JPH05333546A - Adhesive photoresist composition - Google Patents

Abstract

PURPOSE:To obtain a composition capable of forming a uniform thin film on a substrate to be worked, capable of forming a film sufficiently withstanding the transfer pressure of a mask pattern and capable of fixing a transfer mask by incorporating specified photosensitive resin and photosensitive monomer. CONSTITUTION:The composition contains a photosensitive resin having -100 to 20 deg.C glass transition point and having >=2 active beam-setting vinyl groups having >=1000 mol.wt. and a photosensitive monomer having >=2 active beam- setting vinyl groups having <=1000 mol.wt. A single thin-film resist layer is formed by the combination of the two components, the mask pattern acceptability and maintainability are satisfied, and the composition capable of forming a high-resolution cured picture excellent in etching resistance is obtained. Consequently, since a thin coating film is formed on a substrate to be etched from this composition, a large area is rapidly resist-patterned with high precision without using a stepper.

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. It has an adhesive force capable of receiving and fixing the mask pattern as a transfer image on the surface of the coating film, and it is possible to form an image in a large area by batch exposure through the transfer mask, and to be etched by the development process. The present invention relates to a novel photoresist composition capable of exposing a surface and forming a cured image portion having excellent etching resistance.

[0002]

2. Description of the Related Art Recently, in the display field, the demand for display devices using liquid crystals has increased, and the demand for large-area electrode circuit elements for 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 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), a metal pattern is formed by an electrodeposition method using the pattern on this substrate, and this metal thin film pattern is formed. This is a process of forming a pattern without using a stepper by transferring onto a resist layer provided on a substrate to be etched.

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, it is possible to impart the transferability of the mask pattern by newly providing an adhesive layer on the photoresist layer, but it is necessary to remove the adhesive layer uniformly during the development process. Becomes difficult,
There is a problem in that 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 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 it is possible to coat a processed substrate in a uniform thin film, and to form a film having sufficient film-forming property to withstand the transfer pressure of the mask pattern and to fix the transfer mask. Adhesive that can form a coating film that has the same surface adhesiveness and that can form high-resolution image areas that have excellent etching resistance and non-image areas that can be removed by development processing, as with conventional photoresists. To provide a positive photoresist composition.

[0010]

In order to solve the above problems, the present invention (1) has a glass transition point in the range of -100 to 20 ° C and a molecular weight (number average molecular weight) of 1.00.
0 or more, preferably a molecular weight of 1,000 to 10,000
A photosensitive resin having two or more actinic ray-curable vinyl groups (hereinafter referred to as the first component) and (2) having a molecular weight of 1,000 or less, preferably 100-1.
And a photosensitive monomer having two or more actinic radiation-curable vinyl groups (hereinafter referred to as a second component) in the range of 000, and a photoresist composition.
Further, it is possible to form a non-image area that can be developed and removed and a non-adhesive cured image area by irradiating an actinic ray through a mask pattern fixed to an adhesive resist layer composed of this photoresist composition. A method of forming a characteristic resist pattern is provided.

By the combination of the first component and the second component, both the formation of a thin film resist layer in a single layer, the acceptance of a mask pattern in a transfer process and the transfer mask holding aptitude, which are indispensable as a printing type resist material, are satisfied, And,
Provided is a composition which forms a high-resolution cured image having excellent etching resistance. Therefore, by forming the photoresist composition of the present invention as a thin film coating on a substrate to be etched, it becomes possible to perform resist patterning of a large area with high accuracy and quickly without using a stepper.

The first component and the second component used in the present invention are characterized by the following points.

The first component used in the present invention is a polymerizable compound containing two or more actinic ray-curable vinyl groups, such as an acrylic or methacrylic group, which can be polymerized by actinic rays. It can effectively act as a component for imparting surface tackiness of the film, a component for imparting mask transferability to the resist film and a component for preventing deformation of the resist film during transfer, and may be a single photosensitive resin. Two
It is also possible to use one or more photosensitive resins in combination.

The following are specific examples of the first component used in the present invention.

(1) 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 further reacted with β-hydroxyalkyl (meth) acrylate to give 2 in the molecule. An addition-polymerizable compound having one or more (meth) acryloyloxy groups.

(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,
An epoxy (meth) acrylate such as a tetrabasic acid anhydride or an epoxy (meth) acrylate having a carboxyl group obtained by adding trimellitic anhydride, and a modified product thereof.

(3) Dibasic acid such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, or hettic anhydride as described in JP-B-47-3262. A linear polyester compound obtained by ring-opening polymerization of an anhydride and glycidyl (meth) acrylate and having a large number of (meth) acryloyloxy groups as pendants.

