KR101291935B1 - Film type transfer material - Google Patents

Abstract

The present invention is a support film; A film type photodegradable transfer material comprising a photoresist layer containing an alkali-soluble resin, a diazide photosensitive compound, and a polyalkylene glycol, wherein the photodegradable composition is used as a photoresist layer to produce a film transfer material. Provided is a film type photodegradable transfer material free of chipping.

Description

Film type transferable material {Film type transfer material}

The present invention relates to a film type photodegradable transfer material, also known as a positive dry film photoresist.

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.

In recent years, the TFT-LCD manufacturing method using the liquid photoresist composition has become more complicated and difficult as the substrates have become larger in size and problems related to the liquid photoresist composition are more highlighted. Positive type liquid photoresist has problems such as poor resolution and sensitivity due to precipitation phenomenon during storage, and residues on the coating surface, resulting in poor pattern shape.

For example, as disclosed in Japanese Patent Laid-Open No. 3-249654, an alkali-soluble novolac resin and a substance containing 1,2-naphthoquinone diazido-4-sulfonic acid ester and a substance containing an acid-decomposable group as a photoacid generator For compositions containing alkali-soluble novolac resins and 1,2-naphthoquinonediazido-4-sulfonic acid polyhydroxybenzophenone esters, acid-decomposable groups, as disclosed in Japanese Patent Application Laid-Open No. 6-202320 In storage, insoluble matters are generated to reduce resolution and sensitivity, as well as residues on the coating surface, such that the pattern is not well formed.

As another example of the related art, US Pat. No. 3,666,473 discloses the use of a mixture of two phenolformaldehyde novolak resins and a typical photosensitive compound. U.S. Patent No. 4,115,128 discloses a technique for adding organic acid cyclic anhydrides to phenolic resins and naphthoquinone diazide photosensitizers to improve photosensitivity. The use of PGMEA as a solvent and a novolak resin and o-quinonediazide photosensitive compound for improving is disclosed. In addition, Japanese Patent No. 189,739 discloses the use of a method of treating a novolak resin to increase resolution and heat resistance, and the above contents are well known to those skilled in the art.

In addition, expensive photoresist materials are lost when spin coating a liquid photoresist onto a semiconductor substrate. Resist spin coating machines are quite expensive and in addition to spin coating time and maintenance. Filtration when using photoresist is also an expensive process. The loss of photoresist at any point in the spin coating process also accounts for a large proportion of the photoresist cost.

Due to the disadvantages of the conventional positive liquid photoresist, the development of a positive dry film resist is required.

Meanwhile, conventional dry film photoresist technology was first developed in the 1960s when liquid negative photoresists were adapted to dry film technology for the production of large and low resolution devices such as printed circuit board (PCB) patterns. However, the low resolution of these negative dry film resists has hampered the application of dry film technology to high resolution applications such as ICs and LCDs.

As a result, when the conventional liquid positive photoresist composition is used to form fine patterns such as LCD and organic ELD, the thickness variation, smoothness, deflection, entanglement, bubble generation, coating loss, etc. of the coating layer due to the essential steps of spin coating, etc. It overcomes the problems of high resolution, excellent line width control characteristics, high heat resistance, high sensitivity, high residual film ratio, high dry etching resistance, high development, etc., and new photosensitivity that can be applied to micro processing of LCD, organic ELD, etc. Development of resin products is urgently required.

In one embodiment of the present invention is to provide a film type to more efficiently utilize a photodegradable composition that can express high resolution and adhesion.

In one embodiment of the present invention to provide a film-type photodegradable transfer material that does not collapse the film in the production of a film-type transfer material using a photodegradable composition as a photoresist layer.

In one embodiment of the present invention; And a photoresist layer comprising an alkali-soluble resin, a diazide-based photosensitive compound, and a polyalkylene glycol.

According to a preferred embodiment, the polyalkylene glycol may have a weight average molecular weight of 100 to 100,000.

According to another preferred embodiment, the polyalkylene glycol may be polyethylene glycol or polypropylene glycol.

In the film type photodegradable transfer material according to an embodiment of the present invention, the polyalkylene glycol may be included so that the glass transition temperature of the photoresist layer is -20 to 10 ° C.

