JPH06266103A - Photosensitive self-adhesive resist composition - Google Patents

Abstract

PURPOSE:To provide a photosensitive self-adhesive resist compsn. capable of forming a high resolution resist pattern excellent in etching resistance by a general exposure system without using a stepper and enabling easy production of a circuit element board having a large area with high productivity as a photoresist material capable of coating in a thin single layer and having function to transfer and fix a metallic mask, etc., on the surface. CONSTITUTION:This photosensitive self-adhesive resist compsn. having surface adhesiveness of a coating film sufficient to fix a mask pattern and forming a non-image part which can be removed by development and a nonsticky hardened image part by irradiation with an active light is made of a polymerizable acrylic oligomer contg. a compd. represented by the formula (where X is a residue of polyol and (n) is an integer of 2-6).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pattern forming material which can be suitably used for manufacturing a large area electrode circuit element substrate, and more specifically, it can be applied uniformly on a processed substrate, It has an adhesive force that can receive and fix a pattern mask as a transfer image on the surface of the coating film, and an image can be formed in a wide area by batch exposure through the transfer mask, and the surface to be etched is exposed by a developing process. In addition, the present invention relates to a novel photosensitive adhesive resist composition capable of forming a cured image portion having excellent etching resistance.

[0002]

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

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 pattern image is 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), a metal mask pattern is formed by an electrodeposition method using the pattern on this substrate, and this metal thin film pattern is formed. Is transferred to 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 accepting and fixing a 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 problem, it is possible to impart mask pattern transferability by newly providing an adhesive layer on the photoresist layer, but it is difficult to remove the adhesive layer uniformly during development processing. Therefore, there arises a problem that the surface to be etched cannot be exposed with high precision, or even if the developing process is performed,
There is a problem that the image resolution is reduced due to the layer structure.

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

The problems to be solved by the present invention are excellent in that a uniform thin film can be coated on a processed substrate, and sufficient film-forming properties that can withstand the transfer pressure of the mask pattern and fixation of the transfer mask are possible. It is an object of the present invention to provide a photosensitive pressure-sensitive adhesive resist composition capable of forming a coating film having a surface adhesive force and capable of forming a fine image having excellent etching resistance.

[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 problems, the present invention applies a photopolymerizable composition onto a substrate to form a photosensitive thin film layer having a surface adhesive force, the first step, the photosensitive thin film layer. The second step of transferring and fixing the light-shielding solid mask on the surface,
The third step of cross-linking and curing the photosensitive thin film layer in the mask opening by irradiating actinic rays from the fixed solid mask side and peeling and removing the solid mask, and then developing and removing the unexposed photosensitive thin film layer on the substrate. A photosensitive pressure-sensitive adhesive resist composition comprising a photopolymerizable composition used in the method for forming a high-definition pattern image comprising the fourth step of forming a high-definition pattern image on a substrate, wherein the photopolymerizable composition is represented by the general formula: (1)

[0012]

[Chemical 2]

There is provided a photosensitive pressure-sensitive resist composition containing a compound represented by the formula (wherein X represents a polyhydric alcohol component residue and n represents an integer of 2 to 6).

The compound represented by the general formula (1) used in the present invention can be synthesized by reacting vinyl azlactone with a polyhydric alcohol compound. Specific examples of the polyhydric alcohol compound include, for example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, Diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, bisphenol A, bisphenol F, bisphenol S, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, Spiro glycol, tricyclodecane dimethanol, hydroxypivalic acid neopentyl glycol ester, dimethylol propionic acid, 4,
4'-thiodiphenol etc. are mentioned.

The compound represented by the general formula (1) effectively acts to suppress the curing shrinkage strain at the time of forming a fine pattern on the substrate, improves the image adhesion to the substrate and the etching resistance of the image. Can be improved.

By using the acrylic oligomer represented by the general formula (1) in combination with another polymerizable acrylic oligomer, a photosensitive pressure sensitive resist composition having a better balance can be obtained.

The polymerizable acrylic oligomer which can be preferably 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-butanetriol trimethacrylate, trimethylolethane triacrylate,
Pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol polyacrylate, 1,3-propanediol diacrylate, 1,5-pentane Unsaturated esters of polyols such as diol 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 with acrylic acid or methacrylic acid as described in US Pat. No. 3,377,406.

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

[0026]

[Chemical 3]

(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.

[0029]

[Chemical 4]

(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) The general formula described in JP-B-48-37246

[0032]

[Chemical 5]

(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) Saturated or unsaturated dibasic acids or their anhydrides as described in US Pat. No. 3,485,732 or, if necessary, 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.

