive layer 5 is applied, and the protective film 4 is pressure-bonded to form a rib-forming structure 500.

As a method of applying each of the insulating paste and the adhesive, a roll coat, a curtain coat, a gravure coat, a screen printing, etc. can be used in this case as well. These coating methods are appropriately used according to the material and the viscosity characteristics.

Next, an example of forming the ribs 14 on the glass substrate 1 using the rib forming structure 500 will be described with reference to the process chart of FIG. First, the adhesive layer 5 is pressure-bonded to the glass substrate 1 using a laminator device while peeling off the protective film 4. Next, a photomask 2 having a predetermined pattern is brought into close contact with the support film 3 and irradiated with a predetermined exposure amount in a vacuum exposure apparatus (FIG. 10A). After the exposure, the support film 3 is peeled off, sand blasting is performed with a sand material, and cut into a rib shape (FIG. 10B). At this time,
The unexposed portion 8 of the photosensitive resist layer 10 is fragile and is cut by a sand material. However, the exposed portion 7 exhibits excellent sand blast resistance due to an increase in elasticity, and is not cut by the sand material. It remains in a rib shape together with the insulating layer 6.

Also in this case, the selection of the sand material is not particularly limited as long as the sand material has a higher hardness than the photosensitive resist layer 10 and does not cut the exposed portion 7 of the photosensitive resist layer 10. The above materials can be used as the sand material.

The exposed portion 7 usually has a photosensitive resist layer 10
Exposure over the entire thickness of After that, since the exposed portion 7 of the photosensitive resist layer 10 is of a complete combustion type, the step of removing the resist pattern becomes unnecessary, and the process directly proceeds to the baking step.
It is fired to form ribs 14 (FIG. 10c).

The rib forming structure 600 shown in FIG.
Shows a photosensitive resist layer 10 of a peeling development type. The peeling development is a technique in which a portion cured by the exposure step is fixed to the support film 3 and peeled from the dry paste 9. The rib forming structure 600 includes a support film 3 / photosensitive resist layer 10 / insulating layer 9 /
The laminated structure of the adhesive layer 5 and the protective film 4 is formed.

The material of the rib forming structure 600 will be described. The peel-developing type photosensitive resist layer 10 used here is of an exposed portion curing type (negative type) and has sandblast resistance when not exposed, and loses sandblast resistance when exposed. Solvents, radiation polymerizable oligomers, radiation polymerizable monomers, radiation polymerization initiators, and additives are the basic materials. In the peeling development type, it is not necessary to use a solvent or an alkaline solution at the time of development. Therefore, the binder resin is not limited to hydrophilicity, hydrophobicity, etc., as long as it gives uniform film-forming ability. Also, by blending a hot-melt resin with these binder resins, thermocompression bonding to a dry film becomes possible. For example, styrene-isoprene type, ethene-vinyl acetate type, and the like can be used.

The solvent is preferably one that uniformly dissolves or disperses the above-mentioned binder and ink components. For example, aliphatic hydrocarbons, aromatic hydrocarbons, alcohols,
Examples thereof include ketones, esters, glycol ethers, and glycol esters.

The radiation-polymerizable oligomer is not particularly limited, but acrylic oligomers such as ester acrylate, ether acrylate, epoxy acrylate and urethane acrylate are preferred in view of the reaction rate.

Further, a (meth) acrylic monomer may be used for the purpose of adjusting the viscosity in forming the film and the hardness after forming the film. Specific examples include ethylhexyl acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, butoxyethyl acrylate, methoxyethylene glycol acrylate, and ethylene glycol diacrylate.

As the radiation polymerization initiator, benzoin ether type, benzophenone type, ketal type, acetophenone type, thioxanthone type and the like are used. As additives, wetting agents, dispersants, plasticizers, antifoaming agents and the like are used as necessary.

As the support film 3, the protective film 4, and the adhesive layer 5, the same materials as those of the rib forming structure 500 and the like can be used.

An example of a method for manufacturing the rib forming structure 600 will be described with reference to FIG. First, a photosensitive resist solution is applied on the support film 3, and a solvent component is sufficiently evaporated and dried in a drying step to form a photosensitive resist layer 10. Then, a non-photosensitive insulating paste is applied on the photosensitive resist layer 10 and dried to form a non-photosensitive insulating layer 9. Thereafter, an adhesive is applied on the insulating layer 9 to form an adhesive layer 5, and the protective film 4 is further pressed to form a rib forming structure 600.