The film type photodegradable transfer material according to another embodiment of the present invention may further include a developable acrylic polymer in the photoresist layer.

In the film type photodegradable transfer material according to an embodiment of the present invention, the alkali-soluble resin may be a novolak resin.

In the film type photodegradable transfer material according to an embodiment of the present invention, the alkali-soluble resin may be a cresol novolac resin.

In this case, the cresol novolak resin may have a weight average molecular weight (when measured by GPC) of 2,000 to 30,000.

In this case, the cresol novolak resin may be a mixture of meta / para cresol in a ratio of 4: 6 to 6: 4 by weight.

In addition, cresol novolac resins have cresol novolac resins having a weight average molecular weight (measured by GPC) of 8,000 to 30,000 and cresol novolac resins having a weight average molecular weight (measured by GPC) of 2,000 to 8,000. It may be a resin mixed in a weight ratio of 3: 3 to 9: 1.

In the film type photodegradable transfer material according to an embodiment of the present invention, the diazide photosensitive compound is 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5- Sulfonate, 2,3,4-trihydroxybenzophenone-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 the film type photodegradable transfer material according to an embodiment of the present invention, the photoresist layer is 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone and 1- One or more sensitivity enhancers selected from [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene.

The film type photodegradable transfer material according to the embodiment of the present invention may include a protective layer formed on the photoresist layer. In this case, the protective layer may have a thickness of 15 to 30 μm.

According to one embodiment of the present invention, a photodegradable composition capable of expressing high resolution and adhesion may be more easily provided in a film form. In addition, it is possible to provide a photodegradable film transfer material which is easy to be distributed on a roll because there is no film chipping or edge fusion.

Hereinafter, the present invention will be described in detail.

As described above, the positive liquid photoresist composition is generally required to be filmed for various reasons. In general, the positive liquid photoresist composition includes a component causing a photolysis reaction, usually a diazide-based photosensitive compound, which is liable to break the film. It is a component that gives a property.

In this regard, production of a film type photodegradable transfer material using a positive liquid photoresist composition has not been actively performed.

Thus one embodiment of the present invention is a support film; And a photoresist layer comprising an alkali-soluble resin, a diazide photosensitive compound, and a polyalkylene glycol.

In the case where the polyalkylene glycol is included in the photoresist layer, flexibility can be imparted to the film after applying the photoresist layer crude liquid onto the support film. Thereby, film-forming can be made easy and the process on a roll can be made easy.

Preferably, the polyalkylene glycol may have a weight average molecular weight of 100 to 100,000, but if the weight average molecular weight is too small, it may be difficult for the polyalkylene glycol to remain in the photoresist layer and the weight average molecular weight may be too high. It may impair its properties and degrade its solubility.

Specific examples of such polyalkylene glycols include polyethylene glycol or polypropylene glycol, but are not limited thereto.

The content of the polyalkylene glycol is not particularly limited, but it is advantageous to include the glass transition temperature of the photoresist layer in a content of -40 ° C to 40 ° C in consideration of weight average molecular weight and the like.

More preferably, the glass transition temperature of the photoresist layer includes polyalkylene glycol in a content of -20 to 10 ° C, most preferably -10 to 0 ° C.

In the above and the following description, the glass transition temperature of the photoresist layer may be defined as a value measured by DSC-60, which is a DSC (Differential Scanning Calorimeter) manufactured by SHIMADZU.

On the other hand, if the polyalkylene glycol content is increased, the glass transition temperature may be controlled by mixing the developable acrylic polymer. Here, the "developable acrylic polymer" may be understood as an acrylic acid polymer having acrylic acid, and specific examples thereof include polyacrylic acid, polymethacrylic acid, or a copolymer thereof.

In the film type photodegradable transfer material of the present invention, the photoresist layer may use a novolak resin as the alkali-soluble resin, and more preferably may include a cresol novolak resin.

