KR20070106131A - Positive type photoresist film - Google Patents

Abstract

A positive photoresist film is provided to form directly a metal electrode on an insulation substrate deposited with a plating catalyst under strong alkali conditions due to excellent metal coating properties and adhesion properties. A positive photoresist film includes a support film(10) and a photoresist layer(20) formed on the support film. The photoresist layer contains a photosensitive compound of 30 to 80 parts by weight, a thermosetting resin of 10 to 30 parts by weight, a solvent of 190 to 250 parts by weight and an isocyanate compound of 0.5 to 3 parts by weight on the basis of an alkali soluble resin of 100 parts by weight.

Description

Positive photoresist film {Positive type photoresist film}

1 is a cross-sectional view of a positive photoresist film according to the present invention.

The present invention relates to a positive type photoresist film, and specifically, is excellent in heat resistance, adhesion, alkali resistance and plating resistance, and is suitable for the field of metal plating under strong alkali conditions, such as a silver (Ag) electrode manufacturing process of PDP. It is about a film. More specifically, the present invention relates to a photoresist film useful for directly forming a metal electrode on an insulating substrate having excellent heat resistance, adhesion, alkali resistance, and plating resistance at the same time as photosensitive speed, development contrast, sensitivity, resolution, and the like.

Photoresist and photoresist films include Cathode Ray Tubes (CRTs), liquid crystal displays (LCDs) and organic electroluminescent displays (EL or ELD), integrated circuits (ICs), printed circuit boards (PCBs), and electronic displays. It is used for manufacturing highly integrated semiconductors such as Photolithography and photo-fabrication techniques are used in the fabrication of these devices. The photoresist film requires a resolution that is capable of forming a pattern having very thin lines and a small space area of 7 μm or less.

The chemical properties of the photoresist resin or the photoresist may change the physical properties of the photoresist, such as changes in solubility, coloration, and curing of a specific solvent. Physical properties of the photoresist may change, such as change in solubility in solvents, coloring, curing, and the like.

Looking at the conventional method of manufacturing the silver (Ag) electrode of the PDP as an example of the prior art for forming a metal electrode, the front surface of the resin composition in which silver (Ag) particles are dispersed on the glass substrate by screen printing method, and then in turn Silver (Ag) electrodes were prepared in a pre-bake, exposure, development, drying and firing manner.

In the conventional method, since the silver paste is completely coated on the glass substrate, and the other parts of the electrode formation are removed through development, the loss of silver paste and the metal for forming the electrode (Ag, etc.) is too high, leading to an increase in manufacturing cost. .

On the other hand, in the plating method for forming the electrode, the etching process replaces the silver paste method, which requires a high-temperature sintering process, so that there is no deformation of the substrate and the pattern, and an electrode pattern can be formed inside the photoresist layer. Although there is an advantage of preventing, various studies have been conducted due to the adhesion of the plating pattern to the insulating substrate and the resistance of the photoresist composition. Conventional photoresist compositions have poor plating resistance, making it difficult to manufacture metal electrodes by metal plating for strong alkaline plating solutions.

The object of the present invention is to provide an excellent plating resistance to the metal electrode plating process performed under strong alkali conditions so as to solve the conventional problems. It is possible to provide a positive photoresist film that is possible and excellent in adhesion and useful for forming a metal electrode on an insulating substrate.

The present invention is excellent in photosensitivity, development contrast, sensitivity and resolution, and also has excellent alkali resistance and plating resistance, so that the metal electrode such as silver (Ag) electrode for PDP can be applied to the process of producing metal electrode under strong alkali conditions. It is intended to provide a positive photoresist film. In addition, the present invention is to provide a positive type photoresist film that can significantly reduce the manufacturing cost by reducing the amount of metal (Ag, etc.) for forming the electrode, such as Ag (silver) when manufacturing the metal electrode.

The present invention also provides a positive photoresist film useful for directly forming a metal electrode on an insulating substrate having excellent adhesion to a plating catalyst.

The present invention and the support film to achieve the above object; Provided is a positive photoresist film comprising a photoresist layer on the support film, wherein the photoresist layer comprises an alkali soluble resin, a photosensitive compound, a thermosetting resin, a solvent, and an isocyanate compound. The present invention may include a sensitivity sensitizer, a mold release agent and the like in addition to the compound.