Alternatively, the photosensitive resist layer 10 separately formed and the film of the non-photosensitive insulating layer 9 are bonded to each other. For this bonding, an adhesive can be used. However, if a dry film that develops tackiness by heating is used, the step of applying the adhesive can be omitted.
A roller laminator or the like is used for adhesion.

As a method for applying the photosensitive resist solution and the insulating paste, roll coating, curtain coating, gravure coating, screen printing, and the like can be used. These coating methods are appropriately used according to the material and the viscosity characteristics.

Next, an example of a method of forming the ribs 14 on the glass substrate 1 using the rib forming structure 600 will be described with reference to the process chart of FIG. First, the adhesive layer 5 is pressure-bonded to the glass substrate 1 using a laminator while peeling off the protective film 4 of the rib forming structure 600. next,
A photomask 2 having a predetermined pattern is supported on a supporting film 3.
And a predetermined exposure amount is exposed (FIG. 12A). After the exposure, the support film 3 is peeled off. At this time, the exposure unit 7 is fixed to the support film 3 and peels off together with the support film 3 (FIG. 12B). Therefore, the photosensitive resist layer 10 can be developed by peeling off the support film 3. For this reason, it is not necessary to use a solvent at the time of development, and it is possible to avoid penetration of the solvent into the insulating layer 9 forming the rib.

After the peeling is completed, sand blasting is performed.
A portion of the insulating layer 9 covered by the unexposed portion 8 of the photosensitive resist layer 10 having excellent sandblast resistance
And cut into a rib shape (FIG. 12c). Next, on the unexposed portion 8 of the photosensitive resist layer 10 remaining on the upper part of the rib shape, the same thing as the support film 3 peeled off in the peeling and developing step (FIG. 12B) is coated and adhered. Then, by exposing from above, the unexposed portion 8 becomes the exposed portion 7.
And it is fixed to the support film 3. Therefore, it can be separated by the same method as described above (FIG. 12).
d).

As described above, by using the peel-developing type photosensitive resist layer 10, the unexposed portions 8 of the photosensitive resist layer 10 remaining on the ribs can be easily removed. After the separation, the ribs 14 are formed by a firing step (FIG. 12E).

In this case, the selection of the sand material requires that the hardness of the sand material is higher than that of the insulating layer 9 and lower than that of the photosensitive resist layer 10. The above-mentioned materials can be used as the sand material.

When the photosensitive resist layer 10 is made of a complete burning type material, the process of FIG.

Seventh Embodiment Rib Forming Structure 700
Will be described with reference to FIG. This rib forming structure 70
The portion of the photosensitive resist layer 10 decomposed in the exposure step adheres to the insulating layer 9, and the unexposed part adheres to the support film 3, and is developed by peeling.

The photosensitive resist layer 10 is of an exposed part decomposition type (positive type) exhibiting the above-described peeling development function and complete combustion characteristics, and the following material system used as a positive type resist can be used. . o-naphthoquinonediazidosulfonic acid ester-novolak resin system, 5-diazomeldrum acid-nolabok resin system, diazodimedone-polyvinylphenol system, o-nitrobenzylcarboxylic acid ester and acrylic acid-methacrylic acid copolymer system, etc. Molding, photolysis of polymethyl methacrylate compound, polymethyl isopropenyl ketone, methacrylic acid and 3-methacryloxyimino-2-butanone copolymer, methacrylic acid and indanone copolymer, polyglutarimide, polyolefin sulfone, etc. Polymerization type.

The photosensitive resist layer 10 may be formed by using the above-mentioned photosensitive substance alone, or may be used by mixing with a binder resin. As the binder resin, a cellulose resin or an acrylic resin is preferable. Further, as additives, wetting agents, dispersants, plasticizers, defoamers and the like are used as necessary.

Next, an example of a method of forming the ribs 14 on the glass substrate 1 using the rib forming structure 700 will be described with reference to the process chart of FIG. First, the adhesive layer 5 is pressure-bonded to the glass substrate 1 using a laminator device while peeling off the protective film 4 of the rib forming structure 700 (FIG. 14).
a). Next, a photomask 2 having a predetermined pattern is brought into close contact with the support film 3, and a predetermined exposure amount is exposed (FIG. 14B). After the exposure, the support film 3 is peeled off. At this time,
The exposed portion 7 adheres to the insulating layer 9 serving as a rib insulating layer, and the unexposed portion 8 peels off at the same time as the support film 3 (FIG. 14).
c). Therefore, the photosensitive resist layer 10 can be developed by peeling the support film 3. For this reason, it is not necessary to use a solvent at the time of development, and it is possible to avoid penetration of the solvent into the insulating layer 9 for ribs. After the peeling is completed, sand blasting is performed with a sand material, and the insulating layer 9 is cut into a rib shape (FIG. 14D).