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

The phenols are not particularly limited, and phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3, 5-xylenol, 2,3,5-trimethylphenol-xylenol, 4-t-butylphenol, 2-t-butylphenol, 3-t-butylphenol, 4-methyl-2-t-butylphenol Monovalent phenols; And 2-naphthol, 1,3-dihydroxy naphthalene, 1,7-dihydroxy naphthalene, 1,5-dihydroxy naphthalene, resorcinol, pyrocatechol, hydroquinone, bisphenol A, fluoroglucinol, Polyhydric phenols, such as a pyrogallol, etc. are mentioned, These can be selected individually and can be used 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, alpha or beta-phenyl propylaldehyde, o-, m- or p-hydroxy Benzaldehyde, glutaraldehyde, terephthalaldehyde, etc. are mentioned, It can be used individually or in combination of 2 or more types.

The cresol novolak resin preferably has a weight average molecular weight (based on GPC measurement) of 2,000 to 30,000, and the cresol novolak resin may have different physical properties such as photosensitivity and residual film ratio depending on the content ratio of meta / para cresol. Therefore, it may be preferable that the meta / para cresol content is mixed in a ratio of 4: 6 to 6: 4 by weight.

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

The cresol novolak resin may be used alone of the cresol novolak resin having a meta / para cresol content of 4: 6 to 6: 4 by weight, and more preferably, different resins may be mixed. In this case, it is preferable to use the cresol novolak resin in a ratio of cresol novolac resin having a weight average molecular weight of 8,000 to 30,000 and a novolak resin 7: 3 to 9: 1 having a weight average molecular weight of 2,000 to 8,000. .

"Weight average molecular weight" above and below is defined in terms of the polystyrene equivalent, as determined by gel permeation chromatography (GPC).

In the composition of the photoresist layer, the diazide-based photosensitive compound acts as a dissolution inhibitor to reduce the solubility of alkali-soluble resin in alkali, and when irradiated with light, the diazide-based photosensitive compound is converted into alkali-soluble material to increase alkali solubility of alkali-soluble resin. do. As such, due to the change in solubility due to light irradiation, the exposed portion of the film type photodegradable transfer material of the present invention is developed.

A diazide photosensitive compound can be synthesized by esterification of a polyhydroxy compound and a quinone diazide sulfonic acid compound. The esterification reaction for obtaining a diazide photosensitive compound is performed by dioxane, acetone, tetrahydrofuran, methyl ethyl ketone, N-methylpyrrolidone, chloroform, triethylamine, and polyhydroxy compound and quinone diazide sulfonic acid compound. A basic catalyst such as N-methylmorpholine, N-methylpiperazine or 4-dimethylaminopyridine can be added dropwise and condensed, and then the obtained product can be washed, purified and dried.

The quinone diazide sulfonic acid compound is, for example, 1,2-benzoquinone diazide-4-sulfonic acid, 1,2-naphthoquinone diazide-4-sulfonic acid, 1,2-benzoquinone diazide-5-sulfonic acid and O-quinone diazide sulfonic acid compounds such as 1,2-naphthoquinone diazide-5-sulfone phase, other quinone diazide sulfonic acid derivatives, and the like.

The quinonediazide sulfonic acid compound has a function as a dissolution inhibiting agent which lowers the solubility of alkali-soluble resin in alkali by itself. However, it is decomposed to be alkali-soluble at the time of exposure and thereby rather has the property of promoting dissolution of alkali-soluble 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 ; Tetrahydroxy benzophene such as 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxy benzophenone, and 2,3,4,5-tetrahydroxybenzophenone Rice field; 2,2 ', 3,4,4'-pentahydroxy benzophenone, 2,2', 3,4,5-pentahydroxy benzophenone ed pentahydroxy benzophenone; Hexahydroxy benzophenones such as 2,3,3 ', 4,4', 5'-hexahydroxybenzophenone and 2,2 ', 3,3', 4,5'-hexahydroxy benzophenone; Gallic acid alkyl esters; Oxyflavones etc. are mentioned.

Specific examples of the diazide photosensitive compound obtained from these include 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonate, 2,3,4-tri Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate and (1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxy Phenyl) ethyl] benzene) 1, 2- naphthoquinone diazide-5-sulfonate 1 or more types chosen are mentioned.

The diazide-based photosensitive compound may be advantageously 30 to 80 parts by weight based on 100 parts by weight of the alkali-soluble resin in the photoresist layer composition in view of developability or solubility.

