JPH05297587A - Sticky photoresist composition - Google Patents

Abstract

PURPOSE:To obtain a sticky photoresist compsn. capable of forming a high resolution resist pattern image by an integrated exposure system without using a stepper as a photoresist material capable of coating in the form of a thin single layer and having function to transfer and fix a metal mask, etc., on the surface. CONSTITUTION:This sticky photoresist compsn. has such surface stickiness of a coating film as to fix a mask pattern, forms a non-image area which can be removed by development under irradiation with active light and a nonsticky hardened image area and contains an acrylic oligomer having an acrylic or methacrylic terminal group and an org. polymer binder.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive photoresist composition which can be suitably used for producing a large area electrode circuit element substrate, and more specifically, it can be applied uniformly onto a processed substrate. Pattern is formed on the surface of the coating film.
It has an adhesive force to receive and fix the image mask as a transfer image. Through the transfer mask, it is possible to form an image in a large area by batch exposure, and the surface to be etched is exposed by the development process, and the etching resistance The present invention relates to a novel photoresist composition capable of forming a cured image area excellent in heat resistance.

[0002]

2. Description of the Related Art Recently, the demand for display devices using liquid crystals has increased in the display field, and needs for large-area devices such as wall-mounted televisions have also become strong.

Conventionally, in the production of an electrode circuit element substrate for a liquid crystal display device, a resist is applied on a processed substrate and a stepper is applied to the resist layer, as is found in the production of semiconductors, ICs, LSIs and the like. The desired resist image formation was carried out using this. However, in the image forming method on a resist using this stepper, when a large-area circuit element substrate such as a TFT-LCD is to be manufactured, the number of divided exposures is significantly increased, and as a result, the yield is significantly reduced. There was a problem. Further, not only the throughput but also the feasibility of the exposure apparatus itself is difficult.

Therefore, as a method for efficiently manufacturing a large-area circuit element substrate, a printing method has been proposed in which a resist image can be formed without using a stepper. (Electronic display EID 91-41 (1991)).

In this method, a pattern is formed on a conductive printing substrate by using a photosensitive resin (preparation of a printing plate), and a metal pattern is formed by an electrodeposition method using the pattern on this substrate. This metal thin film pattern is transferred onto the resist layer provided on the substrate to be etched to form a pattern without using a stepper.

The resist material used in this method is required to have a dimensionally stable film-forming property and a strong adhesive force capable of receiving and fixing the metal thin film pattern as a transfer mask. Further, by irradiation with actinic rays in the presence of a transfer mask, it is also required that the non-image portion that can be developed and removed and the image portion that can withstand etching processing can be formed with high resolution.

[0007]

However, conventional photoresist materials usually do not have surface tackiness at all, and a metal mask is transferred to the coating film surface,
The transfer mask cannot be fixed in a dimensionally stable manner. In order to solve this, it is possible to impart the transferability of the mask pattern by newly providing an adhesive layer on the photoresist layer, but it is possible to remove the adhesive layer uniformly during the development processing. There is a problem that it becomes difficult and the surface to be etched cannot be exposed with high precision, or even if the development processing is possible, the image resolution is lowered due to the two-layer structure.

On the other hand, when an ultraviolet curable adhesive or the like is used as a resist, there is a problem in that the film forming property of the coating film is insufficient and the mask pattern cannot be transferred accurately.

The problem to be solved by the present invention is that a uniform thin film can be coated on a processed substrate, and a sufficient film-forming property capable of withstanding the transfer pressure of the mask pattern and fixing of the transfer mask can be achieved. It is possible to form a coating film that has excellent surface adhesiveness, and, like conventional photoresists,
An object of the present invention is to provide an adhesive photoresist composition capable of forming a high-resolution image area having excellent etching resistance and a non-image area removable by a development process.

[0010]

As a result of intensive studies, the inventors of the present invention have solved the above problems.

That is, in order to solve the above-mentioned problems, the present invention has sufficient tackiness of the coating film surface to fix the mask pattern and is non-tacky with the non-image area which can be developed and removed by irradiation with actinic rays. A tacky photoresist composition for forming a cured image portion of (1) an acrylic or methacrylic end group-containing acrylic oligomer (hereinafter referred to as the first component), and (2) an organic polymer conjugate ( Hereinafter, referred to as a second component) is provided, and an adhesive photoresist composition is provided.