Advantages of the present invention will become apparent from the detailed description given hereinafter. However, the detailed description and embodiments are intended to illustrate the preferred embodiment of the present invention, so those skilled in the art will understand that various changes and modifications are possible within the spirit and scope of the present invention.

Hereinafter, the configuration of the present invention will be described in more detail with the accompanying drawings.

As shown in FIG. 1, the positive photoresist resin film of the present invention includes a support film 10 and a photoresist layer 20 laminated on the support film 10. In some cases, a protective layer (not shown) may be further included on the photoresist layer 20 to improve storage safety and transportability of the positive photoresist film of the present invention. The photoresist layer 20 includes an alkali soluble resin, a photosensitive compound, a thermosetting resin, a solvent, and an isocyanate compound.

The support film 10 of the present invention should have suitable physical properties for the positive photoresist film. Non-limiting examples of suitable support film materials include polycarbonate films, polyethylene (PE) films, polypropylene (PP) films, stretched polypropylene (OPP) films, polyethylene terephthalate (PET) films, polyethylene naphthalates (PEN) ) Films, ethylene vinyl acetate (EVA) films, polyvinyl films, other suitable polyolefin films, epoxy films, and the like. Particularly preferred polyolefin films are polypropylene (PP) films, polyethylene (PE) films, ethylene vinyl acetate (EVA) films and the like. Preferred polyvinyl films are polyvinyl chloride (PVC) films, polyvinyl acetate (PVA) films, polyvinyl alcohol (PVOH) films and the like. Particularly preferred polystyrene films are polystyrene (PS) films, acrylonitrile / butadiene / styrene (ABS) films and the like. In particular, the support film is preferably transparent so that light can pass through the support film to irradiate the photoresist resin layer.

The support film 10 preferably has a thickness in the range of about 10 to 50 μm, preferably about 15 to 50 μm, more preferably about 15, to serve as a framework for supporting the shape of the positive type photoresist resin film. It may have a thickness in the range from 25㎛.

Next, the components of the photoresist layer 20 according to the present invention will be described in detail.

The alkali-soluble resin is not particularly limited but includes a thermosetting novolak resin which is a condensation product of phenol and aldehyde, and most preferably cresol novolak resin.

Novolak resins are obtained by polycondensation of phenol alone or in combination with aldehydes and acidic catalysts.

Although it does not specifically limit as phenols, Phenol, o-cresol, m-cresol, p-cresol, 2, 3- xylenol, 2, 5- chisylenol, 3, 4- chisylenol, 3, 5- kisylenol, 2 Monohydric phenols such as 3,5-trimethylphenol-chisylenol, 4-t-butyl phenol, 2-t-butyl phenol, 3-t-butyl phenol and 4-methyl-2-t-butyl phenol; And 2-naphthol, 1,3-dihydroxy naphthalene, 1,7-dihydroxy naphthalene, 1,5-dihydroxy naphthalene, resorcinol, pyrocatechol, hydroquinone, bisphenol A, phloroglucinol, Polyhydric phenols, such as a pyrogallol, etc. are mentioned, It can be used individually or in combination of 2 or more types. In particular, a combination of m-cresol and p-cresol is preferable.

Examples of the aldehyde include, but are not particularly limited to, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α- or β-phenyl propylaldehyde, o-, m- or p-hydroxybenzaldehyde And glutaraldehyde, terephthalaldehyde and the like, and can be used alone or in combination of two or more thereof.

The cresol novolac resin used in the present invention preferably has a weight average molecular weight (based on GPC) of 2,000 to 30,000.

In addition, the cresol novolak resin used in the present invention will vary the physical properties such as the photosensitivity rate and the residual film ratio according to the content ratio of meta / para cresol, the content of meta / para cresol is 4: 6 to 6 by weight It is preferable to mix in a ratio of 4: 4.

When the content of the meta cresol in the cresol novolak resin exceeds the above range, the photoresist rate is increased while the residual film rate is drastically lowered. When the content of the para cresol exceeds the above range, the photosensitivity is slowed.

