JP2936984B2 - Photosensitive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION This invention is applied to a color filter pattern or the like in the color display for a plasma display panel, and relates to a method of forming a colored pattern layer heat resistance is required, in particular, the color display plasma
The present invention relates to a photosensitive resin composition used in a formation method capable of controlling the shape and formation position of a colored pattern layer in a display panel with high accuracy.

[0002]

2. Description of the Related Art Generally, a plasma display panel for color display includes a front substrate a as shown in FIG.
A rear substrate b disposed opposite to the front substrate a
A low-melting glass c for fixing the front substrate a and the rear substrate b to each other at the peripheral portion; and a discharge space d surrounded by the front substrate a, the rear substrate b, and the low-melting glass c.
The main part is composed of a mixed gas containing a rare gas as a main component filled therein, and details of the screen display area are shown in FIG.

That is, as shown in FIG.
Are formed on a glass substrate a1, color filter layers Ra, Ga, and Ba provided for each pixel in a pixel portion on the inner surface side of the glass substrate a1 and coloring transmitted light for each color, and on the color filter layers Ra, Ga, and Ba. The main part is constituted by the first discharge electrode a3 arranged on the other side, while the back side substrate b is composed of a glass substrate b1 and the glass substrate b1.
A second discharge electrode b2 provided for each pixel in a pixel portion on the inner surface side of the pixel, a bank b4 separating each pixel, and a pixel at a portion around an intersection of the second discharge electrode b2 facing the first discharge electrode a3. The main part is constituted by the phosphor layer b3 provided for each. In a discharge cell surrounded by the first discharge electrode a3, the second discharge electrode b2, and the bank b4, which are these discharge spaces, a mixed gas mainly composed of a rare gas that generates ultraviolet rays by discharge is used as a priming path. introduced from b5.

In this plasma display panel for color display, a discharge is caused between the first discharge electrode a3 and the second discharge electrode b2 of a pixel to be displayed, and the mixed gas mainly composed of a rare gas is excited by the discharge. The fluorescent layer b3 using ultraviolet rays generated from the generated atoms and molecules.
Is emitted to convert it into visible light. The color filter layers Ra, Ga, and Ba remove unnecessary color light components from both the visible light generated from the phosphor layer b3 and the extraneous light reflected by the phosphor layer b3, and remove the color of the display screen. Purity is increased to improve the contrast.

[0005] The plasma display panel for color display has been conventionally manufactured through the following steps. First, a color filter layer Ra, Ga, Ba and a first discharge electrode a3 are sequentially formed on a glass substrate a1 to produce a front substrate a. On the other hand, a second discharge electrode b2, a bank b4, and a phosphor layer b3 are formed on a glass substrate b1 to produce a rear substrate b. The front substrate a and the rear substrate b are overlapped with each other via a glass paste containing the low-melting glass c, and the glass paste is baked so that the front substrate a and the back substrate b
And fix. Finally, the front substrate a or the rear substrate b
The above-mentioned mixed gas is introduced into the discharge space d through an introduction hole (not shown) provided in the plasma display panel to produce a plasma display panel for color display.

As described above, since the baking step of the glass paste containing the low melting point glass c is included in the manufacturing process of the plasma display panel for color display, the material constituting the color filter layers Ra, Ga, and Ba is used. Is required to have heat resistance such that discoloration and deformation do not occur in this firing step.

Therefore, conventionally, a glass material in which an inorganic color pigment is dispersed is generally applied as a material constituting the color filter layer, and is formed by the following method. That is, a paste mainly composed of a low melting glass powder, an inorganic color pigment, a resin binder for temporarily fixing the glass powder and the inorganic color pigment to the glass substrate a1 is screened at a pixel portion on the glass substrate a1. After printing, the printed paste is baked to melt the glass powder, fix the inorganic coloring pigment to the glass substrate a1, and burn off other components such as a resin binder to form the color filter layer Ra,
Ga and Ba are formed (see JP-A-61-6150 and JP-A-61-6151).

[0008]

According to the screen printing method, the paste is supplied onto a screen plate having openings of a predetermined pattern, and the paste is extruded from the openings by rubbing with a flexible squeegee. Is a method of printing on the glass substrate a1, and the screen plate expands and contracts depending on conditions such as the temperature and humidity around the printing press, the pressure applied to the squeegee, and the moving speed of the squeegee, so that the opening is easily deformed. There is. In addition, the thickness of a print film that can be formed by one printing is limited to 10 μm, and in order to form a film having a thickness larger than that, it is necessary to repeatedly print the same pattern. However, it is usually difficult to print a pattern whose register is perfectly matched because the above-mentioned printing conditions vary every time printing is performed and the opening is easily deformed.
For this reason, there was a problem that the pattern shape of the color filter layers Ra, Ga, and Ba obtained by printing many times was easily distorted.