By the combination of these components, both the formation of a single-layer thin film resist layer, the acceptability of a mask pattern in the transfer process and the transfer mask holding suitability, which are indispensable as a printing type resist material, are satisfied, and etching is performed. A composition for forming a high resolution cured image having excellent durability is provided. Therefore, by forming the composition of the present invention as a thin film coating on a substrate to be etched, it becomes possible to perform resist patterning over a large area with high precision and quickly without using a stepper.

These components in the present invention are characterized by the following points.

The first component oligomer is a polymerizable compound containing an acrylic or methacrylic end group which can be polymerized by actinic rays, and serves as a component for imparting surface tackiness to a resist film before actinic ray irradiation, and for forming an image. It acts effectively as a crosslink density adjusting component, and need not be a single oligomer, but it is also possible to use two or more kinds of oligomers in combination.

The acrylic or methacrylic end group-containing acrylic oligomer used in the present invention is, for example,

(1) ethylene glycol diacrylate,
Glycerin triacrylate, polyacrylate, ethylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, polyethylene glycol dimethacrylate, 1,2,4-butanol trimethacrylate, trimethylol Ruetan triacrylate,
Pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate. Unsaturated esters of polyol such as dipentaerythritol polyacrylate, 1,3-propanediol diacrylate and 1,5-pentanediol dimethacrylate.

(2) Epoxy (meth) acrylate obtained by esterifying bisphenol A type epoxy resin with (meth) acrylic acid and optionally long chain fatty acid such as coconut oil fatty acid or its long chain fatty acid modified product, hydroxyl group An epoxy (meth) acrylate having a dibasic acid anhydride,
Epoxy (meth) acrylates such as tetrabasic acid dianhydride and epoxy (meth) acrylate having a carboxyl group obtained by adding trimellitic anhydride, and modified products thereof.

(3) British Patent No. 1,147,732 (JP-A-51-37193 and JP-A-51-1)
No. 38797), a terminal isocyanate compound obtained by previously reacting a diisocyanate compound with a polyol is added to a molecule obtained by further reacting β-hydroxyalkyl acrylate and / or methacrylate. An addition polymerizable compound having two or more acryloyloxy groups and / or methacryloyloxy groups.

(4) Dibasic acid such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, or head acid anhydride as described in JP-B-47-3262. A linear polyester compound obtained by ring-opening polymerization of an anhydride and glycidyl acrylate and / or glycidyl methacrylate and having a large number of pendant acrylyloxy groups and / or methacryloyloxy groups.

(5) A polyhydric alcohol having at least three esterifiable hydroxyl groups at adjacent carbon atoms as described in JP-B-47-23661, and acrylic acid and / or methacrylic acid. Polymerizable esters prepared by co-esterification with dicarboxylic acids selected from the group consisting of dicarboxylic acids and their anhydrides.

(6) British Patent No. 628,150,
U.S. Pat. No. 3,020,255 and monthly magazine "Macromolecules", Vol. 4, No. 5, 630-63.
Polyacryl (or polymethacryl) modified triazine resin obtained by reacting melamine or benzoguanamine with formaldehyde, methyl alcohol and β-hydroxyalkyl acrylate (or methacrylate) as described on page 2 (1971).

(7) An unsaturated polyester resin obtained by reacting a glycidyl ether of a polyhydroxy compound as described in US Pat. No. 3,377,406 with acrylic acid or methacrylic acid.

(8) The general formulas described in US Pat. No. 3,455,801 and US Pat. No. 3,455,802.

[0024]

[Chemical 1]

(In the formula, R represents a divalent saturated or unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms, and R'is a divalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. R'represents a hydrogen atom or a methyl group, and n is 1 to 1.
Represents an integer of 4. ) A polyester compound having an acryloyloxy group or a methacryloyloxy group at both ends, represented by

(9) The general formula described in US Pat. No. 3,483,104 and US Pat. No. 3,470,079.

[0027]

[Chemical 2]

(In the formula, A represents —O— or —NH—, at least two in one molecule are —NH—, and R is a divalent saturated aliphatic or unsaturated aliphatic hydrocarbon. Group, R'represents a divalent saturated or unsaturated aliphatic or cyclic hydrocarbon, R "represents a hydrogen atom or an alkyl group, and n represents an integer of 1 to 14). Modified (or dimethacryl modified) polyamide compound.