The cresol novolac resin may be used alone as a cresol novolac resin of the meta / para cresol content of 4: 6 to 6: 4 by weight as described above, more preferably mixed resins having different molecular weights Can be. In this case, the cresol novolac resin (i) contains a cresol novolac resin having a weight average molecular weight (GPC basis) of 8,000 to 30,000 and (ii) a cresol novolac resin having a weight average molecular weight (GPC basis) of 2,000 to 8,000. It is preferable to mix and use in the ratio of 3: 3 to 9: 1.

Here, the term 'weight average molecular weight' is defined in terms of polystyrene equivalents, as determined by gel permeation chromatography (GPC). In the present invention, if the weight average molecular weight of the novolak resin is less than 2,000, the photoresist resin film may have a large thickness reduction in the non-exposed part after development, whereas if it exceeds 30,000, the development speed is lowered and the sensitivity is lowered. The novolak resin of the present invention can achieve the most preferable effect when the resin obtained after removing the low molecular weight component from the reaction product has a weight average molecular weight (2,000 to 30,000) in the above-described range. In removing the low molecular weight component from the novolak resin, it is convenient to use techniques including fractional precipitation, fractional dissolution, tube chromatography, and the like. Thereby, the performance of a photoresist resin film can be improved, especially scumming, heat resistance, etc. can be improved.

The novolac resin is soluble in an aqueous alkali solution without volume increase and provides an image capable of providing high resistance to plasma etching when used as a mask during etching.

The photosensitive compound is a diazide-based photosensitive compound, and also acts as a dissolution inhibitor that reduces the solubility of alkali in the novolak resin. However, when the compound is irradiated with light, the compound is converted into an alkali-soluble material, which increases the alkali solubility of the novolak resin.

The diazide photosensitive compound can be synthesized by esterification of a polyhydroxy compound and a quinone diazide sulfonic acid compound. The esterification reaction for obtaining the photosensitive compound is carried out by dioxane, acetone, tetrahydrofuran, methylethylketone, N-methylpyrrolidine, chloroform, trichloroethane, trichloro and the polyhydroxy compound and the quinonediazide sulfonic acid compound. Dissolved in a solvent such as ethylene or dichloroethane, and condensed by dropwise addition of a basic catalyst such as sodium hydroxide, sodium carbonate, sodium bicarbonate, triethylamine, N-methylmorpholine, N-methylpiperazine or 4-dimethylaminopyridine The obtained product is washed, purified and dried. It is possible to selectively esterify only specific isomers and the esterification ratio (average esterification rate) is not particularly limited, but the diazide sulfonic acid compound for the OH group of the polyhydroxy compound is 20 to 100%, preferably 60 to 90 Range of%. Too low an esterification ratio results in deterioration of pattern shape or resolution, and too high an effect of deterioration of sensitivity.

As the quinone diazide sulfonic acid compound, for example, 1,2-benzoquinone diazide-4-sulfonic acid, 1,2-naphthoquinone diazide-4-sulfonic acid, 1,2-benzoquinone diazide-5-sulfonic acid and 1, O-quinone diazide sulfonic acid compounds, such as 2-naphthoquinone diazide-5-sulfonic acid, other quinone diazide sulfonic acid derivatives, etc. are mentioned. The diazide photosensitive compound is preferably 1,2-benzoquinone diazide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2-naphthoquinone diazide-5- At least one of sulfonic acid chlorides.

The quinonediazide sulfonic acid compounds themselves have a function as a dissolution inhibitor which lowers the solubility of the novolak resin in alkali. However, it decomposes in order to produce alkali-soluble resins upon exposure, thereby having the property of promoting dissolution of the novolak resin in alkali.

As the polyhydroxy compound, trihydroxy benzophenones such as 2,3,4-trihydroxy benzophenone, 2,2 ', 3-trihydroxy benzophenone, and 2,3,4'-trihydroxy benzophenone ; Tetrahydroxybenzophenones such as 2,3,4,4-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone and 2,3,4,5-tetrahydroxybenzophenone ; Pentahydroxybenzophenones such as 2,2 ', 3,4,4'-pentahydroxybenzophenone and 2,2', 3,4,5-pentahydroxybenzophenone; Hexahydroxybenzophenones such as 2,3,3 ', 4,4', 5'-hexahydroxybenzophenone and 2,2,3,3 ', 4,5'-hexahydroxybenzophenone; Gallic acid alkyl esters; And oxyflavanes.