Meanwhile, in the film type photodegradable transfer material according to the embodiment of the present invention, the photoresist layer may include a sensitivity enhancer, which is intended to improve sensitivity. Examples thereof include 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone and 1- [1- (4-hydroxyphenyl) isopropyl] -4- [ 1,1-bis (4-hydroxyphenyl) ethyl] benzene.

When the sensitivity enhancer is included in an amount of 3 to 15 parts by weight based on 100 parts by weight of the alkali-soluble resin, it may be advantageous in terms of improving the photosensitive effect and margin of the window process.

In addition, the photoresist layer may include other components or additives such as a leveling agent, a filler, and an antioxidant.

When a composition comprising such an alkali-soluble resin, a diazide-based photosensitive compound, a polyalkylene glycol, and the like is dispersed in a predetermined amount of a solvent to be prepared and then coated on a support film and dried, a film type according to an embodiment of the present invention. A photodegradable transfer material can be obtained.

Examples of the solvent include ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, acetone, methyl ethyl ketone, ethyl alcohol, methyl alcohol, propyl alcohol, iso And at least one selected from the group consisting of propyl alcohol, benzene, toluene, cyclopentanone, cyclohexanone, ethylene glycol, xylene, ethylene glycol monoethyl ether and diethylene glycol monoethyl ether.

The support film of the present invention should have suitable physical properties for the positive dry film photoresist. 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 may be transparent enough to allow light to pass through the support film to irradiate the photoresist layer. The support film preferably has a thickness in the range of about 10 to 50 μm, preferably about 15 to 50 μm, more preferably about 15 to 25 μm, to serve as a framework for supporting the shape of the positive type photoresist resin film. It can have a thickness in the range.

In the present invention, a photoresist layer is prepared by mixing a composition containing an alkali-soluble resin, a diazide photosensitive compound, a polyalkylene glycol, a sensitivity enhancer, and the like as described above with a predetermined amount of a solvent. The mixture is applied to the support film to a thickness of 5 to 100㎛. The method of forming a photoresist layer on the support film is a coating method of the composition mixed with the solvent on the support film by a coating method such as roller, roll coater, meyer rod, gravure, spray, etc. which are generally used. And drying to volatilize the solvent in the composition. You may heat-harden the apply | coated composition as needed.

The positive photoresist film according to one embodiment of the present invention is usually attached to the substrate surface by lamination or the like and then irradiated with light without peeling the support film and then peeled off the support film or after the lamination, the support film is peeled off. After the light irradiation, it can be used to select the method of light irradiation. However, irradiation can be made before or after peeling a support film.

Furthermore, the positive type photoresist film of the present invention may further include a protective layer on top of the photoresist layer, and the protective layer serves to protect the photoresist layer from air blocking and foreign matter. As to carry out, it is preferable that it is formed of a polyethylene film, polyethylene terephthalate film, 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 the present invention comprises (I) forming a dry film photoresist on a glass substrate such that the photoresist layer of the dry film photoresist produced in accordance with the present invention is in contact with it. Bar, if necessary, peeling the support film from the photoresist resin film; (II) directly irradiating ultraviolet light through or without a mask to obtain a desired pattern on the film; And (III) in the case where the support film is not peeled from the photoresist resin film, after the peeling of the support film, a photoresist layer of the irradiated portion is removed by a development treatment to form a resist pattern film.

The said step (I) is a step of forming a positive photoresist resin film by adhering the photoresist layer of a positive dry film photoresist on a board | substrate so that it may contact. At this time, the support film of the dry film photoresist does not need to be peeled off. In addition, it is not necessary to dry the photoresist film formed on the substrate.

If necessary, a baking process is required before or after step (II) as necessary to strengthen the binding force with the substrate so that the resist pattern film is not washed off when developing in step (III). In more detail, if the positive type photoresist resin film is formed on the substrate before the step (II), the support film is peeled from the photoresist resin film, and then heat treatment (Baking) is performed to enhance the binding force with the substrate. Alternatively, after the step (II), the support film of the photoresist resin film is peeled off, and heat treatment (Baking) may be performed to enhance the binding strength with the substrate. Alternatively, after performing step (II), the support film may be peeled from the photoresist resin, and the peeled film may be heat treated to enhance adhesion to the substrate. That is, the heat treatment step may be variously repeated according to the requirements of the photoresist film, the complexity of the solvent system, and the boiling point.

