KR20100074617A - Negative photosensitive resin composition for forming a barrier rib of pdp - Google Patents

Abstract

PURPOSE: A negative photoresist resin composition for forming a PDP barrier rib, and a plasma display panel(PDP) including the barrier rib are provided to remove an unnecessary laminating process, and to prevent the reduction of the production efficiency. CONSTITUTION: A negative photoresist resin composition for forming a PDP barrier rib is capable of forming the barrier rib at the coating thickness of 5~10 micrometers. The negative photoresist resin composition contains 50~60wt% of modified epoxy acrylate resin marked with chemical formula 1, 10~20wt% of radical polymerization initiator containing more than one photopolymerization initiator, 10~20wt% of monomer with a radical polymerizable double bond within a molecule, 1~2wt% of antifoaming agent, 1~2wt% of leveling agent, and 10~30wt% of solvent.

Description

Negative photosensitive resin composition for PD partition formation {NEGATIVE PHOTOSENSITIVE RESIN COMPOSITION FOR FORMING A BARRIER RIB OF PDP}

The present invention relates to an intaglio-type photosensitive resin composition for forming partition walls of a plasma display panel (PDP) back plate.

When at least one potential difference is applied between two spatially separated contacts in a non-vacuum gas atmosphere, a discharge is generated. The plasma display device is a flat panel display device in which such a gas discharge phenomenon is applied to image display. The plasma display panel which is generally used at present is a reflective AC drive plasma display panel. In the case of a back substrate structure, a phosphor layer is formed on a partition wall.

As a manufacturing method for forming the partition layer of the back panel of the plasma display panel (PDP), a colored material is applied and dried to a predetermined thickness on a glass substrate, and a sandblast resistant mask is formed on the pattern and then sanded. Sandblasting is performed by blasting to remove parts other than partitions and firing to form desired partitions, and etching is performed by coating, exposing, developing and etching processes using photoresist or DFR film. In addition, there is a method of directly forming a partition by exposing and developing a paste containing a photosensitive polymer resin, a filler for the partition wall and a filler material serving as an aggregate.

In general, a method of manufacturing a plasma display panel (PDP) back plate by an etching method is described as follows.

Place the electrode paste on the back glass substrate on the electrode plate and print the electrode pattern with squeegee to form the electrode pattern, and then dry it for 5 to 10 minutes at a temperature of 120 to 150 ℃, and then to 10 to 500 to 600 ℃. Firing for about minutes. Subsequently, a dielectric paste was placed on the dielectric plate on the fired body and the entire surface was printed with a squeegee to form a dielectric layer. The dielectric layer was dried at a temperature of 120 to 150 ° C. for about 5 to 10 minutes, and then to 550 to 580 ° C. Firing is performed for about 10 minutes. Subsequently, the partition paste is placed on the partition plate on the dielectric layer and the front surface of the partition is printed by squeegee to form a partition layer. The partition layer is dried at a temperature of 120 to 150 ° C. for 5 to 10 minutes, and then the partition wall is formed on the partition wall layer. After performing the front printing process and the drying process about 8 to 10 times, the photoresist is coated on the dried body to perform exposure and development, and then a barrier layer is formed through an etching process. Then, the photoresist is removed and then calcined at 550 to 600 ° C. for about 10 minutes to complete the partition wall.

Korean Laid-Open Patent Publication No. 2002-0058939 discloses a method for manufacturing a back substrate of a plasma display panel which is processed after firing without the photosensitive resin coating, exposure, development, and thin film processing, and Korean Laid-Open Patent Publication No. 2001-0113340 No. 2001-0113341 discloses a plasma display panel in which a colored material is coated and baked on a back substrate, a mask having resistance to etching is formed in a pattern, and then selectively etched with an acid-based liquid combination to form a partition wall. It describes the colored material for the rear substrate. However, all of the above inventions are made of a barrier material mainly composed of amorphous mother glass, so that the etching rate is relatively slow and etching is required for a long time, causing cracks in the photosensitive resin, and also causing many problems in terms of production yield. Doing. Therefore, the method of improving crack resistance with respect to a long etching time is performed by raising the coating film thickness of the photosensitive resin. However, this method leads to problems of lower production efficiency and lower price competitiveness due to excessive coating thickness.