Since the photosensitive resist layer 10 is a complete burning type, the exposed portion 7 of the photosensitive resist layer 10 remaining above the ribs formed by cutting after the sand blasting process burns and disappears in the firing process. . Therefore, according to the rib forming structure 700, the step of removing the photosensitive resist layer 10 can be omitted, and the process directly shifts to the firing step.
Ribs 14 can be formed (FIG. 14e).

In the step of attaching the exposed portion 7 to the insulating layer 9 and peeling off the unexposed portion 8 with the support film 3, the photosensitive component is decomposed in the exposure step to become flexible and exhibit adhesiveness. Is Photolitho tacking resist PT
R (manufactured by Fuji Pharmaceutical), DHP-E, DHP-M (manufactured by DuPont) or the like may be used. Also, the support film 3,
As the protective film 4, the adhesive layer 5, and the like, those described above can be used.

In summary of the above-described embodiment of the present invention, a portion to be cut can be easily cut by a sand material, a portion to be left is hard to be cut, or a portion to be cut should be easily cut and left. Make the part hard to scrape.

Hereinafter, the present invention will be described more specifically with reference to examples. Example 1 The formulation of the photosensitive insulating composition is shown below. Glass frit 57 parts by weight _{PbO 50wt% SiO 2 29wt% Al} 2 O 3 12wt% B 2 O 3 7wt% ZnO 1wt% SnO 2 1wt% of alumina powder 23 parts by weight of epoxy acrylate, 6 parts by weight of dipentaerythritol hexaacrylate 6 parts by weight acetophenone 1 part by weight Ethyl cellulose 6 parts by weight Isophthalic acid 1 part by weight Diethylene glycol ethyl ether 24 parts by weight

These materials were kneaded by a roll mill to obtain a paste of a photosensitive insulating composition. The step of forming the ribs 14 using this paste will be described with reference to FIG.

The above paste is applied on a glass substrate 1 for 20 minutes.
The first layer of the photosensitive insulating layer 6 was formed by applying a screen printing to a thickness of μm and drying at 90 ° C. (FIG. 15)
a). Next, a photomask 2 having a rib pattern having a width of 30 μm was placed on the photosensitive insulating layer 6, placed in a vacuum exposure apparatus, and exposed to a light amount of 300 mJ / cm ² by a high-pressure mercury lamp (FIG. 15B). . This operation was repeated seven times (FIGS. 15C to 15D) to form a laminate of the photosensitive insulating layer 6 having a thickness of 160 μm on the glass substrate 1 (FIG. 15E).

Then, the unexposed portion 8 of the photosensitive insulating layer 6 was cut with a sand blasting device using a sand material made of glass beads (FIG. 15F). At this time, the exposed portion 7 having a rib shape in the laminate of the photosensitive insulating layer 6 exhibits excellent sandblast resistance because the photosensitive material is cured by a radiation response reaction, and has a rib shape having a width of 30 μm and a height of 160 μm. I was holding.

After sandblasting, the process was shifted to a firing step. By the firing step (580 ° C.), the ribs 14 made of only the insulating material could be formed on the glass substrate 1 (FIG. 15G).

[Embodiment 2] FIG.
Subsequent to the step e, a completely-burning photosensitive resist having a sand blast resistance was applied by screen printing to a thickness of 20 μm and dried to form a photosensitive resist layer. Thereafter, the photomask 2 was covered and exposed in a vacuum exposure apparatus, and the unexposed portion of the photoresist layer was developed with a developing solution and dried to form a resist mask having a 30 μm rib pattern.

Then, the uncoated part of the photosensitive resist was cut with a sand blasting device using a sand material made of glass beads. At this time, since the photosensitive material has been cured by the radiation response reaction, the rib-shaped exposed portion 7 in the laminated body of the photosensitive insulating layer 6 exhibits excellent sandblast resistance and has a rib having a width of 30 μm and a height of 160 μm. The shape was retained.

After the sandblasting, the process was shifted to the baking step without stripping the resist mask remaining on the ribs with a stripper. After the firing step (580 ° C.), the ribs 14 made of only the insulating material could be formed on the glass substrate 1.

Example 3 The photosensitive insulating composition paste prepared in Example 1 was roll-coated to a thickness of 25 μm on a polyethylene terephthalate (30 μm) support film 3 and dried at 90 ° C. . Next, an adhesive obtained by adding phthalic acid to the octyl acrylate-methacrylic acid copolymer / toluene system to provide sand blast resistance is applied and dried to form an adhesive layer 5, and a polyethylene film (10 μm ) Was pressed to form a rib-forming structure 200. Further, a rib-forming structure 100 having no adhesive layer 5 was also formed at the same time.