In this way, a desired resist pattern film is formed by steps (I), (II) and (III).

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

The positive type photoresist film including the photoresist layer on the support film according to the present invention prepared as described above is deteriorated in the resolution, sensitivity, etc. of the liquid composition, which is a problem that occurs when the conventional liquid photoresist resin composition is used. By eliminating the problem, spin coating and drying process, which are necessary when applying to the glass substrate, it is possible to eliminate the thickness variation problem and the bubble generation during drying, and to improve the yield. It allows you to reduce it considerably.

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.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely illustrative of one embodiment of the present invention and the scope of the present invention is not limited by the following examples.

In the above and the following description, the glass transition temperature of the photoresist layer is a value measured by DSC-60 which is a DSC (Differential Scanning Calorimeter) manufactured by SHIMADZU.

Example 1

Cresol novolac resin (cresol formaldehyde novolak resin, meta / para cresol content of 4: 6 by weight, weight average molecular weight of 8,000 cresol novolac resin and cresol novolac of 2,000 weight average molecular weight as alkali-soluble resin Cresol novolac resins having a volac resin mixed at a ratio of 7: 3); 34 parts by weight of 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate as a photosensitive compound based on 100 parts by weight of the alkali-soluble resin; 3.6 parts by weight of 2,3,4-trihydroxybenzophenone as a sensitivity enhancer; 165 parts by weight of methylethyl ketone as low boiling solvent; 50 parts by weight of polyalkylene glycol (polyethylene glycol having Mw = 100); 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 of 19 μm) to a thickness of 5 μm to form a photoresist layer (photoresist layer Tg = −19 ° C.). A polyethylene film protective layer was applied to the photoresist layer having a thickness of 23 µm to prepare a positive photoresist resin film.

Example 2

Cresol novolac resin (cresol formaldehyde novolak resin, meta / para cresol content of 4: 6 by weight, weight average molecular weight of 8,000 cresol novolac resin and cresol novolac of 2,000 weight average molecular weight as alkali-soluble resin Cresol novolac resins having a volac resin mixed at a ratio of 7: 3); 34 parts by weight of 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate as a photosensitive compound based on 100 parts by weight of the alkali-soluble resin; 3.6 parts by weight of 2,3,4-trihydroxybenzophenone as a sensitivity enhancer; 165 parts by weight of methylethyl ketone as low boiling solvent; 40 parts by weight of polyalkylene glycol (polypropylene glycol having Mw = 1300); 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 form a photoresist layer (photoresist layer Tg = 3 deg. C). A polyethylene film protective layer was applied to the photoresist layer having a thickness of 23 µm to prepare a positive photoresist resin film.

Example 3

Cresol novolac resin (cresol formaldehyde novolak resin, meta / para cresol content of 4: 6 by weight, cresol novolac resin with weight average molecular weight of 8,000, and cresol with weight average molecular weight of 2,000 as alkali-soluble resin Cresol novolac resin in which novolac resin is mixed at a ratio of 7: 3); 34 parts by weight of 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate as a photosensitive compound based on 100 parts by weight of the alkali-soluble resin; 3.6 parts by weight of 2,3,4-trihydroxybenzophenone as a sensitivity enhancer; 165 parts by weight of methylethyl ketone as low boiling solvent; 40 parts by weight of developable acrylic polymer (butyl acrylate: acrylic acid: methyl acrylate: styrene is copolymerized in a weight ratio of 3: 1: 1: 1, an acrylic polymer having a weight average molecular weight of 60000), and 50 parts by weight of polyalkylene glycol ( Polyethylene glycol with Mw = 400); 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 form a photoresist layer (photoresist layer Tg = -11 deg. C). A polyethylene film protective layer was applied to the photoresist layer having a thickness of 23 µm to prepare a positive photoresist resin film.