The diazide photosensitive compound used in the present invention is preferably 2,3,4,4-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-sulfonate, 2,3,4-trihydrate Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate and (1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl ) Ethyl] benzene) -1,2-naphthoquinonediazide-5-sulfonate. In addition, diazide photosensitive compounds prepared by reacting diazide compounds such as polyhydroxy benzophenone, 1,2-naphthoquinone diazide, and 2-diazo-1-naphthol-5-sulfonic acid can also be used. .

For such diazide photosensitive compounds, see Light Sensitive Systems, Kosar, J .; See John Wiley & Sons, New York, 1965, chapter 7.

Such a photosensitive compound (photosensitive agent) used as one component of the photoresist layer 20 of the present invention is selected from substituted naphthoquinone diazide photosensitive agents generally applied as a positive photoresist resin composition. Such photosensitive compounds are described, for example, in US Pat. No. 2,797,213; 3,106,465; 3,148,983; 3,201,329; 3,785,825, 3,802,885 and the like.

The diazide photosensitive compound may be used alone or in combination of two or more of 30 to 80 parts by weight based on 100 parts by weight of the alkali-soluble resin. If it is 30 parts by weight or more, the developing solution is more easily developed, and the residual ratio of the photoresist film is considerably higher. If it is more than 80 parts by weight, it is not economical and the solubility in the solvent is low.

The photosensitive speed of the positive photoresist resin film of the present invention can be controlled by using the diazide photosensitive compound. For example, a method of controlling the amount of the photosensitive compound and 2,3,4-trihydroxybenzophene There is a method of controlling the ester reactivity between a polyhydroxy compound such as rice paddy and a quinonediazide sulfonic acid compound such as 2-diazo-1-naphthol-5-sulfonic acid.

The diazide-based photosensitive compound decreases the solubility of the alkali-soluble resin in the aqueous alkali solution developer before exposure by about 100 times, but after exposure, the diazide-based photosensitive compound becomes soluble in the aqueous alkali solution and becomes soluble in the aqueous alkali solution, compared with the non-exposed positive photoresist composition. Solubility is increased by about 1000 to 1500 times. The formation of microcircuit patterns such as LCDs and organic ELs utilizes these properties of photoresists. More specifically, when UV rays are applied to a photoresist coated on a silicon wafer or a glass substrate through a circuit-shaped semiconductor mask and treated with a developer, only a desired circuit pattern remains on the silicon wafer or the glass substrate.

The thermosetting resin is a methoxymethylmelamine-based resin and the like is preferably 10 to 30 parts by weight based on 100 parts by weight of alkali-soluble resin. When it is 10 parts by weight or more, the alkali resistance and plating resistance of the present invention are excellent, and when it is 30 parts by weight or less, the developing process becomes easy.

In addition, the methoxymethyl melamine-based resin is more preferably hexamethoxy methyl melamine (Hexamethoxy melamine) resin.

Since the present invention includes a thermosetting resin in the photoresist layer as described above, a cross-linking reaction of the thermosetting resin occurs during the heat treatment process after fabricating the metal electrode, thereby greatly improving alkali resistance and plating resistance.

The solvent is ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and propylene glycol monoethyl ether acetate, acetone, methyl ethyl ketone, ethyl alcohol, methyl alcohol, propyl alcohol, isopropyl alcohol , Benzene, toluene, cyclopentanone, cyclohexanone, ethylene glycol, xylene, ethylene glycol monoethyl ether and diethylene glycol monoethyl ether.

The content of the solvent is preferably about 190 to 250 parts by weight based on 100 parts by weight of the alkali-soluble resin. Less than about 190 parts by weight, the film formability and lamination of the photoresist resin layer are less improved. The coating property of this invention becomes excellent in the said range.

The isocyanate compound serves to improve the adhesion between the photoresist and the plating catalyst such as palladium (Pd), and the content thereof is preferably 0.5 to 3 parts by weight based on 100 parts by weight of the alkali-soluble resin.

Isocyanate compounds are very reactive and especially react easily with compounds having active hydrogens. It reacts easily with alcohol, amine, water, carboxylic acid and epoxide as well as self reaction.