The present invention is to improve the production efficiency and lower the price competitiveness due to the excessive film thickness caused by using conventional DFR or other embossed photosensitive resin, etc., it is coated with a low film thickness containing a modified epoxy acrylate resin It is an object of the present invention to provide an intaglio-type photosensitive resin composition for forming a PDP partition wall which is excellent in etch resistance even if it forms a high-sensitivity and high resolution pattern. In particular, it is an object of the present invention to provide an intaglio-type photosensitive resin composition which has a greater effect on the formation of partition walls of 113 pitches or less accessible to low-cost mass production equipment in current PDP devices.

The present invention provides an intaglio-type photosensitive resin composition for forming PDP barrier ribs capable of forming barrier ribs having a pitch of 113 µm or less at a coating thickness of 5 µm to 10 µm.

The negative photosensitive resin composition for PDP partition wall formation,

(A) modified epoxy acrylate resin represented by the following formula (1);

(B) a radical polymerization initiator comprising at least one photoinitiator and a photoinitiator adjuvant;

(C) a monomer having a radical polymerizable double bond in the molecule;

(D) antifoams;

(E) leveling agents; And

(F) It contains a solvent.

Wherein R 1 is H or CH ₃ and n is an integer from 1 to 7.

In addition, the present invention provides a plasma display panel comprising a partition wall formed using the composition.

The intaglio-type photosensitive resin composition for forming PDP barrier ribs of the present invention is economical in terms of power consumption and installation area because it does not require a lamination process that is essentially performed when DFR or an embossed photocurable resin is used for barrier rib formation of a plasma display panel. In particular, there is no problem of deterioration in production efficiency and price competitiveness due to excessive coating thickness, and the use of a thin coating film having a etch resistance of about 10 μm enables not only to form a good pattern of high sensitivity and high resolution, but also storage stability. Excellent cost savings for the formation of bulkheads.

In particular, the negative photosensitive resin composition for forming a PDP partition wall of the present invention has a greater effect on the formation of a partition pitch of 113 pitch or less that is accessible to low-cost mass production equipment in PDP devices currently in use.

The present invention relates to an intaglio-type photosensitive resin composition for forming PDP barrier ribs capable of forming barrier ribs of 113 µm or less in a coating thickness of 5 µm to 10 µm.

The negative photosensitive resin composition for PDP partition wall formation,

(A) modified epoxy acrylate resin represented by the following formula (1);

(B) a radical polymerization initiator comprising at least one photoinitiator and a photoinitiator adjuvant;

(C) a monomer having a radical polymerizable double bond in the molecule;

(D) antifoams;

(E) leveling agents; And

(F) It contains a solvent.

[Formula 1]

Wherein R 1 is H or CH ₃ and n is an integer from 1 to 7.

In the above description, the pitch means a distance between one partition wall and another partition wall. As the distance between the partition walls is smaller, a larger amount of pixels can be realized in a predetermined area, thereby enabling a high brightness display.

The negative photosensitive resin composition for PDP partition wall formation, with respect to the total weight of the composition,

(A) 50 to 60% by weight of modified epoxy acrylate resin represented by the following formula (1);

(B) 10 to 20% by weight of a radical polymerization initiator comprising at least one photoinitiator and a photoinitiator adjuvant;

(C) 10 to 20% by weight of a monomer having a radical polymerizable double bond in the molecule;

(D) 1-2 wt% of antifoaming agent;

(E) 1-2 wt% leveling agent; And

(F) It is characterized by containing 10-30 weight% of solvents.

Compound represented by the formula (1) can be obtained by a manufacturing method comprising the steps (a) and (b) described below.

(a) As the reaction catalyst, at least one selected from the group consisting of triphenylphosphine, triethylamine, benzyldimethylamine, methyltriethylammonium chloride, chromium octanoate and zirconium octanoate, is used for the total weight of the reaction mixture. Using 0.1 to 1% by weight, the epoxy compound of the formula (2) and the acrylic acid of the formula (3) in an organic solvent at 90 to 110 ℃, with a reaction ratio of 0.8 to 1.2 moles of acrylic acid, preferably 1 mole per 1 equivalent of the epoxy group Reacting to obtain an epoxy acrylate of the following formula (4):

Wherein R 1 is H or CH ₃ and n is an integer from 1 to 7.