(10) General formula described in Japanese Patent Publication No. 48-37246

[0030]

[Chemical 3]

(Wherein X represents a hydrogen atom or an acyl group, R represents a divalent saturated or unsaturated aliphatic or cyclic hydrocarbon group, and R ¹ represents a divalent aliphatic hydrocarbon group. , R ² represents a hydrogen atom or an alkyl group, and A is —O.
Represents -or -NH-, at least two in one molecule are -NH-, and n represents an integer of 1 to 14. ) A diacryl-modified (or dimethacryl-modified) polyamide compound represented by:

(11) A saturated or unsaturated dibasic acid or an anhydride thereof as described in US Pat. No. 3,485,732, or if necessary, by reacting them with a diol. A diacryl-modified (or dimethacrylate-modified) polyester compound obtained by further reacting the obtained compound having a carboxyl group at both ends with glycidyl acrylate or glycidyl methacrylate.

(12) The general formula in the molecule as described in Japanese Patent Publication No. 48-12075.

[0034]

[Chemical 4]

(In the formula, X represents an acyl group or a urethane group, and R represents a hydrogen atom, a chlorine atom, a methyl group or a cyano group.) The unsaturated acid ester bond is present in the side chain having a repeating unit. Examples thereof include compounds based on (meth) acrylic copolymers having

Among these, as the acrylic oligomer, one selected from amide, urea and urethane in the molecular chain.
One or more groups containing at least one group, and the bond between these groups and / or the bond between these groups and an acrylic or methacrylic group is selected from polyalkylene polyether, polyalkylene polysulfide, and polyalkylene polyester. An oligomer having the above structure and having an acrylic or methacrylic group bonded to the terminal of the molecular chain can be preferably used in the present invention. This type of acrylic oligomer has a large effect of imparting surface adhesion to the resist film before actinic ray irradiation, and is useful for enhancing the transfer / holding property of the metal mask to the resist layer in the mask transfer step. Further, since the unexposed portion can be easily dissolved and removed by the developing solution, it is possible to form a highly precise fine image. Further, an acrylic or methacrylic end group-containing acrylic oligomer containing a carboxyl group is useful for improving the adhesion of the resist image to the substrate, and it is possible to prevent the fine image formed by actinic ray irradiation from being lost during the developing step. It can be effectively prevented.

Specific examples of the acrylic or methacrylic end group-containing acrylic oligomer used in the present invention include ethylene oxide-modified phthalate acrylate (Toa Gosei).
"Aronix M-5400" manufactured by Co., Ltd.), ethylene oxide modified succinic acid acrylate ("Aronix M-5500" manufactured by Toagosei Co., Ltd.), acrylic acid dimer (Aronix M- manufactured by Toagosei Co., Ltd.) 5600 ”) and the like.

Examples of the organic polymer conjugate as the second component include polystyrene, polyvinyl chloride, polyvinyl acetate, polyacrylic acid, polymethyl acrylate, ethyl polyacrylate, butyl polyacrylate, polymethacrylic acid, Polymethyl methacrylate, polyvinyl ether, polyvinyl acetal and copolymerized adducts thereof, copolymerized nylon, polyamide resin such as N-alkoxymethylated nylon, condensation reaction of dicarboxylic acid compound and diol compound Examples of the polyester resin, polyurethane resin containing diisocyanate compound and diol compound, aliphatic cyclic hydrocarbon resin, polyterpene resin, polyisoprene rubber, synthetic rubber, chlorinated rubber and the like.

This organic polymer conjugate is effective in improving the mask transfer suitability to the resist film, prevents the resist film from being deformed at the time of transfer, and resist required for fixing and holding the transfer mask. The adhesive strength of the surface can be increased.

The amount of the second component organic polymer conjugate used is
The range of 5 to 80% by weight in the composition is preferable, and 10 to 5
A range of 0% by weight is particularly preferred. When the amount used is less than 5% by weight, the surface adhesive force for receiving the transfer mask is lowered,
If it is used in an amount exceeding 5% by weight, the adhesion to the substrate, the etching resistance, etc. tend to deteriorate, which is not preferable.

The adhesive photoresist composition of the present invention comprises:
Image formation can be performed by irradiation with actinic rays, and when general-purpose ultraviolet rays are used as actinic rays, it is preferable to add a photopolymerization initiator and / or a photosensitizer.

Examples of the photopolymerization initiator or photosensitizer include 2-hydroxy-2-methyl-1-phenylpropan-1-one (“Darocur 1173” manufactured by Merck & Co., Inc.),
1-hydroxycyclohexyl phenyl ketone (Ciba
Geigy "Irgacure 184"), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (Merck "Darocur 111")
6 "), benzyl dimethyl ketal (" Irgacure 651 "manufactured by Ciba-Geigy), 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholinopropanone-1 (“Irgacure 907” manufactured by Ciba-Geigy),
A mixture of 2,4-diethylthioxanthone ("Kayacure DETX" manufactured by Nippon Kayaku Co., Ltd.) and ethyl p-dimethylaminobenzoate ("Kayacure EPA" manufactured by Nippon Kayaku Co., Ltd.),
Examples include a mixture of isopropyl thioxanthone (“CANTACURE ITX” manufactured by Ward Prekinsop) and ethyl p-dimethylaminobenzoate, acylphosphine oxide (“Lucirin LR8728” manufactured by BASF), and the like.