The process of forming the ribs 14 on the glass substrate 1 using the rib forming structures 100 and 200 will be described with reference to FIG. That is, while the protective film 4 of the rib-forming structure 200 was peeled off, the rib-forming structure 200 was pressed on the glass substrate 1 with a roll laminator to form the first layer of the photosensitive insulating layer 6 (FIG. 3A). ). Next, a photomask 2 having a rib pattern having a width of 30 μm was placed on the photosensitive insulating layer 6, placed in a vacuum exposure apparatus, and exposed to light of 300 mJ / cm ² with a high-pressure mercury lamp (FIG. 3).
b). Next, the same process is performed on the rib forming structure 100 by 4 steps.
This was repeated twice to form a laminate of the photosensitive insulating layer 6 having a thickness of 125 μm (FIGS. 3C to 3E).

Next, the unexposed portion 8 of the photosensitive insulating layer 6 was cut with a sand blasting device using a sand material made of glass beads (FIG. 3F). At this time, since the photosensitive material was cured by the radiation response reaction in the rib-shaped exposed portion 7 in the laminated body of the photosensitive insulating layer 6 as in Example 1, excellent sandblast resistance was exhibited, and the line thinning and The rib had a width of 30 μm and a height of 125 μm without chipping (FIG. 3F).

After the sand blast, the firing step (580)
C) to form the ribs 14 made of only the insulating material on the glass substrate 1 (FIG. 3g).

In the third embodiment, as in the second embodiment with respect to the first embodiment, a photosensitive resist having sandblast resistance is further laminated on the photosensitive insulating layer 6 laminated on the glass substrate 1. Sandblasting was possible.

Example 4 Glass powder 57 parts by weight Alumina powder 23 parts by weight Epoxy acrylate 5 parts by weight Dipentaerythritol hexaacrylate 5 parts by weight acetophenone 2 parts by weight Ethyl cellulose 6 parts by weight Diethylene glycol ethyl ether 24 parts by weight Isophthalic acid 2 parts by weight These materials were mixed by a roll mill to obtain a photosensitive insulating paste.

The above paste was coated on a support film 3 of polyethylene terephthalate (50 μm) to a thickness of 200 μm.
m, and dried at 70 ° C. to form a photosensitive insulating layer 6. Next, an adhesive obtained by adding phthalic acid to an octyl acrylate-methacrylic acid copolymer / toluene system is applied to form an adhesive layer 5, and a polyethylene film (20 μm) is pressed as a protective film 4 to form ribs. The structure 200 was formed.

Next, a process of forming the ribs 14 using the rib forming structure 200 will be described with reference to FIG. While peeling off the protective film 4 of the rib forming structure 200,
The rib forming structure was pressed onto the glass substrate 1 with a roll laminator. Next, the photomask 2 having a predetermined pattern was placed on the support film 3, and was placed in a vacuum exposure apparatus and exposed (FIG. 4A). After the exposure, the photomask 2 was removed from the vacuum exposure apparatus, and the support film 3 was peeled off.

Next, the photosensitive insulating layer 6 was cut by a sandblasting device (FIG. 4B). At this time, since the exposed portion 7 of the photosensitive insulating layer 6 is hardened by exposure, it exhibits excellent sand blast resistance due to its hardness characteristics, and the photosensitive insulating layer 6 below the exposed portion 7 is not cut and the rib shape is not cut. Remained. Conversely, the unexposed portion 8 of the surface layer was cut with a sand material to the position of the adhesive layer 5 due to its hardness.

After the sand blasting, since the exposed portion 7 is also an insulator derived from the photosensitive insulating layer 6, the step of removing the resist pattern as in the conventional case is unnecessary, and therefore, the process directly proceeds to the baking step. After the firing step (600 ° C.), the ribs 14 made of only the insulating material could be formed on the glass substrate 1 (FIG. 4C). In addition, the adhesive layer 5 was completely burned and disappeared in the firing step, and no damage was confirmed because the surface of the glass substrate 1 was protected by the adhesive layer 5 having sandblast resistance.

Example 5 A photosensitive insulating paste kneaded in Example 4 was roll-coated on a support film 3 of polyethylene terephthalate (50 μm) to a thickness of 20 μm, dried at 70 ° C., and exposed to light. A conductive insulating layer 6 was formed.