In the formula, R1 is as defined in formula (2).

(b) 0.8 to 1.2 moles of phthalic anhydride, preferably 1% reaction product (Formula 4) and tetrahydrophthalic anhydride of formula (5) below with respect to 1 equivalent of the hydroxy group of formula (4) Reacting at a reaction ratio of 1 mole to obtain a compound of Formula 1, wherein a phthalic acid residue is introduced at the terminal or side chain.

Hereinafter, the present invention will be described in more detail.

The negative photosensitive resin composition of the present invention has a feature that can be developed at high speed by an alkaline developer after coating with various kinds of coating methods.

(A) Modified epoxy acrylate resin represented by the formula (1)

In the method for preparing a compound represented by Chemical Formula 1, the epoxy compound of Chemical Formula 2 may include, for example, an epoxy phenol novolak resin (when R1 is H) or an epoxy cresol novolak resin (wherein R1 is CH _3). Is an epoxy equivalent of 200 to 230 and a softening point of 75 to 85 ° C. Specific examples include YDCN-500-90P (National Chemical Epoxy), N-680 (manufactured by LG Chemical), EOCN-103S (manufactured by NIPPON KAYAKU), or ECN-1280 (manufactured by Shiva-Geigi). As the organic solvent used, for example, butyl carbitol acetate, methyl ethyl ketone, cyclohexanone, toluene, dipropylene glycol dimethyl ether, ethyl acetate, butyl cellosolve acetate, petroleum Ether and the like, and these may be used alone or in combination of two or more. The usage-amount is 5-30 weight% with respect to the total weight of (A) component.

In addition, the polymerization inhibitor used may include, for example, methylethyl hydroquinone, hydroquinone, methylhydroquinone, catechol, pyrogallol, and the like, which may be used alone or in combination of two or more. . The usage-amount is 100-400 ppm with respect to the total weight of (A) component, Preferably it is 200 ppm.

In the composition of the present invention, the modified epoxy acrylate resin represented by Formula 1 is preferably included in an amount of 50 to 60% by weight based on the total weight of the negative photosensitive resin composition.

If the modified epoxy acrylate resin is included in less than 50% by weight may cause a problem of poor development of the final product, when it exceeds 60% by weight may be gelation (Gelation) during synthesis.

(B) radical polymerization initiator

The radical polymerization initiator used in the negative photopolymerizable composition of the present invention includes at least one photopolymerization initiator and a photopolymerization initiator. The photoinitiator is a compound that generates radicals when exposed to active light such as ultraviolet rays or visible light. For example, benzoin-based photoinitiators such as benzoin, benzoin methyl ether, benzoin benzopropyl ether, and a-acrylbenzoin. ; Aryl ketone photopolymerization initiators such as benzophenone, p-methylbenzophenone, p-chlorobenzophenone, tetrachlorobenzophenone and acetone benzo; Dialkylaminoaryl ketone-based photopolymerization initiators such as 4,4'-bisdiethylaminobenzophenone and p-dimethylaminoacetonephenone; Polyvalent carbonyl photoinitiators such as halogen substituents such as thioxanthone, xanthone and 2-chlorothioxanthone; IRGACURE 907 etc. These can be used individually or in combination of 2 or more types.

The photoinitiator adjuvant is used to increase the activity of the photopolymerization initiator, and examples thereof include benzophenone series, benzoin methyl ether series, or tetraethyl thiurane disulfide series, and these may be used alone or in combination of two or more. Can be used together.

The content of the radical polymerization initiator is preferably 10 to 20% by weight based on the total weight of the negative photosensitive resin composition. When the amount of the radical polymerization initiator is included in less than 10% by weight, no pattern formation or pattern tearing occurs in the process, and when it exceeds 20% by weight, difficulty may occur in the developing process.