Example 4

Cresol novolac resin (cresol formaldehyde novolak resin, meta / para cresol content of 4: 6 by weight, weight average molecular weight of 8,000 cresol novolac resin and cresol novolac of 2,000 weight average molecular weight as alkali-soluble resin Cresol novolac resins having a volac resin mixed at a ratio of 7: 3); 34 parts by weight of 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate as a photosensitive compound based on 100 parts by weight of the alkali-soluble resin; 3.6 parts by weight of 2,3,4-trihydroxybenzophenone as a sensitivity enhancer; 165 parts by weight of methylethyl ketone as low boiling solvent; 40 parts by weight of developable acrylic polymer (butyl acrylate: acrylic acid: methyl acrylate: styrene is copolymerized in a weight ratio of 3: 1: 1: 1, an acrylic polymer having a weight average molecular weight of 60000), and 50 parts by weight of polyalkylene glycol ( Polyethylene glycol with Mw = 800); 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 form a photoresist layer (photoresist layer Tg = -7 deg. C). A polyethylene film protective layer was applied to the photoresist layer having a thickness of 23 µm to prepare a positive photoresist resin film.

Example 5

Cresol novolac resin (cresol formaldehyde novolak resin, meta / para cresol content of 4: 6 by weight, weight average molecular weight of 8,000 cresol novolac resin and cresol novolac of 2,000 weight average molecular weight as alkali-soluble resin Cresol novolac resins having a volac resin mixed at a ratio of 7: 3); 34 parts by weight of 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate as a photosensitive compound based on 100 parts by weight of the alkali-soluble resin; 3.6 parts by weight of 2,3,4-trihydroxybenzophenone as a sensitivity enhancer; 165 parts by weight of methylethyl ketone as low boiling solvent; 40 parts by weight of developable acrylic polymer (butyl acrylate: acrylic acid: methyl acrylate: styrene is copolymerized in a weight ratio of 3: 1: 1: 1, an acrylic polymer having a weight average molecular weight of 60000), and 50 parts by weight of polyalkylene glycol ( Polyethylene glycol with Mw = 2000); 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 of 19 μm) to a thickness of 5 μm to form a photoresist layer (photoresist layer Tg = 5 ° C.). A polyethylene film protective layer was applied to the photoresist layer having a thickness of 23 µm to prepare a positive photoresist resin film.

Example 6

Cresol novolac resin (cresol formaldehyde novolak resin, meta / para cresol content of 4: 6 by weight, weight average molecular weight of 8,000 cresol novolac resin and cresol novolac of 2,000 weight average molecular weight as alkali-soluble resin Cresol novolac resins having a volac resin mixed at a ratio of 7: 3); 34 parts by weight of 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate as a photosensitive compound based on 100 parts by weight of the alkali-soluble resin; 3.6 parts by weight of 2,3,4-trihydroxybenzophenone as a sensitivity enhancer; 165 parts by weight of methylethyl ketone as low boiling solvent; 40 parts by weight of polyalkylene glycol (polypropylene glycol having Mw = 425); 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 of 19 μm) to a thickness of 5 μm to form a photoresist layer (photoresist layer Tg = −8 ° C.). A polyethylene film protective layer was applied to the photoresist layer having a thickness of 23 µm to prepare a positive photoresist resin film.

Example 7

Cresol novolac resin (cresol formaldehyde novolak resin, meta / para cresol content of 4: 6 by weight, weight average molecular weight of 8,000 cresol novolac resin and cresol novolac of 2,000 weight average molecular weight as alkali-soluble resin Cresol novolac resins having a volac resin mixed at a ratio of 7: 3); 34 parts by weight of 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate as a photosensitive compound based on 100 parts by weight of the alkali-soluble resin; 3.6 parts by weight of 2,3,4-trihydroxybenzophenone as a sensitivity enhancer; 165 parts by weight of methylethyl ketone as low boiling solvent; 40 parts by weight of polyalkylene glycol (polypropylene glycol having Mw = 725); 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 form a photoresist layer (photoresist layer Tg = -2 deg. C). A polyethylene film protective layer was applied to the photoresist layer having a thickness of 23 µm to prepare a positive photoresist resin film.