Further, a non-photosensitive insulating paste obtained by kneading the following composition with a roll mill was roll-coated so as to have a thickness of 180 μm, and dried at 70 ° C. to form an insulating layer 9. Thereafter, an adhesive layer 5 in which phthalic acid was added to an octyl acrylate-methacrylic acid copolymer / toluene system was applied, and a polyethylene film (20 μm) was pressed as a protective film 4 to obtain a rib-forming structure 300.

Glass powder 67 parts by weight Alumina powder 25 parts by weight Ethyl cellulose 6 parts by weight Wetting agent 2 parts by weight Diethylene glycol ethyl ether 24 parts by weight

The ribs 14 are formed by using the rib forming structure 300.
6 are shown in FIG. Each of the steps of exposure, sandblasting, and firing is the same as the rib forming step using the rib forming structure 200 shown in FIG. Since the exposed portion 7 of the photosensitive insulating layer 6 was hardened by exposure, it exhibited excellent sand blast resistance due to its hardness characteristics, as in Example 4, and the insulating layer 9 below the exposed portion 7 was not cut but ribbed. The shape remained. Conversely, the unexposed portion 8 of the surface layer was cut with a sand material to the position of the adhesive layer 5 due to its hardness.

The step of peeling the exposed portion 7 after sandblasting is not necessary. After the sandblasting step, the process directly proceeds to the firing step, and the firing step (600 ° C.) places the ribs 14 made of only an insulating material on the glass substrate 1. Could be formed. In addition, the adhesive layer 5 was completely burned and disappeared in the firing step, and no damage was confirmed because the surface of the glass substrate 1 was protected by the adhesive layer 5 having sandblast resistance.

Example 6 Glass powder 50 parts by weight Alumina powder 6 parts by weight Nolabock resin 10 parts by weight 2.3.4-Trihydroxybenzophenone 10 parts by weight Isophthalic acid 2 parts by weight Methyl ethyl ketone 150 parts by weight Wetting agent 1 part by weight

The above materials were kneaded by a roll mill to form a paste. This paste is coated on a support film 3 of polyethylene terephthalate (50 μm) to a thickness of 200 μm.
m, and dried at 70 ° C. Next, an adhesive layer 5 in which phthalic acid was added to an octyl acrylate-methacrylic acid copolymer / toluene system was applied, and a polyethylene film (20 μm) was pressed as a protective film 4 to produce a rib forming structure 400. .

Next, a process of forming the ribs 14 using the rib forming structure 400 will be described with reference to FIG. While peeling off the protective film 4 of the rib forming structure 400,
The rib forming structure 400 was pressed on the glass substrate 1 by a roll laminator. Next, the photomask 2 having a predetermined pattern was placed on the support film 3, and was placed in a vacuum exposure apparatus and exposed (FIG. 8A). After the exposure, the photomask 2 was removed from the vacuum exposure apparatus, and the support film 3 was peeled off.

Next, the photosensitive insulating layer 6 was cut by a sandblasting device (FIG. 8B). At this time, since the exposed portion 7 of the photosensitive insulating layer 6 was decomposed by exposure, it exhibited excellent sand blast resistance due to its elasticity. Remained.
Conversely, the unexposed portion 8 of the surface layer was cut with a sand material to the position of the adhesive layer 5 due to its hardness.

After the sand blasting, since the exposed portion 7 is also an insulator derived from the photosensitive insulating layer 6, the step of removing the resist pattern as in the related art is unnecessary, and therefore, the process directly proceeds to the baking step. After the firing step (600 ° C.), the ribs 14 made of only the insulating material could be formed on the glass substrate 1 (FIG. 8C). In addition, the adhesive layer 5 was completely burned and disappeared in the firing step, and no damage was confirmed because the surface of the glass substrate 1 was protected by the adhesive layer 5 having sandblast resistance.

Example 7 A photosensitive resist solution was roll-coated on a support film 3 of polyethylene terephthalate (50 μm) to a thickness of 20 μm and dried at 70 ° C. to form a photosensitive resist layer 10.

Further, a non-photosensitive insulating paste obtained by kneading the following composition by a roll mill was roll-coated so as to have a thickness of 180 μm, and dried at 70 ° C. to form an insulating layer 9. Thereafter, an adhesive layer 5 was formed by applying 2-ethylhexyl acrylate, vinyl acetate, and toluene-based adhesives, and a polyethylene film (20 μm) was pressure-bonded as the protective film 4 to obtain a rib-forming structure 500.