 (C) monomers having radically polymerizable double bonds in the molecule

The monomer serves to impart etching resistance and solvent resistance to the cured resist film. As said monomer, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, diethylene glycol diacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacryl Latex, trimethylolpropane ethylene oxide modified triacrylate, trimethylolpropanepropylene oxide modified triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and the respective methacrylates corresponding to the acrylates Ryu; Mono-, di-, tri- or more polyesters of polybasic acids such as phthalic acid, adipic acid, maleic acid, itaconic acid, succinic acid, trimellitic acid and terephthalic acid with hydroxyalkyl (meth) acrylates However, the present invention is not limited thereto, and these may be used alone or in combination of two or more.

Among these radically polymerizable monomers, a polyfunctional monomer having two or more acryloyl groups or methacryloyl groups in one molecule is preferable.

In the composition of the present invention, the content of the monomer having a radical polymerizable double bond in the molecule is preferably 10 to 20% by weight based on the total weight of the negative photosensitive resin composition. When the monomer is contained in less than 10% by weight, the composition is difficult to obtain sufficient photocurability, and when it exceeds 20% by weight, the curing of the surface portion is likely to occur because the photocuring of the surface portion is faster than the deep portion of the coating.

(D) antifoam

In the present invention, the antifoaming agent is added to facilitate miscibility in the preparation of the resin composition, and to reduce the defects caused by the pinhole generation and the nonuniformity of the film in the process of producing the thick film. Specific examples thereof include anionic copolymer, aralkyl-modified polymethylalkylsiloxane, polyester-modified polymethylalkylsiloxane, polysiloxane, non-silicone polymer mixture, modified urea solution, polyester-modified dimethylpolysiloxane, polyester-modified dimethyl Polysiloxane copolymers and the like.

The content of the antifoaming agent in the composition of the present invention is preferably 1 to 2% by weight based on the total weight of the negative photosensitive resin composition. If the content of the antifoaming agent is less than 1% by weight, it is difficult to expect the effect. If the content of the antifoaming agent exceeds 2% by weight, a residual film is likely to be left during the development process.

 (E) Leveling agent

In the present invention, the leveling agent is used to secure flatness and improve staining in the application of the resin composition. As a specific example, a silicon type or a fluorine type can be used.

The content of the leveling agent in the composition of the present invention is preferably 1 to 2% by weight based on the total weight of the negative photosensitive resin composition. If the leveling agent is included in less than 1% by weight, a problem may occur such that a step occurs when coating occurs, and when the leveling agent exceeds 2% by weight, a sensitivity may be lowered during exposure.

(F) solvent

Examples of the solvent for dissolving the alkali-soluble novolak resin, the crosslinking agent and the like include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, 2-heptanone and cyclohexanone; Amides such as N, N-dimethylacetamide and N-methylpyrrolidone; Lactones, such as (gamma) -butyrolactone, etc. are mentioned. These solvents may be used alone or in combination of two or more.

The content of the solvent in the composition of the present invention is preferably 10 to 30% by weight based on the total weight of the negative photosensitive resin composition. If the solvent is contained in less than 10% by weight, the problem of gelation (Gelation) due to the rapid increase in viscosity may occur, and if it exceeds 30% by weight may cause problems of productivity and yield decrease due to excessive reaction time.

When the partition of the plasma display panel is formed using the intaglio photosensitive resin composition of the present invention, it is possible to form a pattern having a high resolution of 113 μm even when the coating thickness of the composition is 5 μm to 10 μm.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Preparation Example 1 Preparation of Compound Represented by Formula 1

While injecting nitrogen, 210 g of YDCN-500-90P (epoxy cresol novolak resin, manufactured by Kukdo Chemical Epoxy), 400 g of butylcarbitol acetate, and 1 g of hydroquinone were placed in a reaction vessel, and heated and stirred at 80 ° C. for 1 hour to uniform contents. Mixed. 1 g of triethylamine was added thereto, and 72 g of acrylic acid was added thereto while maintaining at 90 ° C. for 2 to 4 hours. When acrylic acid is added, the epoxy ring opens, causing a serious exotherm, and when a sudden exotherm occurs, it cools rapidly.

After the reaction was completed, the reaction was cooled to the temperature of the reaction to room temperature, placed into a tetrahydrophthalic anhydride 152g and butyl carbitol acetate 100g while maintaining the reaction temperature at 100 ~ 110 ℃ for a few hours, 1780 ~ 1850cm ^- After confirming that there is no absorption peak of the anhydride functional group in ¹ , the temperature of the reaction was quenched to room temperature.