Example 8

Cresol novolac resin (cresol formaldehyde novolak resin, meta / para cresol content of 4: 6 by weight, weight average molecular weight of 8,000 cresol novolac resin and cresol novolac of 2,000 weight average molecular weight as alkali-soluble resin Cresol novolac resins having a volac resin mixed at a ratio of 7: 3); 34 parts by weight of 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate as a photosensitive compound based on 100 parts by weight of the alkali-soluble resin; 3.6 parts by weight of 2,3,4-trihydroxybenzophenone as a sensitivity enhancer; 165 parts by weight of methylethyl ketone as low boiling solvent; 40 parts by weight of polyalkylene glycol (polypropylene glycol having Mw = 3500); 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 form a photoresist layer (photoresist layer Tg = 8 deg. C). A polyethylene film protective layer was applied to the photoresist layer having a thickness of 23 µm to prepare a positive photoresist resin film.

Example One 2 3 4 5 6 7 8
Polyalkylene glycol PEG ○ - ○ ○ ○ PPG - ○ ○ ○ ○ Mw 100 1300 400 800 2000 425 725 3500 content
(Parts by weight relative to 100 parts by weight of alkali-soluble polymer)
50
40
50
50
50
40
40
40 Developable Acrylic Polymer Content
(Parts by weight relative to 100 parts by weight of alkali-soluble polymer)
-
-
40
40
40
-
-
- Photoresist Layer Tg (℃) -19 3 -11 -7 5 -8 -2 8

Comparative Example 1

Cresol novolac resin (cresol formaldehyde novolak resin, meta / para cresol content of 4: 6 by weight, weight average molecular weight of 8,000 cresol novolac resin and cresol novolac of 2,000 weight average molecular weight as alkali-soluble resin Cresol novolac resins having a volac resin mixed at a ratio of 7: 3); 33.8 parts by weight of 1,2-naphthoquinone-2-diazide-4-sulfonic acid polyhydroxybenzophenone ester as a photosensitive compound relative to 100 parts by weight of alkali-soluble resin; 407.0 parts by weight of propylene glycol monoethyl ether acetate as a solvent; And 5.5 parts by weight of 2,2 ', 4,4'-tetrahydroxybenzophenone as a sensitivity enhancer, 2.2 parts by weight of dye are added thereto, and the mixture is stirred for 2 hours to form a photoresist resin layer. The solution was prepared.

The prepared photoresist resin composition was applied to a 10 cm × 10 cm glass substrate by spin coating to obtain a thickness of 1.5 μm (photoresist layer Tg = 105 C). The coated substrate was exposed to ultraviolet light using a photomask, developed in a 2.38% TMAH alkaline developer for 60 seconds, washed, and dried for 30 seconds to form a fine pattern.

On the other hand, the following items were evaluated.

[Film Release Evaluation]

The positive film type transfer material produced according to the Example was laminated on a glass substrate coated with ITO at a depth of 2000 mm and a width of 100 × 100 mm 2 at a speed of 2.0 m / min, a temperature of 110 ° C., and a heating roll pressure of 10 to 90 psi. After that, the support film was separated from the positive photoresist layer. At this time, the release property was evaluated by UTM (Unversal Test Maccine; Instron Co., Ltd.), and the peel strength measured in the UTM at release was measured.

As a result, the peel strength is indicated by O when the range is 0.001 to 0.01 kg / 100 × 100 mm 2, and by X when 0.01 kg / 100 × 100 mm 2 or more.

[Sensitivity evaluation]

Each film-type transfer material was laminated on a glass substrate coated with ITO at a thickness of 2000Å and a width of 100 × 100 mm2 at a speed of 2.0 m / min, a temperature of 110 ° C., and a heating roll pressure of 10 to 90 psi. Peel and prebaked at 100 degreeC.

After exposure by exposure amount with a contact type exposure machine, it was developed for 60 seconds in a 2.38% by weight TMAH aqueous solution at room temperature for 60 seconds (development for 64 seconds in Example 1-3), washed with water for 30 seconds and dried. The exposure amount required to form a fine pattern of Line / Space 1/1 was measured. At this time, the size of the fine pattern was performed while observing through an optical microscope.