The proportions of the photopolymerization initiator and the photosensitizer used are
The range of 0.5 to 5% by weight in the resist composition is preferable, and the range of 1.0 to 3.0% by weight is particularly preferable.

Each of the components described above is the main component of the adhesive photoresist composition of the present invention. Of course, an antioxidant, a chain transfer agent, a thermal polymerization inhibitor, and a coloring agent such as a dye / pigment may be added to the composition of the present invention, if necessary.

[0045]

EXAMPLES The present invention will be described more specifically below by showing examples of the present invention. However, the invention is not limited to these examples.

Example 1 Acrylic end group-containing urethane acrylic oligomer prepared by adding 3 mol of tolylene diisocyanate to 2 mol of polypropylene glycol having a molecular weight of 3000 and further adding 2 mol of hydroxypropyl acrylate. -(A) was synthesized.

Using this, a liquid photoresist composition was prepared with the following composition. Urethane acrylic oligomer (A) 40 g Ethylene oxide modified phthalate acrylate 30 g (Toagosei Co., Ltd. "Aronix M-5400") Styrene acrylic acid resin 30 g (Johnson Polymer Co., Ltd. "John Cryl 68", M _W = 10000) 1-Hydroxycyclohexyl phenyl ketone 5 g (“Irgacure 184” manufactured by Ciba-Geigy Co., Ltd.) Methyl cellosolve 250 g ────────────────────── ─────────── 355g

The above photoresist solution was spin-coated (2000 rpm) on a slide glass substrate, and 100
It was dried at 0 ° C. for 10 minutes to form a uniform resist coating having a thickness of 2.5 μm. This resist coating has a sufficiently sticky surface at room temperature, and when a finger is pressed from above, it sticks to the fingertips, and in this state it can be lifted up in the air together with the slide glass substrate. Had.

When a metal mask was roller-pressed onto the resist coating film, it was sufficiently adhered to the resist surface and no drop of the metal mask was observed even when the glass substrate was turned upside down. 80W / for resist with metal mask adhered
400mJ / with a metal halide lamp with an output of cm
A single exposure was performed by irradiating with ultraviolet rays of cm ² . Next, when developed with a methyl cellosolve solvent for 1 minute and washed with water,
The part shielded from light by the mask was dissolved and removed, and only the light irradiation part remained as a non-adhesive cured resist image on the substrate.
The cured image area resolved the line and space of 3 μm width of the metal mask.

When this resist image-forming glass plate was immersed in a 1% aqueous solution of hydrofluoric acid for 1 minute, no peeling of the resist was observed and it was confirmed that the etching resistance and image adhesion were excellent.

Example 2 Acrylic end group-containing urethane acrylic oligomer in which 1 mol of tolylene diisocyanate was added to 1 mol of polypropylene glycol having a molecular weight of 2000 and 2 mol of hydroxypropyl acrylate was further added. -(B) was synthesized.

Using this, a liquid photoresist composition was prepared with the following composition. Urethane acrylic oligomer (B) 30 g Ethylene oxide modified phthalate acrylate 25 g Tetramethylolmethane tetraacrylate 25 g ("A-TMMT" manufactured by Shin-Nakamura Chemical Co., Ltd.) Styrene acrylic resin 25 g Acylphosphine oxide 1 g ( BASF Corporation "Lucillin TPO") t-Butyl hydroquinone 0.05 g Methyl cellosolve 250 g ─────────────────────────────── ── 351g

The above photoresist was roll-coated on a glass substrate having an ITO conductive layer and dried at 100 ° C. for 10 minutes to form a uniform resist coating film having a thickness of 2.5 μm.

This resist coating film had sufficient surface tackiness at room temperature. After transferring a metal mask onto the resist coating film, a metal halide lamp having an output of 80 W / cm was irradiated with ultraviolet rays of 150 mJ / cm ² to perform batch exposure. Then, after developing with a methyl cellosolve solvent for 1 minute to dissolve and remove the unexposed portion, the product was washed with water, whereby a high-resolution non-adhesive resist pattern image could be formed.