The molecular structure through the triple bond of isocyanate is as follows.

Through such compositions, it is possible to improve the adhesion to the insulating substrate and to provide heat resistance for the metal plating process, thereby enabling stable pattern formation.

In addition to the composition of the above-mentioned components, sensitivity enhancers are used to improve the sensitivity of the positive photoresist film. The sensitivity enhancer is a polyhydroxy compound having 2 to 7 phenolic hydroxyl groups and having a weight average molecular weight of less than 1,000 compared to polystyrene. Preferred examples include 2,3,4-trihydroxybenzophenone, 2,3,4,4-tetrahydroxybenzophenone, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [ It is preferable that it is 1 or more types chosen from 1, 1-bis (4-hydroxyphenyl) ethyl] benzene.

The polyhydroxy compound used as the sensitivity enhancer is preferably used 3 to 15 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the sensitivity enhancer is less than 3 parts by weight, the photosensitivity effect is insignificant, so that resolution, sensitivity, and the like are insufficient. When the sensitivity enhancer is more than 15 parts by weight, the sensitivity is increased and the window process margin is narrowed in the process.

In addition, the photoresist layer 20 of the present invention may further include a release agent in order to improve the release property of the support film after lamination in addition to the above components. Preferred examples of the release agent include silicone resins, fluororesins, olefin resins, waxes and the like. Especially preferred among these are fluororesins having a viscosity in the range of about 1,000 to 10,000 cps.

The content of the release agent is preferably in the range of about 0.5 to 4 parts by weight based on 100 parts by weight of the alkali-soluble resin.

When the support film 10 is a stretched polypropylene (OPP) film, the stretched polypropylene (OPP) film does not need to add a release agent to the positive photoresist layer because it has excellent release property due to its hydrophobicity.

However, when the support film 10 is a polyethylene terephthalate (PET) film, it is preferable to add a release agent to the positive type photoresist layer because the PET film has poor releasability due to its hydrophilicity.

In addition to the composition of the above-mentioned constituents, the photoresist layer according to the present invention may be any conventionally known components used in conventional photoresist resin compositions such as leveling agents, fillers, pigments, dyes, surfactants and the like. Or additives.

In the method of forming the positive photoresist layer on the support film, a composition mixed with the solvent by a coating method such as a roller, a roll coater, a meyer rod, gravure, and a spray, which is generally used, may be used. It is performed by coating onto a phase and drying to volatilize the solvent in the composition. You may heat-harden the apply | coated composition as needed.

Moreover, the positive photoresist film of the present invention prepared above may further include a protective layer on top of the positive photoresist layer, and the protective layer may be a positive photoresist resin layer from air blocking and foreign substances. As a role of protecting the film, it is preferably formed of a polyethylene film, a polyethylene terephthalate film, a polypropylene film, or the like, and the thickness thereof is more preferably 15 to 30 μm.

On the other hand, the method of forming a pattern using the photoresist resin film of this invention,

(1) forming a photoresist resin film coated with a photoresist resin layer on a support prepared according to the present invention on a glass substrate, and peeling the support film of the photoresist resin film as necessary;

(2) directly irradiating ultraviolet light through or without a mask to obtain a desired pattern on the film; And

(3) In the case where the support film of the photoresist resin film is not peeled off, the film is peeled off, and then the positive photoresist film of the irradiated portion is removed by a development treatment to form a resist pattern film.

The developer for developing the positive photoresist resin film of the present invention is preferably 2.38% TMAH (tetramethylammonium hydroxide).

The step (1) is a step of forming a positive photoresist resin film by attaching a positive photoresist film on a substrate so that the photoresist resin layer is in contact with the support film. The support film does not need to be peeled off. In addition, it is not necessary to dry the photoresist film formed on the substrate.

In this way, a desired resist pattern film is formed by steps (1), (2) and (3).

The positive type photoresist resin film including the photoresist resin layer on the support film according to the present invention manufactured as described above has a resolution, sensitivity, etc. when the liquid composition is stored, which is a problem that occurs when the conventional liquid photoresist resin composition is used. By eliminating the problem of deterioration, the spin coating and the drying process necessary for application to the glass substrate, it is possible to eliminate the thickness variation problem, the bubble generation during drying, and to improve the yield. Can be significantly reduced.