[Resolution evaluation]

The unexposed portion remained to form a circuit, and the resolution was observed with an electron microscope.

[Film formability evaluation]

After the resin composition was applied to the support film, the film formation was visually observed and evaluated.

The above evaluation results are shown in Table 2 below.

division Sensitivity (mJ / cm ³ ) Resolution (탆) Film formability Film release
(kg / 100 × 100㎡) Example 1 65.1 5.1 ○ ○ Example 2 63.2 4.2 ○ ○ Example 3 61.5 4.3 ○ ○ Example 4 64.0 4.9 ○ ○ Example 5 72.7 6.2 ○ ○ Example 6 65.1 5.5 ○ ○ Example 7 63.2 4.5 ○ ○ Example 8 71.5 6.8 ○ ○ Comparative Example 1 45.5 4.1 × ×

From the results in Table 2, it can be seen that in the case of Examples, the film formability is excellent, and after laminating such a film transfer material on a substrate, it is easy to release the support film from the photoresist layer. In addition, in the case of forming a pattern using the film-type transfer material of the embodiment, in the case of forming the pattern after applying the spin coating method on the substrate using the liquid photoresist composition in terms of sensitivity and resolution (Comparative Example 1) It can be seen that the physical properties are equivalent or substantially better than that. In addition, the photoresist resin composition of the comparative example 1 does not form a film on a support film.

The above detailed description and embodiments are merely illustrative of the ideal methods and principles of the present invention, and those skilled in the art may make modifications and further modifications without departing from the spirit and scope of the present invention and thus are attached. It is readily understood that it is limited only by the scope of the claims.

Claims (15)

Support film; And A photoresist layer comprising an alkali-soluble resin, a diazide photosensitive compound, and a polyalkylene glycol having a weight average molecular weight of 100 to 100,000; The polyalkylene glycol is a film type photodegradable transfer material, characterized in that it is contained so that the glass transition temperature of the photoresist layer -20 to 10 ℃. delete The film type photodegradable transfer material according to claim 1, wherein the polyalkylene glycol is polyethylene glycol or polypropylene glycol. delete The film type photodegradable transfer material according to claim 1, wherein the photoresist layer further comprises a developable acrylic polymer. The film type photodegradable transfer material according to claim 1, wherein the alkali-soluble resin is a novolak resin. The film type photodegradable transfer material according to claim 1, wherein the alkali-soluble resin is a cresol novolac resin. The film type photodegradable transfer material according to claim 7, wherein the cresol novolac resin has a weight average molecular weight (as measured by GPC) of 2,000 to 30,000. The film type photodegradable transfer material according to claim 7, wherein the cresol novolac resin is mixed in a ratio of 4: 6 to 6: 4 by weight of meta / para cresol. 10. The cresol novolac resin according to claim 9, wherein the cresol novolac resin is a cresol novolac resin having a weight average molecular weight (measured by GPC) of 8,000 to 30,000, and a cresol having a weight average molecular weight (measured by GPC) of 2,000 to 8,000. A novolak resin is a film type photodegradable transfer material, characterized in that the resin is mixed in a weight ratio of 7: 3 to 9: 1. The method of claim 1, wherein the diazide photosensitive compound is 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonate, 2,3,4-trihydro Oxybenzophenone- 1,2-naphthoquinonediazide-5-sulfonate and (1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl ) Ethyl] benzene) -1,2-naphthoquinone diazide-5-sulfonate The film type photodegradable transfer material characterized by the above-mentioned. The photoresist layer of claim 1, wherein the photoresist layer is 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone and 1- [1- (4-hydroxyphenyl) iso Propyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene A film type photodegradable transfer material, characterized in that it comprises at least one sensitivity enhancer selected from benzene. The film type photodegradable transfer material according to claim 1, further comprising a protective layer formed on the photoresist layer. The film type photodegradable transfer material according to claim 13, wherein the protective layer is formed of any one selected from the group consisting of polyethylene film, polyethylene terephthalate film, and polypropylene film. The film type photodegradable transfer material according to claim 13, wherein the protective layer has a thickness of 15 to 30 mu m.