(4) Polyhydric alcohols having at least three esterifiable hydroxyl groups at adjacent carbon atoms as described in JP-B-47-23661, (meth) acrylic acid, and dicarboxylic acid. And polymerizable esters prepared by co-esterification with dicarboxylic acids selected from the group consisting of and its anhydrides.

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

(6) Divalent saturated or unsaturated group having 2 to 10 carbon atoms as described in US Pat. No. 3,455,801 and US Pat. No. 3,455,802. A polyester compound having a (meth) acryloyloxy group at both ends, which is obtained by reacting a reaction product of a fatty acid and a divalent saturated aliphatic diol having 2 to 10 carbon atoms with (meth) acrylic acid.

(7) Divalent saturated or unsaturated fatty acids and saturated or unsaturated fatty acids as described in US Pat. No. 3,483,104 and US Pat. No. 3,470,079. A di (meth) acryl-modified polyamide compound obtained by reacting (meth) acrylic acid with a reaction product of the aliphatic, aromatic or alicyclic diol or diamine.

(8) Glycidyl is a reaction product of a saturated or unsaturated aliphatic, aromatic or alicyclic dibasic acid with an aliphatic diol or diamine as described in JP-B-48-37246. A (meth) acrylic-modified polyamide compound obtained by reacting with a group-containing acrylic monomer.

(9) Saturated or unsaturated dibasic acids or their anhydrides as described in US Pat. No. 3,485,732, or if necessary, by reacting them with a diol. A (meth) acryl-modified polyester compound obtained by further reacting the obtained compound having a carboxyl group at both ends with glycidyl (meth) acrylate.

(10) Compounds based on a (meth) acrylic copolymer having an unsaturated acid ester bond in the side chain as described in JP-B-48-12075 can be mentioned.

The amount of the photosensitive resin used as the first component is preferably in the range of 10 to 90% by weight in the composition of the present invention.

The second component used in the present invention effectively acts as a component for adjusting the cross-linking density of the image. For example, ethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, 1,3-propane. Diol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri ( Unsaturated acid esters of polyols such as (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, 1,5-pentanediol di (meth) acrylate, or British Patent No. 628,15. Pat, US Pat. No. 3,020,255 Pat and monthly magazine "Macromolecules" Vol. 4, No. 5, pp. 630-632 (19
71) to melamine or benzoguanamine as described in formaldehyde, methyl alcohol and β-
Examples thereof include poly (meth) acryl-modified triazine-based resins obtained by reacting hydroxyalkyl (meth) acrylate.

The amount of the second component used is preferably 10 to 90% by weight in the composition of the present invention. If it is less than 10% by weight, the etching resistance tends to decrease, and if it exceeds 90% by weight, the surface adhesive force for receiving the transfer mask tends to decrease, which is not preferable.

The above-mentioned two components are the main components of the photoresist composition of the present invention.

Further, in the photoresist composition of the present invention,
Non-photosensitive organic polymers such as polystyrene, polyvinyl chloride, polyvinyl acetate, poly (meth) acrylic acid,
Polyamides such as methyl poly (meth) acrylate, ethyl poly (meth) acrylate, butyl poly (meth) acrylate, polyvinyl ether, polyvinyl acetal and copolymerized adducts thereof, copolymerized nylon, N-alkoxymethylated nylon Resin, polyester resin by condensation reaction of dicarboxylic acid compound and diol compound, polyurethane resin by diisocyanate compound and diol compound, aliphatic cyclic hydrocarbon resin, polyterpene resin,
Improve the mask transfer suitability of polyisoprene rubber, synthetic rubber, chlorinated rubber, etc. to the resist film, prevent the resist film from deforming during transfer, and enhance the adhesive strength of the resist surface required to fix and hold the transfer mask It can also be used to

In addition to the photoresist composition of the present invention,
If necessary, a photosensitive resin having a glass transition point of 20 ° C. or higher and a molecular weight of 1,000 or higher, a polymerization initiator, a photosensitizer, a chain transfer agent, a colorant, etc. may be added and used.

In the photoresist composition of the present invention, a photopolymerization initiator can be used in combination when ultraviolet rays are used as actinic rays.