In addition, the microcircuit pattern using the positive type photoresist resin film according to the present invention can form a pattern of a high resolution of 2 to 7㎛ similar to the conventional liquid positive type photoresist resin composition is fine, such as LCD, organic ELD It can be used for circuit formation.

Meanwhile, the process of manufacturing the silver (Ag) electrode of the PDP using the present invention will be described. First, the positive photoresist film of the present invention is laminated on a glass substrate on which a plating catalyst is deposited, and then a metal electrode is formed through pre-bake, exposure, development, and post-bake processes. After forming a photoresist layer on the remaining portions except for the portion to be formed, an electroless silver (Ag) plating process was performed to form a silver (Ag) electrode on the portion where the photoresist layer was not formed, and then the photoresist layer was peeled off. Next, a silver electrode may be directly formed on the glass substrate through a process of etching the plating catalyst deposited on the portion where the photoresist layer is separated.

At this time, in the post-heat treatment step, heat treatment is performed at 125 to 150 ° C. for 3 to 20 minutes so that crosslinking reaction of the thermosetting resin in the composition can occur, and it is carried out under strong alkali conditions of pH 11 to 12 so that silver (Ag) plating becomes dense.

Features and other advantages of the invention as described above will become more apparent from the description of the non-limiting examples described below. However, the following examples are only to be illustrated as specific embodiments of the present invention and should not be understood as limiting the scope of the present invention.

Example 1

Cresol novolac resins as alkali-soluble resins; 34 parts by weight of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride as a photosensitive compound based on 100 parts by weight of the alkali-soluble resin; 15 parts by weight of hexamethoxymethylmelamine as the thermosetting resin; 165 parts by weight of methyl ethyl ketone and 55 parts by weight of diethylene glycol monoethyl ether acetate; 2 parts by weight of isocyanate compound; 3.6 parts by weight of 2,3,4-trihydroxybenzophenone as a sensitivity enhancer; And 0.5 part by weight of a fluorine-based silicone resin as a release agent was prepared. The prepared solution was filtered through a 0.2 μm millipore teflon filter to remove insolubles. The resulting solution was applied on a polyethylene terephthalate (PET) film (thickness 19 mu m) to a thickness of 5 mu m to prepare a positive photoresist resin film. The positive photoresist resin film prepared as described above was laminated on a glass substrate on which palladium (Pd), a plating catalyst, was deposited, and then pre-bake, exposure, development, and post-bake processes. After forming a photoresist layer on the remaining portion except the portion where the metal electrode is to be formed, and then performing an electroless silver (Ag) plating process to form a silver (Ag) electrode on the portion where the photoresist layer is not formed, After peeling the photoresist layer from the substrate through a peeling process, a plating catalyst deposited on the portion where the photoresist layer was peeled off was etched to prepare a silver (Ag) electrode for PDP. At this time, the post-bake process was performed at 130 ° C. for 10 minutes, and the silver (Ag) plating process was performed under strong alkali conditions of pH 12. The results of evaluating various physical properties of the prepared positive photoresist film are shown in Table 2.

Example 2-Example 4 and Comparative Example 1

Except that the content of hexamethoxymethylmelamine, a thermosetting resin, the content of isocyanate compounds, the temperature and time of post-bake, and the pH of the silver (Ag) plating process were changed as shown in Table 1 In the same manner as in 1, a positive photoresist resin film and Ag (silver) electrode were prepared. The results of evaluating various physical properties of the prepared positive photoresist film are shown in Table 2.

Manufacture conditions division Hexamethoxymethylmelamine content (parts by weight) After heat treatment condition PH when silver (Ag) plating Isocyanate Content (parts by weight) Temperature (℃) Minutes Example 1 15 130 10 12 2 Example 2 10 125 15 11 One Example 3 20 140 10 11 3 Example 4 30 150 3 11 4 Comparative Example 1 0 100 10 12 0

Property results division Availability of silver (Ag) electrodes Physical properties of photoresist resin film Sensitivity (mJ / cm 3) Resolution (μm) Example 1 possible 120 4.5 Example 2 possible 120 5.0 Example 3 possible 120 5.0 Example 4 possible 120 5.0 Comparative Example 1 impossible 120 5.0

In the case of Comparative Example 1, the positive photoresist portion was peeled off during the silver (Ag) plating process, so that silver (Ag) electrode production was virtually impossible.