Under the above technical background, the present inventors have developed a method capable of forming a colored pattern layer such as a color filter layer on a transparent substrate with high precision with respect to its pattern shape, formation position and thickness accuracy together with the present application. is suggesting.

That is, this method comprises forming a photosensitive resin composition containing an acrylic resin, an acrylic monomer, a photopolymerization initiator for initiating polymerization of the acrylic monomer by light irradiation, and a diluting solvent on a transparent substrate. It is coated, exposed and developed to form a pattern, and the low melting glass powder and the coloring pigment are contained in a concave portion formed by a mold formed of the patterned photosensitive resin composition layer and an exposed portion of the transparent substrate.
After filling colored glass paste having, in the firing process
And remove the above mold to remove the colored glass paste on the transparent substrate.
To form a color pattern layer of a plasma display panel for color display comprising: The photosensitive resin composition applied to this forming method is composed of 3.0 to 40.00% by weight of an acrylic resin, 1.00 to 30.00% by weight of an acrylic monomer, and 0.30% by weight of a photopolymerization initiator. ~
7.50% by weight, and a diluting solvent of 10.00 to 95.0.
What is blended at a ratio of 0% by weight is applied.

According to this method for forming a colored pattern layer, the patterning of the photosensitive resin composition layer is determined by exposure through a mask. It becomes possible to control. In addition, the colored glass corresponding to the pattern shape and the formation position of the mold formed of the patterned photosensitive resin composition layer.
Since the shape and formation position of the paste layer are accurately determined, it is possible to accurately control the pattern shape and formation position of the colored pattern layer in the plasma display panel for color display up to the optical limit. Become. Therefore , since a color filter layer (colored pattern layer) of each color corresponding to each pixel of the display panel is formed accurately, it is possible to sufficiently color the transmitted light of the pixel portion and to improve the color purity of the display screen. It was a method that could be achieved.

Accordingly, an object of the present invention is to provide a photosensitive resin composition suitably used in the method for forming a color pattern layer in the above-described plasma display panel for color display. .

[0013]

That is, the invention according to claim 1 comprises an acrylic resin, an acrylic monomer, a photopolymerization initiator for initiating polymerization of the acrylic monomer by light irradiation, and a diluting solvent. The photosensitive resin composition is applied on a transparent substrate, and is exposed and developed to form a pattern, and the inside of a concave portion formed by a mold formed of the patterned photosensitive resin composition layer and an exposed portion of the transparent substrate. Low melting point
After filling a colored glass paste containing a lath powder and a colored pigment, the mold is removed by a baking treatment , and a plasma for color display comprising a colored glass paste is formed on a transparent substrate.
On the premise of the photosensitive resin composition used in the method for forming a colored pattern layer of a display panel, the acrylic resin is a monomer represented by the following chemical formula (1) and a monomer represented by the following chemical formula (2) And a copolymer of a monomer represented by the following chemical formula (3).

[0014]

Embedded image (Wherein, R1 represents an alkyl group having 1 to 5 carbon atoms)

Embedded image

Embedded image According to the photosensitive resin composition according to the first aspect of the present invention, the acrylic resin includes a monomer represented by the chemical formula (1), a monomer represented by the chemical formula (2), and a chemical formula (3)
Since it is a copolymer with a monomer represented by, the acrylic resin generated by polymerization of the acrylic resin and the acrylic monomer in the photosensitive resin composition is three-dimensionally entangled with the transparent substrate. In order to improve the adhesive force of the photosensitive resin composition at the exposed site, the photosensitive resin composition may be peeled off from the transparent substrate during the development process, or a gap may be formed between the photosensitive resin composition layer and the transparent substrate. Deformation can be prevented. For this reason, it is possible to form a mold having a shape exactly corresponding to the exposure pattern, and accordingly, a colored glass pace filled in a recess formed by the mold and an exposed portion of the transparent substrate.
The shape and forming position of the bets is also determined accurately, the color table
It is possible to improve the pattern shape and position accuracy of the colored pattern layer in the display plasma display panel . Furthermore, since the above-described copolymer is applied, the solubility of the developer in the unexposed portion of the photosensitive resin composition layer is improved, and accordingly, the film thickness of the exposed portion is reduced by setting the development time earlier. Thus, the thickness of the photosensitive resin composition layer remaining after the development processing can be accurately controlled. Therefore, it is possible to control with high precision the depth of the concave portion formed by the mold formed of the patterned photosensitive resin composition layer and the exposed portion of the transparent substrate, and accordingly, the concave portion is filled in the concave portion. Since the thickness control of the colored glass paste to be used is also improved , the plasma display panel for color display is improved.
It is possible to improve the thickness accuracy of the colored pattern layer in the tunnel.