Glass powder 68 parts by weight Alumina powder 26 parts by weight Ethyl cellulose 5 parts by weight Wetting agent 1 part by weight Diethylene glycol ethyl ether 24 parts by weight

The ribs 14 are formed by using the rib forming structure 500.
Are formed as shown in FIG. Again,
Since the exposed portion 7 of the photosensitive resist layer 10 was decomposed by exposure, the elasticity exhibited excellent sandblast resistance, and the insulating layer 9 below the exposed portion 7 remained in a rib shape without being cut. Conversely, the portion 8 where the surface layer is not exposed
Was cut with a sand material to the position of the adhesive layer 5 due to its hardness.

Since the photosensitive resist layer 10 is of the complete burning type, the step of removing the exposed portion 7 after sandblasting is unnecessary, and after the sandblasting step, the process directly proceeds to the firing step, and the firing step (600 ° C.) The ribs 14 made of only the insulating material could be formed on the glass substrate 1. Further, the adhesive layer 5 was completely baked in the firing step and disappeared. Since the surface of the glass substrate 1 was protected by the sandblast-resistant adhesive layer 5, no damage was confirmed.

Example 8 30 parts by weight of polyvinyl butyral 11 parts by weight of dipentaerythritol hexaacrylate 5 parts by weight of ethylene-vinyl acetate copolymer 2 parts by weight of acetophenone 2 parts by weight of isophthalic acid 150 parts by weight of methyl ethyl ketone

These materials were kneaded by a roll mill to form a paste. This paste is coated on a support film 3 of polyethylene terephthalate (50 μm) to a thickness of 20 μm.
m, and dried at 70 ° C. to form a photosensitive resist layer 10. Then, a polyethylene film (20 μm) was pressure-bonded as a protective film to obtain a photosensitive resist laminated film. This photosensitive resist layer 10
Is a so-called negative type, and the exposed portion is cured.

Glass powder 50 parts by weight Alumina powder 20 parts by weight Ethyl cellulose 4 parts by weight Wetting agent 2 parts by weight Diethylene glycol ethyl ether 24 parts by weight

These materials were kneaded by a roll mill to form a paste. This paste was roll-coated on a polyethylene terephthalate (20 μm) film so as to have a thickness of 200 μm, and dried at a temperature of 100 ° C. to form an insulating layer 9. Next, an adhesive obtained by adding phthalic acid to an octyl acrylate-methacrylic acid copolymer / toluene system is applied to form an adhesive layer 5, and a polyethylene film (20 μm) is pressed as a protective film 4 to form a laminated film for ribs. did.

The photosensitive resist layer 10 obtained by removing the protective film from the photosensitive resist laminated film and the insulating layer 9 obtained by removing the ethylene terephthalate film from the rib laminated film were both heated with a roll laminator while heating to 80 ° C. Was thermocompression-bonded. Thus, the rib forming structure 600 was prepared.

Next, the step of forming the ribs 14 using the rib forming structure 600 will be described with reference to FIG. While peeling off the protective film 4, the adhesive layer 5 was pressure-bonded to the rib-forming structure 600 on the glass substrate 1 by a roll laminator. Next, the photomask 2 having a predetermined pattern was placed on the support film 3, and was placed in a vacuum exposure apparatus and exposed (FIG. 12A). After the exposure, the photomask 2 was removed from the vacuum exposure apparatus, and the support film 3 was peeled off. At this time, since the exposed portion 7 of the photosensitive resist layer 10 cured by the previous exposure was fixed to the support film 3, it was separated from the insulating layer 9 in the step of peeling the support film 3 and could be developed (FIG. 12B). . Next, the process proceeds to the sandblasting step, and the exposed insulating layer 9 is cut (FIG. 12).
c). At this time, the portion of the insulating layer 9 covered by the unexposed portions 8 of the photosensitive resist layer 10 remained in a rib shape without being cut because the unexposed portions 8 exhibited excellent sandblast resistance. Subsequently, a film made of the same material as the support film 3 was brought into close contact with the unexposed portions 8 of the photosensitive resist layer 10 remaining on the ribs, and was cured by overall exposure. The exposed and cured photosensitive resist layer 10 was fixed to the film and peeled off together with the film (FIG. 12d). Finally, the process was shifted to the firing step (600 ° C.), and the ribs 14 made of only the insulating material could be formed (FIG. 12E). The adhesive layer 5 was completely burned, and there was no damage on the glass substrate 1 due to the sand material.

Example 9 30 parts by weight of polymethacrylic acid 11 parts by weight of dipentaerythritol hexaacrylate 5 parts by weight of ethylene-vinyl acetate copolymer 2 parts by weight of acetophenone 2 parts by weight of isophthalic acid 150 parts by weight of methyl ethyl ketone

These materials were kneaded by a roll mill to obtain a paste for the photosensitive resist layer 10, and the other method was the same as that of Example 8 except that the type of rib forming structure was different from that of Example 8. 600 were produced.