Examples 1-2: Preparation of the negative photosensitive resin composition for PDP partition wall formation

The following components were mixed at the indicated composition ratios to prepare the negative photosensitive resin composition and evaluated for properties.

Example 1 Example 2 (A) Final product of Preparation Example 1 50 55 (B) photopolymerization initiator 15 15 (C) reactive monomer 20 10 (D) Photopolymerization Initiator One 2 (E) Organic Solvent 11 15 (F) antifoam 2 2 (G) leveling agent One One

(Content: wt%)

<Adhesive evaluation>

The board | substrate with which the mother glass paste for partition formation was apply | coated completely was prepared. After coating the engraved photocurable resin of Examples 1 and 2 and DWG-520 (product of the embossed photocurable resin composition of Dongwoo Fine-Chem Co., Ltd.) on the substrate, and forming a constant pattern through the exposure and development processes, , A partition wall having a constant shape was formed through an etching process.

The said etching was performed using the etching liquid containing 0.3-0.5 weight% of nitric acid which is the etching liquid used by the existing line, and residual amount of water. Etching liquid prepared in a spray etching test equipment (manufactured by KDNS, model name: ETCHER (TFT)) was added and heated to 40 ° C., and then the etching process was performed when the temperature reached 40 ± 0.5 ° C. . Etching was performed until the substrate was inserted and spraying was started until the 113 탆 pitch dropped. After the etching was completed, the resultant was removed, washed with deionized water, dried using a hot air dryer, and the resin was removed using a stripper. After washing and drying, the presence, absence, and shape of the partition wall having a pitch of 113 μm were confirmed using an electron scanning microscope (SEM; manufactured by HITACHI, model name: S-4700). The results are shown in Table 2. 　

A / B / C / D / E / F / G Coating thickness 113 pitch fall time Example 1 50/15/20/1/11/2/1 10 탆 5 minutes 30 seconds Example 2 55/15/10/2/15/2/1 10 탆 6 minutes Comparative example DWG-520 (Dongwoo Fine Chem, Inc., embossed photocurable resin composition product) 25 μm 2 minutes

※ Time when 113 pitch falls: Time that it takes for the negative photosensitive resin of 113㎛ pitch to fall completely

1 is an electron scanning microscope (SEM) photograph of a partition wall formed using the embossed photocurable resin composition of the comparative example.

FIG. 2 is an electron scanning microscope (SEM) photograph of a partition wall formed using the negative photocurable resin composition prepared in Example 2. FIG.

Claims (4)

An intaglio-type photosensitive resin composition for forming PDP barrier ribs capable of forming a barrier rib of 113 µm or less at a coating thickness of 5 µm to 10 µm. The intaglio-type photosensitive resin composition for forming a PDP barrier rib according to claim 1, based on the total weight of the composition, (A) 50 to 60% by weight of modified epoxy acrylate resin represented by the following formula (1); (B) 10 to 20% by weight of a radical polymerization initiator comprising at least one photoinitiator and a photoinitiator adjuvant; (C) 10 to 20% by weight of a monomer having a radical polymerizable double bond in the molecule; (D) 1-2 wt% of antifoaming agent; (E) 1-2 wt% leveling agent; And (F) 10-30 wt% of solvent An intaglio-type photosensitive resin composition for forming a PDP partition wall comprising: [Formula 1]

Wherein R 1 is H or CH ₃ and n is an integer from 1 to 7. The monomer according to claim 1 or 2, wherein the monomer having a radical polymerizable double bond in the molecule is 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, diethylene glycol diacrylate, trimethylolpropane triacrylate, Pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane ethylene oxide modified triacrylate, trimethylolpropanepropylene oxide modified triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylic Methacrylates corresponding to the rate and the acrylate; Selected from the group consisting of mono-, di-, tri- or more polyesters with phthalic acid, adipic acid, maleic acid, itaconic acid, succinic acid, trimellitic acid, terephthalic acid, and hydroxyalkyl (meth) acrylates An intaglio type photosensitive resin composition for forming a PDP partition wall, characterized in that it is composed of one or more kinds. A plasma display panel comprising a partition wall formed using the negative photosensitive resin composition for PDP partition wall formation of claim 1.

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