Examples of the photopolymerization initiator include 2, 4,
6-trimethylbenzoyldiphenylphosphine oxide (“Lucirin TPO” manufactured by BASF), 2-hydroxy-2-methyl-1-phenylpropan-1-one (“Darocur 1173” manufactured by Merck), 1-hydroxycyclohexylphenylketone ( Ciba Geigy "Irgacure 184"), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (Merck "Darocur 1116"), benzyl dimethyl ketal (Ciba Geigy) Made "Irgacure 65
1 "), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (" Irgacure 907 "manufactured by Ciba-Geigy), 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.) "Kayakyu DETX")
And a mixture of 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. Etc.

The amount of the photopolymerization initiator used is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the photoresist composition of the present invention.

[0034]

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 Tolylene diisocyanate was added to 2 mol of polypropylene glycol having a molecular weight of 3000.
A photosensitive resin (A), which is an acrylic group-containing polyether urethane compound, was prepared by adding 3 mol and further adding 2 mol of hydroxyethyl acrylate.

Using this, a liquid photoresist composition was prepared with the following composition. Photosensitive resin (A) 50 g "DICLIGHT UE-8200" (Epoxy acrylate manufactured by Dainippon Ink and Chemicals) 30 g Pentaerythritol tetraacrylate 20 g "Irgacure 184" (polymerization initiator manufactured by Ciba Geigy) 3 g Methyl cellosolve 380 g --- ────────────────────────────── 483g

The above-mentioned photoresist solution was spin-coated (2000 rpm) on a slide glass substrate, and 100
After drying at 0 ° C. for 10 minutes, a uniform resist coating film having a thickness of 2.5 μm was formed. This resist coating has a sufficiently tacky surface at room temperature, and when a 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.

When a metal mask was pressure-bonded onto the resist coating film with a roller, 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. The resist having the metal mask fixed thereto was collectively exposed for 3 minutes by a desktop printer (manufactured by Dainippon Screen Mfg. Co., Ltd.). Then, it was developed with a methyl cellosolve solvent for 1 minute and washed with water. The light-shielded portion was removed by dissolution, and only the light-irradiated portion remained as a non-adhesive cured resist image on the substrate. The cured image area resolved a 1-micron wide line and space of the metal mask.

When this resist image-forming glass plate was immersed in a 1% hydrofluoric acid aqueous solution 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) 1,4-butanediol 4
Trimethylhexamethylene diisocyanate 5 mol
A photosensitive resin (B), which is an acrylic group-containing polyurethane compound in which 2 mol of hydroxypropyl acrylate was added, was synthesized.

Using this, a liquid photoresist composition was prepared with the following composition. Photosensitive resin (B) 40 g Pentaerythritol tetraacrylate 30 g Polymethyl methacrylate 30 g “Irgacure 907” (Ciba Geigy polymerization initiator) 3 g Methyl cellosolve 380 g ────────────────── ─────────────── 483g

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 coating film, a metal halide lamp having an output of 80 W / cm was irradiated with ultraviolet rays of 90 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) Using the photosensitive resin (A) shown in Example 1, a liquid photoresist was prepared with the following composition. Photosensitive resin (A) 62 g Trimethylolpropane triacrylate 20 g Polymethylmethacrylate 12 g Polymethacrylic acid 6 g “Irgacure 907” 3 g Methylcellosolve 400 g ───────────────────── ──────────── 503g

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 acceptability for mask transfer.
After transferring the mask onto the resist, the active rays were collectively exposed in the same manner as in Example 2 to form an image, and then the resist was 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,
It was confirmed that the etching resistance and the image adhesion were excellent.

[0046]

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

Therefore, by using the adhesive photoresist composition of the present invention, a large-area circuit element substrate can be easily manufactured with high productivity.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location G03F 7/038 501 H01L 21/027

Claims (3)

[Claims] 1. A glass transition point of -100 to 20 ° C.
And a photosensitive resin having two or more actinic ray-curable vinyl groups having a molecular weight of 1,000 or more and (2) two or more actinic ray-curable vinyl groups having a molecular weight of 1,000 or less. A photoresist composition comprising a photosensitive monomer. 2. A tacky photoresist composition which forms a non-image area that can be developed and removed and a non-tacky cured image area by irradiating an actinic ray through a mask pattern fixed to a tacky resist layer. And (1)
Has a glass transition point in the range of −100 to 20 ° C., and
2 actinic radiation-curable vinyl groups with a molecular weight of 1,000 or more
A photosensitive resin having 1 or more and (2) a molecular weight of 1,000
A photoresist composition comprising the following photosensitive monomer having two or more actinic ray-curable vinyl groups. 3. A non-image area and a non-adhesive cured image which can be removed by development by irradiating with actinic rays through a mask pattern fixed to a resist layer having tackiness, which comprises the photoresist composition according to claim 1. Forming a resist pattern.