[0036]

[Chemical 6]

(Wherein, 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), and an 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 them, the acrylic oligomer contains at least one group selected from amide, urea and urethane in the molecular chain, and the bond between these groups is a polyalkylene polyether, polyalkylene polysulfide or polyalkylene. An oligomer containing one or more structures selected from polyester and having an acrylic or methacrylic group bonded to the end of the molecular chain can be preferably used in the present invention. This type of acrylic oligomer has a large effect of imparting surface adhesiveness 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. In addition, an acrylic or methacrylic end group-containing acrylic oligomer containing a carboxyl group or a phosphoric acid group is useful for improving the adhesion of the resist image to the substrate, and during the development step of a fine image formed by irradiation with actinic rays. Can be effectively prevented. Specific examples thereof include ethylene oxide-modified phthalic acid acrylate (Aronix M-5400 manufactured by Toagosei Co., Ltd.), ethylene oxide-modified succinic acid acrylate (Aronix M-550 manufactured by Toagosei Co., Ltd.).
0), acrylic acid dimer (Aronix M-5600 manufactured by Toagosei Co., Ltd.), 2-methacryloyloxyethyl phosphate (Kayamer PM-1 manufactured by Nippon Kayaku Co., Ltd.), 2
-Hydroxyethyl methacrylate phosphate (Kayamer PM-2 manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned.

If desired, an organic polymer conjugate may be added to the composition of the present invention. As the organic polymer conjugate, for example, polystyrene, polyvinyl chloride,
Polyvinyl acetate, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polymethacrylic acid, polymethyl methacrylate, polyvinyl ether, polyvinyl acetal, and their copolymerized adducts, copolymerized nylon, N A polyamide resin such as an alkoxymethylated nylon, a polyester resin by a condensation reaction of a dicarboxylic acid compound and a diol compound, a polyurethane resin by a diisocyanate compound and a diol compound, an aliphatic cyclic hydrocarbon resin, a polyterpene resin,
Examples thereof include 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 during transfer, and is a resist necessary for fixing and holding the transfer mask. The adhesive strength of the surface can be increased.

The photosensitive adhesive resist composition of the present invention can form an image by irradiation with actinic rays. When general-purpose ultraviolet rays are used as actinic rays, a photopolymerization initiator and / or a photosensitizer is used. Is preferred.

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.),
A mixture of isopropyl thioxanthone (“Cantacure ITX” manufactured by Ward Prekinsop) and ethyl p-dimethylaminobenzoate, acylphosphine oxide (“Lucirin LR8728” manufactured by BASF, 2- (parachlorophenyl) -4,6. -Bis (trichloromethyl)
-1,3,5-triazine, 2- (paramethoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5
-Triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5
-Triazine, 2- (paramethoxystyryl) -4,6
-Bis (trichloromethyl) -1,3,5-triazine and the like. The use ratio of the photopolymerization initiator and the photosensitizer is preferably 0.5 to 5% by weight, and particularly preferably 1.0 to 3.0% by weight in the resist composition.

Each of the components described above is the main component of the photosensitive adhesive resist 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.

[0044]

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 A four-necked flask equipped with a stirrer, a cooling tube and a thermometer was charged with 1000 ml of toluene and 198 g of tricyclodecane dimethylol, stirred to make a homogeneous solution, and then 286 g of vinylazlactone. DBU
9.4 g was added and refluxed for 5 hours. After cooling to room temperature, the reaction solution was concentrated under reduced pressure to synthesize an acrylic oligomer (A).

Using this, a photosensitive adhesive resist composition was prepared with the following composition. Acrylic oligomer (A) 40 g Ethylene oxide modified phthalic acid acrylate ("Aronix M-5400" manufactured by Toagosei Co., Ltd.) 20 g Isocyanuric acid ethylene oxide modified triacrylate (Aronix M-315 manufactured by Toagosei Co., Ltd.) 10g styrene acrylic resin (Johnson polymer Co., Ltd. "Joncryl _{68", M W = 10000) 30g 2-} ( p-methoxy) -4,6-bis (trichloromethyl) -1, 3,5-triazine 3g Methyl cellosolve 100 g Methyl ethyl ketone 150 g ──────────────────────────────── 353g

The above-mentioned photopolymerizable composition solution was spin-coated (3000 rpm) on a slide glass substrate to obtain 100
It was dried at 0 ° C. for 10 minutes to form a uniform photosensitive coating having a thickness of 2.5 μm. This photosensitive coating has a sufficiently tacky surface at room temperature, and when the finger is pressed from above, it sticks to the fingertips, and in this state it is tacky enough to be lifted up into the air together with the slide glass substrate. Had power.

The above photopolymerizable composition solution was roll-coated on a glass substrate on which indium oxide was vapor-deposited to a thickness of 400 Å, and dried at 100 ° C. for 5 minutes to give a thickness of 3.0.
A micron uniform photosensitive layer coating was formed.

When a metal mask was pressure-bonded onto the photosensitive coating film with a roller, it was sufficiently adhered to the surface of the photosensitive layer, and no drop of the metal mask was observed even when the glass substrate was turned upside down. The photosensitive layer to which the metal mask had been fixed was collectively exposed by irradiating it with ultraviolet rays of 150 mJ / cm ² from a metal halide lamp having an output of 80 W / cm.