As described above , the plasma display for color display is used.
The shape of the colored pattern layer in the spray panel forming position improves the thickness precision This will allow for some possible to accurately control the optical characteristics of the sites that are not present with the optical properties of the site present in the colored pattern layer, the Since the spectral transmission characteristics of the color filter layer can be controlled with high precision, the color purity of the display screen is improved, and a colorful screen display is possible. In addition, the colored glass paste constituting the colored pattern layer is necessary for forming a paste and a resin binder for temporarily holding the glass powder and the colored pigment on a transparent substrate, in addition to the low-melting glass powder and the colored pigment. Naturally, it may contain a solvent or the like. Then, after filling the above-mentioned colored glass paste into a concave portion formed by a mold formed of a patterned photosensitive resin composition layer and an exposed portion of the transparent substrate, a baking treatment is performed, so that the colored glass paste contains The resin binder and the photosensitive resin composition constituting the mold can be burned off, and the low-melting glass powder can be melted to fix the color pigment on the transparent substrate.

In such technical means, examples of the monomer represented by the chemical formula (1) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, and isoamyl methacrylate. Applicable.
In addition, as for this monomer represented by the chemical formula (1), at least one of the exemplified monomers may be used, and two or more monomers may be used in combination.

Also, methacrylic acid can be used as the monomer represented by the chemical formula (2), and hydroxyethyl methacrylate can be used as the monomer represented by the chemical formula (3).

In the invention according to claim 1, the monomer represented by the formula (2) is added to the monomer represented by the formula (2) in an amount of 15 to 35 parts by weight based on 15 to 85 parts by weight of the monomer represented by the formula (1).
Parts by weight of the monomer represented by the chemical formula (3)
It is desirable to copolymerize at 5 parts by weight.

In the invention according to the first aspect, when the acrylic monomer polymerized by light irradiation has a functional group represented by the following chemical formula (4), the photosensitivity after the acrylic monomer is exposed and polymerized. The exposed portion of the resin composition layer has excellent developer resistance. Therefore, since the film loss due to the development treatment is reduced, the precision of the mold formed of the patterned photosensitive resin composition layer is further improved, and accordingly, the thickness of the colored pattern layer can be controlled more accurately. Become. The invention according to claim 2 has been made based on such a reason.

That is, the invention according to claim 2 is based on the photosensitive resin composition layer according to the invention according to claim 1, and the acrylic monomer polymerized by light irradiation is represented by the following chemical formula (4). It is characterized by having a functional group.

[0021]

Embedded image When the acrylic monomer is a bifunctional monomer or a polyfunctional monomer having two or more functional groups represented by the chemical formula (4), these monomers are three-dimensionally polymerized and the adhesion to the transparent substrate is reduced. Further increase.

As such a bifunctional monomer, for example, ethylene glycol diacrylate, diacrylate, triethylene glycol diacrylate and the like can be used. As the polyfunctional acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, diacrylate Pentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and the like can be applied.

In the invention according to claims 1 and 2, as the photopolymerization initiator, for example, acetophenone, benzophenone, benzyldimethyl ketal, triazine and the like can be used. As the diluting solvent, for example, ethyl cellosolve, cyclohexanone, etc. can be used,
Cyclohexanone is preferred in that it is excellent in solubility and the like of the acrylic resin.

The colored pattern layer according to the present invention can be applied to a color filter layer of a plasma display panel for color display, and can be a black matrix provided at a portion between pixels (inter-pixel portion). You may apply to a light shielding layer.