Next, a process of forming the ribs 14 using the rib forming structure 600 will be described with reference to FIG. Here, up to the sandblasting step (FIG. 12c)
This is the same step as in the eighth embodiment. Since the photosensitive resist layer 10 is of a complete combustion type, after the sandblasting step, the process proceeds to the baking step (600 ° C.) without peeling (FIG. 12).
e) The ribs 14 made only of the insulating material could be formed. The adhesive layer 5 was completely burned, and the glass substrate 1 was not damaged by the sand material.

Example 10 A photo-tacking resist PTR (manufactured by Fuji Pharmaceutical) was coated on a polyethylene terephthalate (40 μm) support film 3 to a thickness of 10 μm.
After roll coating and drying at 80 ° C. to form a photosensitive resist layer 10, a polyethylene film (20 μm) was pressed as a protective film to obtain a photosensitive resist laminated film.

Glass powder 50 parts by weight Alumina powder 20 parts by weight Ethyl cellulose 4 parts by weight Wetting agent 2 parts by weight Diethylene glycol ethyl ether 24 parts by weight

These materials were kneaded by a roll mill to form a paste. This paste was roll-coated on a polyethylene terephthalate (20 μm) film so as to have a thickness of 170 μm, and dried at a temperature of 90 ° C. to form an insulating layer 9. Next, an adhesive obtained by adding phthalic acid to an octyl acrylate-methacrylic acid copolymer / toluene system is applied to form an adhesive layer 5, and a polyethylene film (20 μm) is pressed as a protective film 4 to form a laminated film for ribs. did.

The photosensitive resist layer 10 obtained by removing the protective film from the photosensitive resist laminated film and the insulating layer 9 obtained by removing the ethylene terephthalate film from the rib laminated film were both heated with a roll laminator while heating to 80 ° C. Was thermocompression-bonded. Thus, the rib forming structure 700 was manufactured.

Next, a process of forming the ribs 14 using the rib forming structure 700 will be described with reference to FIG. While peeling off the protective film 4, the adhesive layer 5 was pressure-bonded to the rib forming structure 700 on the glass substrate 1 by a roll laminator (FIG. 14A). Next, the photomask 2 having a predetermined pattern was placed on the support film 3, and was placed in a vacuum exposure apparatus and exposed (FIG. 14B). After the exposure, the photomask 2 was removed from the vacuum exposure apparatus, and the support film 3 was peeled off. At this time, since the exposed portion 7 of the photosensitive resist layer 10 decomposed by the previous exposure adheres to the insulating layer 9, the unexposed portion 8 of the photosensitive resist layer 10 is separated from the insulating layer 9 in the step of peeling the support film 3. , And could be developed (FIG. 14c). Next, the exposed insulating layer 9 was cut by a sandblasting process (FIG. 14D). At this time, the insulating layer 9 in the portion of the photosensitive resist layer 10 covered with the exposed portion 7 is exposed to the exposed portion 7 of the photosensitive resist layer 10 to be decomposed and exposed, thereby increasing elasticity and exhibiting excellent sandblast resistance. , And remained in a rib shape without being cut. After the sand blasting step, the process directly proceeded to the baking step (600 ° C.) without stripping the exposed portion 7 of the photosensitive resist layer 10 to form the ribs 14 made of only the insulating material (FIG. 14).
e). The adhesive layer 5 was completely burned, and there was no damage on the glass substrate 1 due to the sand material.

[0152]

As described above, according to the photosensitive insulating composition for rib formation, the structure and the method for forming ribs of the present invention, high precision and reproducibility can be ensured at the time of rib formation, and the yield can be improved. Improves. Further, it is possible to manufacture a fine rib having a high aspect ratio and a fine resolution with a high resolution, which cannot be achieved by the conventional sandblasting method.

Further, in addition to greatly reducing the steps before the exposure at the time of forming the ribs, the step of developing with a solvent and the step of removing the resist after sandblasting can be eliminated in the steps after the exposure, and the throughput can be reduced. , Cost reduction, and work environment improvement.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a rib forming structure according to a first embodiment of the present invention.

FIG. 2 is a sectional view of a rib forming structure according to a second embodiment of the present invention.

FIG. 3 is a process chart when a rib is formed using the rib forming structure of the second embodiment.

FIG. 4 is another process diagram when a rib is formed using the rib forming structure of the second embodiment.