Example 3 Bisphenol A (1 mol)
133.2 g of the ethylene oxide (6 mol) adduct and 29.2 g of adipic acid were charged into a reaction vessel equipped with a stirrer, a thermometer, and a distillation tube, and the temperature was raised to 160 ° C. with stirring to start the reaction. . After continuing heating and stirring for 3 hours, 11.0 g of pyromellitic dianhydride was added,
The reaction was continued at 140 ° C. for 20 minutes to obtain a polyester resin (A) as an organic polymer conjugate having a carboxyl group on the side chain with an acid value of 40.5.

Using this, a liquid photoresist composition was prepared with the following composition. Urethane Acrylic Oligomer (B) 50 g Pentaerythritol triacrylate 15 g (“Aronix M-305” manufactured by Toagosei Co., Ltd.) Acrylic acid dimer 15 g (“Aronix M-5600” manufactured by Toagosei Co., Ltd.) Polyester Resin (A) 20 g 2-Hydroxy-2-methyl-1-phenylpropane 1 g-1-one (“Darocur 1173” manufactured by Merck Ltd.) Methyl cellosolve 299 g ─────────────── ────────────────── 400g

The above photoresist solution was spin-coated (2000 rpm) on a glass substrate and dried at 100 ° C. for 10 minutes to form a uniform resist coating film having a thickness of 2 μm.

This resist coating film had a sufficiently tacky surface at room temperature and was excellent in mask transfer acceptability. After the mask was transferred onto the resist, it was collectively exposed to actinic rays to form an image, and then developed with a methyl cellosolve solvent to obtain a high-resolution non-adhesive cured resist image. When this resist image forming glass plate was immersed in 5% hydrochloric acid water for 5 minutes, no peeling of the resist was observed and it was confirmed that the resist image forming glass plate was excellent in etching resistance and image adhesion.

(Example 4) Using the urethane acrylic oligomer (A) shown in Example 1, a liquid photoresist was prepared with the following composition. Urethane acrylic oligomer (A) 40 g Acrylic acid dimer "Aronix M-5600" 30 g Styrene acrylate resin "John Cryl 68" 30 g Darocur 1173 1 g Methyl cellosolve 250 g ──────────────── ───────────────── 351g

The above photoresist was roll-coated on a glass substrate having an ITO conductive layer and dried at 100 ° C. for 10 minutes to form a uniform resist coating film having a thickness of 2.5 μm.

This resist coating film had sufficient surface tackiness at room temperature. After transferring a metal mask on the resist and the coating film, a batch of exposure was carried out by irradiating ultraviolet rays of 400 mJ / cm ² with a metal halide lamp having an output of 80 W / cm. Next, after developing for 1 minute using an aqueous developing solution having the following composition to dissolve and remove the unexposed area, it was washed with water, whereby a high-resolution non-adhesive resist pattern image could be formed.

Aqueous developer composition Triethanolamine 2 g Monoethanolamine 1 g Benzyl alcohol 1 g Perex NBL 1 g (t-butylnaphthalene sulfonic acid surfactant manufactured by Kao Atlas Co., Ltd.) Water 95 g ─────── ────────────────────── 100g

[0063]

The adhesive photoresist composition of the present invention is a photoresist material capable of performing thin film single-layer coating and having the function of transferring and fixing a metal mask or the like on the surface thereof. It is possible to form a high-resolution resist pattern image by a batch exposure method without using.

Therefore, if the adhesive photoresist composition of the present invention is used, a large area circuit element substrate can be easily manufactured with high productivity.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location H01L 21/027

Claims (3)

[Claims] 1. A tacky photo having a tackiness on the surface of a coating film sufficient to fix a mask pattern and forming a non-image area which can be developed and removed by actinic ray irradiation and a non-tacky cured image area. A pressure-sensitive adhesive photoresist composition comprising: (1) an acrylic or methacrylic end group-containing acrylic oligomer and (2) an organic polymer conjugate. 2. The acrylic oligomer contains one or more groups selected from amide, urea and urethane in the molecular chain,
The bond between these groups and / or the bond between these groups and an acrylic or methacrylic group contains at least one structure selected from polyalkylene polyether, polyalkylene polysulfide, polyalkylene polyester, and The tacky photoresist composition according to claim 1, which comprises an oligomer having an acrylic or methacrylic group bonded to the end of the molecular chain and an acrylic oligomer having a carboxyl group-containing acrylic or methacrylic end group. 3. The adhesive photoresist composition according to claim 1, further comprising an initiator and / or a photosensitizer.