[0025]

According to the first aspect of the present invention, the acrylic resin comprises a monomer represented by the chemical formula (1) and a monomer represented by the chemical formula (2).
Is a copolymer of the monomer represented by the formula (3) and the monomer represented by the chemical formula (3), so that the acrylic polymer formed by polymerization of the acrylic resin and the acrylic monomer in the photosensitive resin composition is used. Is three-dimensionally entangled to improve the adhesive strength with the transparent substrate, the photosensitive resin composition at the exposed site may be peeled off from the transparent substrate during the development process or the photosensitive resin composition layer and the transparent substrate It is possible to prevent the form shape from being deformed due to a gap therebetween. Therefore , it is possible to form a mold having a shape exactly corresponding to the above-mentioned exposure pattern, and accordingly , a colored glass paste to be filled in a recess formed by the mold and the exposed portion of the transparent substrate. Since the shape and formation position are accurately determined , the plasma display for color display is used.
It is possible to improve the pattern shape and position accuracy of the colored pattern layer in the ray panel . Furthermore, since the above-described copolymer is applied, the solubility of the developer in the unexposed portion of the photosensitive resin composition layer is improved, and accordingly, the film thickness of the exposed portion is reduced by setting the development time earlier. Thus, the thickness of the photosensitive resin composition layer remaining after the development processing can be accurately controlled. Therefore, it is possible to control with high precision the depth of the concave portion formed by the mold formed of the patterned photosensitive resin composition layer and the exposed portion of the transparent substrate, and accordingly, the concave portion is filled. since the thickness control of the colored glass pastes are improved, color
-It is possible to improve the thickness accuracy of the colored pattern layer in the display plasma display panel .

According to the second aspect of the present invention, the acrylic monomer polymerized by light irradiation has a functional group represented by the chemical formula (4), and the acrylic monomer having this functional group Since the developing solution resistance of the exposed portion of the photosensitive resin composition layer after the exposure polymerization is improved, the film loss due to the development process is reduced, and the accuracy of the mold formed of the patterned photosensitive resin composition layer is improved. Has been further improved, and a plasma display panel for color display has been
It is possible to control the thickness of the colored pattern layer in the tunnel more accurately.

[0027]

Embodiments of the present invention will be described below in more detail with reference to the drawings.

First, an acrylic resin was prepared by copolymerizing 6.98 parts by weight of butyl methacrylate, 1.75 parts by weight of methyl methacrylate, 1.75 parts by weight of methacrylic acid, and 1.16 parts by weight of hydroxyethyl methacrylate. Then, a photosensitive resin composition was prepared using the acrylic resin at the following compounding ratio.

(Photosensitive resin composition) Acrylic resin 11.64% by weight Acrylic monomer 2.79% by weight of dipentaerythritol pentaacrylate 4.19% by weight of dipentaerythritol hexaacrylate 1.40% by weight of photopolymerization initiator triazine Diluent solvent: cyclohexanone 79.98% by weight This photosensitive resin composition was prepared by adding 100 mm in length × 100 mm in width.
300 mesh with a rectangular opening of
Using a stainless steel screen plate of μm, screen printing was performed on the transparent glass substrate 1 and left at room temperature for 5 minutes to dry the film surface.
Drying was performed at 0 ° C. for 20 minutes to form a photosensitive resin composition layer 2 (see FIG. 1A). The thickness of the obtained photosensitive resin composition layer 2 was 15 μm and had a uniform value over the entire surface.

Next, a photomask 3 having a light-shielding film 3y in which a rectangular pattern of 50 μm × 50 μm is repeatedly formed at a pitch of 100 μm is brought into close contact with the photosensitive resin composition layer 2 and exposed with an ultra-high pressure mercury lamp. 40mJ / cm
Contact exposure was performed under the conditions of ² (see FIG. 1B). Subsequent to exposure, the glass substrate 1 was exposed by developing with an alkaline developer to remove the photosensitive resin composition layer 2 at the unexposed portions.
During the development process, phenomena such as peeling of the photosensitive resin composition layer 2 and residual development were not observed. Next, 23
Heat treatment was performed at 0 ° C. for 1 hour to completely cure the photosensitive resin composition layer 2 remaining at the exposed site (see FIG. 1C). The thickness of the remaining photosensitive resin composition layer 2 after the heat curing was 12 μm.

Next, a colored glass paste 4 ′ is supplied onto the remaining photosensitive resin composition layer 2, and a flexible silicon rubber squeegee 5 is moved in a horizontal direction with respect to the glass substrate 1 to form a mold. The colored glass paste 4 ′ was filled in a concave portion formed by the photosensitive resin composition layer 2 and the exposed portion of the glass substrate 1 (see FIG. 1D). As the colored glass paste 4 ', a paste obtained by kneading a low-melting glass powder and a blue inorganic coloring pigment together with a resin binder is used.