Properties of Table 2 were evaluated by the following method.

[Sensitivity evaluation]

After exposing the laminated substrate by the exposure amount, it was developed for 60 seconds with a 2.38% by mass TMAH aqueous solution at room temperature, washed with water for 30 seconds and dried, and the exposure amount was measured through an optical microscope.

[Resolution evaluation]

The prepared film was laminated at a lamination speed of 2.0 m / min, a temperature of 110 ° C., a heating roll pressure of 10 to 90 psi, and then irradiated with ultraviolet light using a photomask, and then peeled off the PET film as a support film, and developed in a 2.38% TMAH alkaline developer. In addition, the unexposed portion remained to form a circuit, and the resolution was observed with an electron microscope.

The present invention is excellent in photosensitivity, development contrast, sensitivity and resolution, and also has excellent alkali resistance and plating resistance, so that the metal electrode such as silver (Ag) electrode for PDP can be applied to a process for producing a metal electrode under strong alkali conditions. Do.

In addition, the present invention is excellent in adhesion with the plating catalyst, and is useful for directly forming a metal electrode on an insulating substrate on which the plating catalyst is deposited.

Claims (15)

A support film; A photoresist layer on the support film; And the photoresist layer comprises an alkali soluble resin, a photosensitive compound, a thermosetting resin, a solvent, and an isocyanate-based compound. According to claim 1, The photoresist layer is based on 100 parts by weight of the alkali-soluble resin 30 to 80 parts by weight of the photosensitive compound, 10 to 30 parts by weight of the thermosetting resin, 190 to 250 parts by weight of the solvent, isocyanate compound 0.5 to 3 A positive type photoresist film comprising a weight part. The positive type photoresist film of claim 1 or 2, wherein the thermosetting resin is a methoxymethylmelamine-based resin. The positive type photoresist film of claim 3, wherein the methoxymethylmelamine-based resin is a hexamethoxymethylmelamine-based resin. The positive type photoresist film of claim 1, wherein the photoresist layer has a thickness of 10 μm or less. The positive type photoresist film of claim 1, wherein the support film has a thickness in a range of about 15 to 50 μm. The positive type photoresist film of claim 1 or 2, wherein the alkali-soluble resin is a cresol novolac resin. The positive type photoresist film according to claim 1 or 2, wherein the photosensitive compound is a diazide photosensitive compound. The method of claim 8, wherein the diazide photosensitive compound is 2,3,4,4-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-sulfonate, 2,3,4-trihydroxybenzo Phenone-1,2-naphthoquinonediazide-5-sulfonate and (1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl ] Benzene) -1,2-naphthoquinonediazide-5-sulfonate The positive type photoresist film characterized by the above-mentioned. 8. The positive type photoresist film of claim 7, wherein the cresol novolac resin has a weight average molecular weight (GPC) of 2,000 to 30,000. The positive type photoresist film of claim 7, wherein the cresol novolac resin has a meta / para cresol content of 4: 6 to 6: 4 by weight. The cresol novolac resin according to claim 7, wherein the cresol novolac resin (i) has a cresol novolac resin having a weight average molecular weight (GPC basis) of 8,000 to 30,000 and (ii) a cresol novolac having a weight average molecular weight (GPC basis) 2,000 to 8,000. A positive photoresist film, wherein the resin is a resin mixed in a ratio of 7: 3 to 9: 1. The method of claim 1, wherein the support film is polyethylene terephthalate, polyethylene naphthalate, polycarbonate, ethylene vinyl acetate, ethylene vinyl alcohol, polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polystyrene, acrylonitrile / butadiene / styrene Positive type photoresist film, characterized in that consisting of one selected from the group consisting of epoxy, polyethylene, polypropylene and stretched polypropylene. The positive type photoresist film of claim 1, wherein the photoresist layer further comprises a solvent having a boiling point of 100 ° C. or higher. 15. The positive type according to claim 14, wherein the solvent is at least one selected from the group consisting of ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and propylene glycol monoethyl ether acetate. Photoresist film.

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