FIG. 5 is a sectional view of a rib forming structure according to a third embodiment of the present invention.

FIG. 6 is a process chart when a rib is formed using the rib forming structure of the third embodiment.

FIG. 7 is a sectional view of a rib forming structure according to a fourth embodiment of the present invention.

FIG. 8 is a process chart when a rib is formed using the rib forming structure of the fourth embodiment.

FIG. 9 is a sectional view of a rib forming structure according to a fifth embodiment of the present invention.

FIG. 10 is a process chart when a rib is formed using the rib forming structure of the fifth embodiment.

FIG. 11 is a sectional view of a rib forming structure according to a sixth embodiment of the present invention.

FIG. 12 is a process chart for forming a rib using the rib forming structure of the sixth embodiment.

FIG. 13 is a sectional view of a rib forming structure according to a seventh embodiment of the present invention.

FIG. 14 is a process chart when a rib is formed using the rib forming structure of the seventh embodiment.

FIG. 15 is a process chart when a rib is formed using the photosensitive insulating composition for forming a rib according to the present invention.

FIG. 16 is a view showing a conventional rib forming process.

FIG. 17 is an explanatory view of a rib formed by a conventional technique.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 glass substrate 2 photomask 3 support film 4 protective film 5 adhesive layer 6 photosensitive insulating layer 7 exposed part 8 unexposed part 9 insulating layer 10 photosensitive resist layer 14 rib 100 rib forming structure 200 rib forming structure 300 Rib forming structure 400 Rib forming structure 500 Rib forming structure 600 Rib forming structure 700 Rib forming structure

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01J 11/02 H01J 11/02 Z (72) Inventor Masayoshi Kobayashi 5-1, Taito 1-chome, Taito-ku, Tokyo Letterpress Printing Co., Ltd. (72) Inventor Katsumi Ohira 1-5-1, Taito, Taito-ku, Tokyo Toppan Printing Co., Ltd.

Claims (13)

[Claims] An insulating material and an electromagnetic wave such as ultraviolet light or β.
A composition having a property of changing its properties upon irradiation with a particle beam such as a beam (this property is called photosensitivity, including property changes due to particle beam irradiation), A photosensitive insulating composition for forming a rib, wherein the sandblasting resistance of the formed structure is changed by the irradiation. 2. A rib-forming structure, wherein the rib-forming photosensitive insulating composition according to claim 1 is applied on a support film, dried and laminated. 3. The structure for forming a rib according to claim 2, wherein a non-photosensitive insulating layer is laminated on the layer made of the photosensitive insulating composition for forming a rib. 4. A structure for forming a rib, comprising: a support film; a photosensitive resist layer laminated on the support film; and a non-photosensitive insulating layer laminated on the resist layer. body. 5. The method according to claim 4, wherein the photosensitive resist layer is formed by applying and drying a photosensitive resist solution, and the non-photosensitive insulating layer is formed by applying and drying an insulating material paste. Rib forming structure. 6. As a photosensitive resist layer, an illuminated portion adheres to a support film and peels off from the non-photosensitive insulating layer, and an unirradiated portion adheres to the non-photosensitive insulating layer and peels off from the support film. 6. The rib forming structure according to claim 4, wherein a photosensitive resist layer is formed. 7. As a photosensitive resist layer, a non-irradiated portion adheres to the support film and peels off from the non-photosensitive insulating layer, and an irradiated portion adheres to the non-photosensitive insulating layer and peels off from the support film. 6. The rib forming structure according to claim 4, wherein a photosensitive resist layer is formed. 8. The rib forming structure according to claim 4, wherein the photosensitive resist layer is formed of a photosensitive resist layer whose sandblast resistance of an irradiated portion changes. 9. The rib-forming structure according to claim 4, wherein the photosensitive resist layer is a complete combustion type photosensitive resist layer from which no residue is formed. 10. The rib forming structure according to claim 2, wherein an adhesive layer is formed on an uppermost layer. 11. The rib-forming structure according to claim 10, wherein the adhesive layer has an excellent sandblast resistance and is made of a completely combustible adhesive from which no residue is generated. 12. The rib forming structure according to claim 10, wherein the protective film is releasably laminated on the adhesive layer. 13. A step of forming a photosensitive insulating layer on a substrate by using the photosensitive insulating composition for forming a rib according to claim 1 or the structure for forming a rib according to claim 2; Covering the layer with a desired mask pattern and irradiating it.
A method of forming a rib, comprising repeating a coating of a resist mask as necessary, coating a resist mask as needed, and then blowing a sand material onto the photosensitive insulating layer to form a remaining rib on the substrate.