Next, the colored glass paste 4 'is
After drying at 20 ° C. for 20 minutes, firing at a maximum temperature of 580 ° C. for a firing time of 10 minutes, the low melting glass powder in the colored glass paste 4 ′ is melted, and the inorganic color pigment is fixed to fix the color filter layer 4. And other components (for example, resin binder and the remaining photosensitive resin composition layer 2 in the colored glass paste 4 ′) were burned off (see FIG. 1E).

The color filter layer 4 thus formed
Is a pattern in which a rectangular pattern having a length of 50 μm and a width of 50 μm is repeated at a pitch of 100 μm, and both the pattern shape and the formation position accurately reflect the pattern of the light-shielding film 3 y of the photomask 3. Further, the thickness was 9 μm and had a uniform value over the entire surface.

According to the first aspect of the present invention, the acrylic resin is a copolymer of the monomer represented by the chemical formula (1), the monomer represented by the chemical formula (2), and the monomer represented by the chemical formula (3). Since it is a polymer, it is possible to form a mold made of a photosensitive resin composition layer having a shape exactly corresponding to the exposure pattern, and thus it is composed of the mold and the exposed portion of the transparent substrate. Colored gas filled in the recess
Since the shape and formation position of the lath paste are also accurately determined, there is an effect that the pattern shape and position accuracy of the colored pattern layer in the plasma display panel for color display can be improved.

Further, since the copolymer described above is applied, the solubility of the unexposed portion in the photosensitive resin composition layer in the developing solution is improved, and accordingly, the developing time is set to be shorter so that the exposed portion can be reduced. The film thickness can be prevented and the thickness of the photosensitive resin composition layer remaining after the development processing can be accurately controlled. Therefore, it is possible to control the depth of the concave portion formed by the mold formed of the patterned photosensitive resin composition layer and the exposed portion of the transparent substrate with high precision, and accordingly, the colored glass filled in the concave portion is formed. Since the control of the thickness of the paste is also improved, there is an effect that the thickness accuracy of the colored pattern layer in the plasma display panel for color display can be improved.

According to the second aspect of the present invention, the acrylic monomer polymerized by light irradiation has a functional group represented by the chemical formula (4), and the acrylic monomer having this functional group is Since the developing solution resistance of the exposed portion of the photosensitive resin composition layer after the exposure polymerization becomes good, the film loss due to the development processing is reduced, and the accuracy of the mold formed of the patterned photosensitive resin composition layer is improved. The plasma display panel for color display
Has the effect of kick can be further improved thickness precision color pattern layers.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a process of manufacturing a color filter according to an embodiment.

FIG. 2 is a schematic sectional view of a plasma display panel for color display.

FIG. 3 is a sectional view taken along the line III-III of FIG. 4;

FIG. 4 is a schematic plan view showing a display area of a rear substrate in a color plasma display panel.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Photosensitive resin composition layer 3 Photomask 3y Light shielding film 4 'Colored glass paste 4 Color filter layer 5 Squeegee

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03F 7/033 G03F 7/004 G03F 7/027 G03F 7/40

Claims (2)

(57) [Claims] A photosensitive resin composition containing an acrylic resin, an acrylic monomer, a photopolymerization initiator for initiating polymerization of an acrylic monomer by light irradiation, and a diluting solvent is coated on a transparent substrate, and exposed to light. Developing and patterning, and having a low melting point in a concave portion formed by a mold formed of a patterned photosensitive resin composition layer and an exposed portion of a transparent substrate;
After filling a colored glass paste containing a glass powder and a colored pigment, the mold is removed by a baking treatment , and a color display plate comprising a colored glass paste is formed on a transparent substrate.
In a photosensitive resin composition used for a method of forming a colored pattern layer of a display panel, the acrylic resin is a monomer represented by the following chemical formula (1) and a monomer represented by the following chemical formula (2): A photosensitive resin composition comprising a copolymer with a monomer represented by the following chemical formula (3). Embedded image (Wherein, R1 represents an alkyl group having 1 to 5 carbon atoms). Embedded image 2. The photosensitive resin composition according to claim 1, wherein the acrylic monomer polymerized by light irradiation has a functional group represented by the following chemical formula (4). Embedded image