Then, after removing the metal mask by peeling, the film was 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 a 3 micron wide line and space of the metal mask.

The resist image-forming glass plate was placed at 36 ° C.
The substrate was immersed in an aqueous solution containing ferric chloride and hydrochloric acid kept for 2 minutes and etched for 2 minutes. The ITO layer in the pattern opening without the resist image was completely removed from the glass substrate. At that time, swelling, peeling in the resist image area,
No detachment was observed and it was confirmed that the etching resistance was excellent.

Example 2 A photosensitive adhesive resist composition was prepared with the following composition. Acrylic oligomer (A) 30 g Ester-based acrylic oligomer ("Aronix M-6400" manufactured by Toagosei Co., Ltd.) 40 g Acrylic oligomer containing carboxyl group "Aronix M-5400" 30 g 2- (paramethoxyphenyl) -4,6-bis (Trichloromethyl) -1,3,5-triazine 5 g Methyl cellosolve 50 g Methyl ethyl ketone 200 g ───────────────────────────────── 355g

The above-mentioned photopolymerizable composition solution was spin-coated (3000 rpm) on a slide glass substrate, and 100
It was dried at 0 ° C. for 10 minutes to form a uniform photosensitive coating having a thickness of 2.5 μm. This photosensitive coating has a sufficiently tacky surface at room temperature, and when the finger is pressed from above, it sticks to the fingertips, and in this state it is tacky enough to be lifted up into the air together with the slide glass substrate. Had power.

As in Example 1, an ITO-treated glass substrate was roll-coated with the above-mentioned photopolymerizable composition solution to give a thickness of 3.
A 0 micron uniform photosensitive layer coating was formed.

When a metal mask was roller-pressed onto this photosensitive coating, it was sufficiently adhered to the surface of the photosensitive layer and no drop of the metal mask was observed even when the glass substrate was turned upside down. The photosensitive layer to which the metal mask had been fixed was collectively exposed by irradiating it with ultraviolet rays of 150 mJ / cm ² from a metal halide lamp having an output of 80 W / cm.

Then, after removing the metal mask by peeling, the film was 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 a 3 micron wide line and space of the metal mask.

The resist image-forming glass plate was placed at 40 ° C.
It was immersed in a 50% strength aqueous solution of hydrochloric acid, and etched for 2 minutes. While the ITO layer in the opening was completely removed, no defects such as swelling, peeling and dropping were observed in the patterned resist image, and it was confirmed that the resist image had excellent etching resistance.

Example 3 A photosensitive adhesive resist composition was prepared by the following composition. Acrylic oligomer (A) 29 g Phosphoric acid group-containing acrylic oligomer (“Kayamer PM-1” manufactured by Nippon Kayaku Co., Ltd.) 17 g Trimethylolpropane acrylic acid benzoate (“BA-134” manufactured by Kyoeisha Yushi Co., Ltd.) 17 g Styrene acrylic acid resin "Johncryl 68" 37 g 2- (paramethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine 5 g Methyl cellosolve 100 g Methyl ethyl ketone 150 g ────────── ─────────────────────── 353g

The above-mentioned photosensitive adhesive resist composition solution was roll-coated on a polysilicon substrate and dried at 100 ° C. for 5 minutes to form a uniform photosensitive layer coating film having a thickness of 2.5 μm.

This photosensitive layer coating film had a sufficiently tacky surface at room temperature and was excellent in mask transfer acceptability. After transferring the mask onto the photosensitive layer, exposing it to actinic rays at one time, forming an image, and developing with a methyl cellosolve solvent, a high-resolution (3 micron L / S) non-adhesive cured pattern image is formed with polysilicon. It could be formed on the substrate.

[0061]

The photosensitive adhesive resist composition of the present invention comprises
It is a photosensitive material that can be coated with a thin film single layer and has the function of transferring and fixing a metal mask etc. on its surface. It is excellent in etching resistance with no chip on the substrate by a batch exposure method without using a stepper. A high-resolution pattern image can be formed.

Therefore, by using the high-definition pattern forming material of the present invention, a large area circuit element substrate can be easily manufactured with high productivity.

Claims (1)

[Claims] 1. A first step of applying a photopolymerizable composition onto a substrate to form a photosensitive thin film layer having surface adhesiveness, transferring and fixing a light-shielding solid mask on the surface of the photosensitive thin film layer. 2nd step, 3rd step of cross-linking and curing the photosensitive thin film layer in the mask opening by irradiating actinic rays from the fixed solid mask side, and after removing and removing the solid mask, developing and removing the unexposed photosensitive thin film layer A photosensitive adhesive resist composition comprising a photopolymerizable composition for use in a method for forming a high-definition pattern image, which comprises the fourth step of forming a high-definition pattern image on a substrate. The product has the general formula: (In the formula, X represents a polyhydric alcohol component residue, and n is 2
Represents an integer of ~ 6. ) A photosensitive adhesive resist composition comprising a compound represented by: