JPH1115131A - Mask for photoresist and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce a time for vacuuming and to prevent a resist pattern obtained by exposure from damage of the resist pattern, by forming a light shielding pattern and a projecting region of a specific height. SOLUTION: On a surface of a transparent substrate, a light shielding pattern and 1 μm or higher projecting region are formed. The height of the projecting area is desirably 1-30 μm, more desirably, 2-10 μm, further more desirably, 3-8 μm. When the substrate surface is brought into contact with a photo-sensitive layer for photo-resist, a space is produced between a mask surface and a photo- resist photo-sensitive layer surface on a non-projecting region area by providing the light shielding pattern and also the projecting part region on the surface of the substrate, therefore, the air existing inside comes off through the space, and the mask for photo-resist is brought into close and sufficient contact with the photo-sensitive material. And, a resist obtained from an exposed photo-sensitive layer by using this mask for photo-resist will not be deformed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoresist mask (master plate) used in a photolithography method for forming a pattern by an exposure / development operation and a method of manufacturing the same, and more particularly, to the surface of a photoresist film and the photoresist. 1. Field of the Invention The present invention relates to a photoresist mask capable of being brought into vacuum contact with a mask surface for a short time, and a method for manufacturing the same.

[0002]

2. Description of the Related Art A method of forming a pixel by using a photolithography method and utilizing it industrially is widely used. PS that uses the obtained pixels as a plate for offset printing
Both the plate and the photoresist for processing the material by etching with a chemical are exposed through a photoresist mask and developed to form a pattern for use.

[0003] In the field where photoresist is used, the manufacture and processing of semiconductors, printed circuit boards, shadow masks and the like are typical. In the working process, a film made of a photosensitive material called photoresist is formed on a material to be processed. Exposure is performed through a photoresist mask, development is performed to form a resist pattern, and then etching is performed. As a method of etching, a method such as a wet etch dissolved with a chemical solution, a dry etch using a gas, or a sand blast method of spraying fine particles for grinding is used. The required characteristics of the photoresist mask differ depending on the conditions used. P
The photoresist mask used for the S plate is rarely used because the same printing plate is rarely made for each of the many printing plates, but the photoresist mask used for etching requires exposure and development for the number of materials to be processed. To be used frequently. Since the fields used are mainly industrial materials, throughput is always an issue. Although the exposure time and the development time are always considered as throughputs of the exposure step and the development step, the preparation time is often overlooked. When exposing using a vacuum printer, the time required for vacuum contact is often longer than the exposure time.

When exposure is performed in a state where a photoresist mask and a resist film (or a photosensitive film) are in contact with each other and precision is required, for example, a PS plate or a shadow mask is used for a photoresist mask and a resist film (or a photosensitive film). )
Is exposed using a vacuum printer in order to make the contact of the particles dense. Vacuum printers generally consist of a glass sheet on the light source side and a rubber sheet on the back side, contact the two and evacuate the air inside with a vacuum pump, and a photoresist mask and resist film inserted between the glass plate and the rubber sheet. (Or a photosensitive film) for exposure after sufficient contact, and various printers such as a horizontal type, a vertical type, a rotary type, a flat type and a conveyor type are known. In the case of an exposure method using a vacuum printer, the time required for evacuation is longer than the time required for normal exposure. In particular, when the size of the material to be processed is large, it comes into close contact with the photoresist mask from the peripheral portion, so that the inside air does not escape and it takes time.

[0005] Exposure conditions vary depending on the material of the substrate used. For example, for a rigid substrate such as glass or a printed circuit board, contact exposure or proximity exposure (a gap of 20 to 80 microns is provided between the mask and the substrate to prevent the mask from being contaminated) because the space between the mask and the substrate can be maintained. Done. In addition, film, aluminum (PS
In the case of a flexible substrate such as a plate or a copper plate (shadow mask) or a mask (when the mask is a film), vacuum contact exposure is performed. In the PS version, U.S. Pat.
The method described in Japanese Patent No. 16,289 addresses the above-mentioned problem by forming fine projections on the surface of the photosensitive layer of the PS plate to form an escape path for air when contact is made. In the case of the PS plate, since the mask is not repeatedly used, it is an economic solution to cope with it by devising the surface of the photosensitive layer.

A shadow mask used for a CRT (Cathode Ray Tube) is formed by etching a steel plate using a photoresist. As the size of the television screen of a CRT increases, the shadow mask used therein also increases, and the evacuation time in the exposure step increases dramatically, thereby significantly reducing the work efficiency.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to reduce the time required for evacuation when exposing a photosensitive film using a vacuum printer, so that the shape of a resist obtained by exposure is not impaired. An object of the present invention is to provide a photoresist mask and a method for manufacturing the same.

[0008]

According to the present invention, (1)
A photoresist mask, wherein a light-shielding pattern and a convex region having a height of 1 μm or more are formed on the surface of the transparent substrate. (2) The convex region forms the light-shielding pattern. (3) The mask for photoresist according to (1), (3) the height of the protrusion in the protrusion region is 1
The photoresist mask according to the above (1) or (2), which has a thickness of from 30 μm to 30 μm;

(4) (1) (a) at least one photopolymerizable monomer having at least one terminal ethylenic group and having a boiling point of 100 ° C. or more under normal pressure; (b) a photopolymerization initiator (C) applying a photopolymerizable composition containing a binder and (d) a light-shielding pigment to the surface of a transparent substrate to form a photosensitive layer, and (2) exposing and developing the photosensitive layer. Forming a light-shielding pattern and a projecting region having a height of 1 μm or more, thereby producing a photoresist mask. (5) (1) A conductive pattern layer on a surface of a transparent substrate (2) forming a light-shielding pattern and a convex region having a height of 1 μm or more on the conductive pattern layer by an electrodeposition method, On the surface of the transparent substrate,
A photoresist mask, wherein a light-shielding pattern and a convex region having a height of 1 μm or more are formed;

(6) (1) A step of forming an opaque metal film by sputtering metal on the surface of a transparent substrate, (2) A step of providing a photosensitive resist layer on the opaque metal film, (3) A step of forming a resist pattern by exposing the photosensitive resist layer to a pattern and developing it; and (4) removing a non-transparent metal film other than the resist pattern by etching to form a light-shielding pattern and a height of 1 μm or more. Forming a convex region, a method for manufacturing a photoresist mask, comprising:
(7) (1) a step of forming an opaque metal film by sputtering metal on the surface of a transparent substrate; (2) a step of providing a photosensitive resist layer on the opaque metal film; Exposing the resist layer in a pattern and developing the resist pattern by developing; (4) removing the opaque metal film other than the resist pattern by etching; and (5) removing the resist on the opaque metal film. Forming a light-shielding pattern, and (6) forming a photosensitive layer on the opaque metal film, exposing the photosensitive layer in a pattern, and developing the light-shielding pattern and a height of 1 μm.
A method of manufacturing a photoresist mask, comprising the step of forming at least m convex regions, to achieve the object of the present invention.

In the photoresist mask of the present invention, by providing a convex region along with a light-shielding pattern on the substrate surface, the non-convex region is reduced when the substrate surface is brought into contact with the photoresist photosensitive layer surface. Since a space is formed between the mask surface and the photoresist photosensitive layer surface, the internal air escapes through the space, and the close contact between the photoresist mask and the photosensitive material is sufficient in a short time. The shape of the resist obtained from the photosensitive layer exposed using the photoresist mask is not impaired.

One of the methods of the present invention for producing a photoresist mask is to form a photosensitive film in which a light-shielding pigment is mixed on a transparent substrate such as glass or plastic, and to expose and develop the light-shielding pattern. And a convex region are formed to obtain a desired mask (hereinafter, also referred to as a first manufacturing method). By using a photopolymerizable monomer as the photosensitive film component, a thick film can be formed. Thus, a mask having sufficient pattern accuracy can be obtained. Another manufacturing method is a method in which a light-shielding pigment dispersed in a resin solution by an electrodeposition method is deposited on a conductive pattern formed in advance on a substrate surface to form a light-shielding pattern and form a convex region. (Hereinafter, also referred to as a second production method). This method also provides a desired film thickness and sufficient light-shielding pattern accuracy. In another manufacturing method, an opaque metal film is first formed by sputtering metal on the surface of a transparent substrate, and a photosensitive resist layer is provided thereon. Next, a resist pattern is formed by exposing and developing the photosensitive resist layer into a pattern, and then the opaque metal film other than the resist pattern is removed by etching to form a light-shielding pattern and a convex region having a height of 1 μm or more. (Hereinafter, also referred to as a third manufacturing method).

Further, in another manufacturing method, after removing the opaque metal film other than the resist pattern as described above, the resist on the opaque metal film is removed to form a light-shielding pattern, and then the opaque metal film is formed. This is a method in which a transparent photosensitive layer is formed on a metal film, and the photosensitive layer is exposed and developed in a pattern to form a light-shielding pattern and a convex region having a height of 1 μm or more (hereinafter, referred to as a fourth manufacturing method). Method).
Hereinafter, the present invention will be described in detail, by which other objects, advantages and effects of the present invention will become apparent.

[0014]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The higher the height of the convex region of the photoresist mask of the present invention, the larger the gap formed in the non-convex region when contacting the photosensitive material. ) Is reduced. However, when the thickness is less than 1 μm, the time required for evacuation can hardly be reduced. On the other hand, if the height of the convex region is too large, the accuracy of the pattern relatively deteriorates.
Therefore, the height of the convex region is naturally limited, and the practical height is preferably 1 to 30 μm, more preferably 2 to 30 μm.
It is 10 μm, more preferably 3 to 8 μm. here,
The height of the protruding area is measured using a stylus type surface profiler, Dektak3
It is the average of the values measured by (manufactured by Japan Vacuum Engineering Co., Ltd.).

As shown in FIG. 1, the shape of the convex region is rectangular (A), semicircular (B), or trapezoidal.
Although (C) and the like can be exemplified, the invention is not limited thereto unless the object of the present invention is impaired. Further, as shown in FIG. 2, the convex region may have a light-shielding pattern itself (a), and (b) the convex region may be formed separately from the light-shielding pattern. (C) the light-shielding pattern may be provided on the convex region, or (d) the convex region may be arbitrarily provided on the light-shielding pattern. Above all, it is preferable that (a) the convex region forms a light-shielding pattern because the convex region can be formed simultaneously with the formation of the light-shielding pattern.

In order to improve the problem of mechanical strength such that the convex region is chipped by an impact or is damaged by repeated contact, after forming the light-shielding pattern and the convex region,
A transparent protective film for increasing mechanical strength can be provided on the entire surface. At this time, the height of the convex region is set to be the height of the protective film surface provided in the convex region with reference to the protective film surface on the substrate surface.

In order to make the convex region hard to be damaged by reducing the frictional force when the convex region comes into contact with the resist film, a slip agent may be present on the surface of the convex region. As a method thereof, there is a method in which a slip agent is applied to the surface after forming the convex region. When the convex region forms a light-shielding pattern, it is added to a photosensitive composition for forming a light-shielding pattern, and the photosensitive composition is applied to a transparent substrate and dried to form a photosensitive film. It can also be carried out by a method of precipitating on the surface of the photosensitive film in the step. here,
Examples of the slipping agent include silicone oligomer and the like, and the protective film can be provided by dissolving the silicone oligomer and the like in a solvent such as propylene glycol monomethyl ether acetate and applying the solution generally at about 1 μm.

Next, a method of manufacturing a photoresist mask according to the present invention will be described with respect to a preferred embodiment in which a convex region forms a light-shielding pattern, but the manufacturing method is not limited thereto.
A person skilled in the art can adopt a desired method according to the type of the light-shielding pattern, the design of the convex region, and the like. First, the first manufacturing method described above, that is, a photosensitive film in which a light-shielding pigment is mixed is formed on a transparent substrate such as glass or plastic, and is exposed and developed to form a light-shielding pattern and a convex portion. A method for forming a region and obtaining a desired mask will be described. The photopolymerizable composition used for forming the photosensitive layer by the above method has a photopolymerizable monomer (a) having at least one terminal ethylenic group and having a boiling point of 100 ° C. or more under normal pressure, Agent (b), binder (c),
And a light-shielding pigment (d).

The photopolymerizable monomer (a) has at least one addition-polymerizable terminal ethylenically unsaturated group,
It is a photopolymerizable monomer having a boiling point of 100 ° C. or more at normal pressure.
Such monomers include, for example, US Pat. No. 3,549,3
No. 67 and the like are disclosed. Specific examples of the monomer include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, Methylolethane tri (meth) acrylate, neopentyl glycol (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, tri Methylolpropane tri (acryloyloxyprooil) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trime After the polyfunctional alcohols such as trimethylolethane by adding ethylene oxide or propylene oxide (meth) those acrylated, JP-B-48-
No. 41708, JP-B-50-6034, JP-A-51-
Urethane acrylates described in JP-A-37193, JP-A-48-64183, JP-B-49
Polyacrylates and methacrylates such as polyester acrylates described in JP-A-43191 and JP-B-52-30490, and epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid are also preferable. Can be mentioned.

Further, the Journal of the Adhesion Society of Japan, Vol. 20. N
o. Compounds introduced as photocurable monomers and oligomers on pages 300 to 308 are also photopolymerizable monomers.
Can be used as (a). The photopolymerizable monomers (a) can be used alone or in combination of two or more. The photopolymerizable monomer (a) is usually 5 to 50% by weight, preferably 10 to 50% by weight, based on the solid content of the photopolymerizable composition.
It is used in a proportion of 40% by weight.

The photopolymerization initiator (b) includes, for example, a trihalomethyl compound. Specific examples of the trihalomethyl compound that can be used include, for example, 2,
4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl 1,3-
(Butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1
-Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl)-
4,6-bis-trichloromethyl-s-triazine, 2
-[4- (2-methoxyethyl) -naphth-1-yl]
-4,6-bis-trichloromethyl-s-triazine,
2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-
Yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4,
6-bis-trichloromethyl-s-triazine, 2-
(6-methoxy-5-methyl-naphth-2-yl)-
4,6-bis-trichloromethyl-s-triazine, 2
-(6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s -Triazine, 2- (4,7-dimethoxy-
Naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphth-2-
Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl)
-4,6-bis-trichloromethyl-s-triazine and the like.

Further, 2- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-
p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6 -Di (trichloromethyl) -s-triazine, 4- [o-methyl-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p -N-chloroethylaminophenyl) -2,6-di (trichloromethyl)-
s-Triazine, 4- (p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (phenyl) aminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s
-Triazine, 4- [p-N- (P-methoxyphenyl) carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (ethoxycarbonylmethyl) Aminophenyl] -2,
6-di (trichloromethyl) -s-triazine, 4-
[M-bromo-p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-p-N, N
-Di (ethoxycarbonylmethyl) aminophenyl]-
2,6-di (trichloromethyl) -s-triazine and the like.

4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN , N-Di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s
-Triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-
Di (trichloromethyl) -s-triazine, 4- [o-
Fluoro-pN, N-di (ethoxycarbonylmethyl)
Aminophenyl] -2,6-di (trichloromethyl)-
s-triazine, 4- [o-bromo-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-
p-N, N-di (chloroethyl) aminophenyl]-
2,6-di (trichloromethyl) -s-triazine, 4
-[O-Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-
Triazine, 4- [m-bromo-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-p-
N, N-di (chloroethyl) aminophenyl] -2,6
-Di (trichloromethyl) -s-triazine, 4- [m
-Fluoro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-p-N-ethoxycarbonylmethylaminophenyl) -2 , 6-di (trichloromethyl) -s-triazine, 4- (m-chloro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine and the like.

Furthermore, 4- (m-fluoro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-p-N-ethoxy) Carbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-p-N-ethoxycarbonylmethylphenyl) -2,6-di (trichloromethyl) -s
-Triazine, 4- (o-fluoro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-p
-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl)- s-Triazine, 4- (m-fluoro-p-N-chloroethylaminophenyl) -2,6
-Di (trichloromethyl) -s-triazine, 4- (o
-Bromo-p-N-chloroethylaminophenyl)-
2,6-di (trichloromethyl) -s-triazine, 4
-(O-chloro-p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-p-N-chloroethylaminophenyl) -2,6 -Di (trichloromethyl) -s-triazine and the like.

The above trihalomethyl compound and the following (1) to (6)
Can be used as the photopolymerization initiator (b). (1) Bicinal polyketo aldonyl compounds disclosed in U.S. Pat. No. 2,367,660. (2) U.S. Pat. Nos. 2,367,661 and 2,36
An α-carbonyl compound disclosed in 7,670. (3) Acyloin ether disclosed in U.S. Pat. No. 2,448,828, U.S. Pat. No. 2,722,51
2. An aromatic acyloin compound substituted with an α-hydrocarbon disclosed in JP-A-2. (4) U.S. Patent Nos. 3,046,127 and 2,95
Polynuclear quinone compounds disclosed in Japanese Patent No. 1,758. (5) Combination of triallylimidazole dimer and p-aminophenyl ketone disclosed in U.S. Pat. No. 3,549,367. (6) Oxadiazole compounds described in U.S. Pat. No. 4,212,976.

The amount of the trihalomethyl compound to be used is generally about 0.2 to 20% by weight, more preferably 0.5 to 15% by weight, based on the photopolymerizable monomer (a). The above used in combination with a trihalomethyl compound
The ratio of the compounds (1) to (6) is preferably from 10 to 800% by weight, more preferably from 20 to 300% by weight, based on the trihalomethyl compound.

The binder (c) is a photopolymerizable monomer
A linear organic high molecular polymer that is compatible with (a), is soluble in an organic solvent, and can be developed with a weak alkaline aqueous solution is preferable. As such a linear organic high molecular polymer, a polymer having a carboxylic acid in a side chain, for example,
-44615, JP-B-54-34327, JP-B-5
Methacrylic acid copolymers, acrylic acid copolymers, and itacones described in JP-A-8-12577, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 and the like. Examples thereof include acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like, and similarly, acidic cellulose derivatives having a carboxylic acid in the side chain. Further, examples of the above-mentioned linear organic high molecular polymer include those obtained by adding an acid anhydride to a polymer having a hydroxyl group. Among them, benzyl (meth) acrylate / (meth) acrylic acid copolymer and benzyl (meth) acrylate / (meth) acrylic acid / multi-component copolymer with other monomers are particularly preferable. The amount of the binder (c) is not particularly limited, but may be 90 to the solid content of the photopolymerizable composition.
If the content is more than 30% by weight, the monomer content relatively decreases, and it becomes difficult to form a pattern. If the content is too small, the monomer content is too large and alkali developability deteriorates.
~ 85% by weight is preferred.

As the light-shielding pigment (d) to be blended in the photopolymerizable composition, carbon black, titanium black,
Nigrosine and the like can be mentioned, and among them, use of carbon black is preferable. The light-shielding pigment (d) is used in an amount of usually 5 to 50% by weight, preferably 10 to 40% by weight, based on the total solid content excluding the pigment.

Further, a thermal polymerization inhibitor may be added to the photopolymerizable composition as an optional component for improving storage stability. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-butyl-
p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-
6-t-butylphenol), 2,2'-methylene (4
-Methyl-6-t-butylphenol), 2-mercaptobenzimidazole and the like are useful. These thermal polymerization inhibitors are generally used in an amount of 500 to the photopolymerizable monomer (a).
About 2000 ppm is added. In many cases, an appropriate amount of a thermal polymerization inhibitor is added to commercially available photopolymerizable monomers (a), and in that case, it is not necessary to further add a thermal polymerization inhibitor.

The above photopolymerizable composition is usually prepared by dissolving and dispersing each component in a solvent to form a solution in which a light-shielding pigment is dispersed.
It is applied on a substrate and dried to form a photosensitive layer.

Examples of the solvent include 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-methoxypropionic acid propyl ester, 3-ethoxypropionic acid methyl ester,
Alkoxypropionic esters such as ethyl ethoxypropionate and propyl 3-ethoxypropionate, 2-methoxypropyl acetate,
Esters of alkoxy alcohols such as ethoxypropyl acetate and 3-methoxybutyl acetate, lactic acid esters such as methyl lactate and ethyl lactate, ketones such as methyl ethyl ketone, cyclohexanone and methylcyclohexanone, other gamma-butyrolactone, N-methylpyrrolidone and dimethyl Sulfoxide and the like are useful,
One type may be used alone, or two or more types may be used in combination. The solvent is preferably used such that the solid content concentration is about 10 to 30% by weight.

The solution of the photopolymerizable composition is prepared by dispersing a pigment such as carbon black using a disperser such as a roll mill, a sand mill, a ball mill or an attritor. At this time, it is preferable to use the same solvent as described above.

As the substrate (support) on which the photosensitive layer is formed, a transparent material such as glass is preferably used.

In order to improve the adhesion between the substrate and the photosensitive layer, various commercially available silane coupling agents or the like were added to the above photopolymerizable composition, or the substrate was previously treated with the silane coupling agent. Thereafter, a solution of the photopolymerizable composition may be applied.

As a method of coating the substrate, a method such as a spinner, a roll coater, a bar coater, and a curtain coater is used. After application, usually 60-130 ° C
At a temperature of 1 to 30 minutes to form a photosensitive layer on the substrate.

The photosensitive layer is exposed to actinic rays, and then subjected to a developing treatment with a developing solution to form a light-shielding pattern, and the formed light-shielding pattern forms a convex region.
As a light source used for the exposure, an ultra-high pressure mercury lamp or the like is usually used. Suitable examples of the developer include an aqueous solution of an alkali metal or alkaline earth metal hydroxide or carbonate, hydrogencarbonate, aqueous ammonia, alkanolamine, and quaternary ammonium salt.
Further, an appropriate amount of a surfactant may be added to the developer for use. After the development processing, the pattern is baked. The bake is at a temperature of 85 to 250 ° C. for 1 to 60 minutes, preferably 200
This is performed at a temperature of about 250 [deg.] C. for about 10 to 60 minutes, thereby forming a light-shielding pattern having a convex region having a predetermined height on the transparent substrate.

Next, a light-shielding pigment dispersed in a resin solution by an electrodeposition method is deposited on a conductive pattern formed in advance on the substrate surface to form a light-shielding pattern. A method for forming the convex region will be described. In the electrodeposition method, the conductive pattern formed on the substrate serves as one electrode. Then, in the electrodeposition liquid tank, a DC voltage is applied between the opposing electrodes, and the ionic resin is deposited on the conductive pattern, and the resin is deposited together with the light-shielding pigment to form a convex region forming a light-shielding pattern. You.

The conductive pattern on the substrate serving as one electrode can be manufactured by a known method. For example, a transparent conductive film such as an ITO film (tin-doped indium oxide film) or a nesa film (antimony-doped tin oxide film) or a transparent conductive film such as aluminum, copper, silver, tin, nickel, etc. is formed on a transparent substrate such as a glass plate. An opaque conductive film is formed. The conductive film is etched according to the shape of the mask or is exposed and developed with a positive resist to expose a region of the mask where a light-shielding pattern is formed.

The material of the plate-shaped conductor used as the counter electrode is not particularly limited as long as it does not react with the electrodeposition liquid. For example, a typical material is stainless steel. The plate-shaped conductor may be plate-shaped, but in order to further improve the flatness of the electrodeposition coating film, a wire mesh is preferable, and the shape may be completely different from that of the substrate. However, it is preferably the same or similar to the substrate. The electrodeposition liquid tank is not particularly limited as long as it is an insulator made of a material capable of holding the electrodeposition liquid. For example, a plastic electrodeposition liquid tank such as hard vinyl chloride or acrylic resin is used.

The electrodeposition liquid is a water-based liquid containing the following ionic resin, light-shielding pigment, surfactant, and ionic compound, and is known per se.

The above-mentioned electrodeposition liquid is put into such an electrodeposition liquid tank, and the substrate and the plate-shaped conductor are placed in parallel so as to face each other. At this time, it is preferable that the substrate is installed so that the center thereof coincides with the center of the plate-shaped conductor. When performing anion electrodeposition, the conductive layer of the above substrate is used as an anode, and the plate-shaped conductor is used as a cathode,
When a DC voltage is applied while oscillating the substrate, a coating film is selectively formed on the conductive layer.

The thickness of the coating film can be controlled by electrodeposition conditions. Electrodeposition conditions are usually 10 to 300 V and about 1 second to 3 minutes. It is desirable that the coating film is thoroughly washed after the formation of the coating film to remove unnecessary substances. If necessary, heat treatment can be performed at 100 to 280 ° C. for 10 to 120 minutes to increase the strength of the coating film.

The ionic resin contained in the electrodeposition solution is as follows:
A water-soluble or water-dispersible polymer resin having an ionic group, which usually has an acidic group such as a carboxyl group in the resin skeleton and is neutralized with a base (eg, organic amine, ammonia). It is dissolved or dispersed in water to be negatively charged (−), and the electrodeposition is used as an anode during electrodeposition coating (anionic), or the resin skeleton has a basic group such as an amino group. Is dissolved or dispersed in water by neutralization with an acid (for example, an organic acid) and charged positively (+), and the object to be coated is used as a cathode during electrodeposition coating (cationic)
It may be a method.

These resins include, for example, conventionally known acrylic resins, epoxy resins, polybutadiene resins, alkyd resins, polyester resins and the like described in Oil Chemistry, Vol. 34, No. 2, pages 1 to 11 (1985). No. Among them, an anionic acrylic resin having an acid group can be preferably used.

The anionic acrylic resin having an acid group is an unsaturated monomer having an acid group (1 to 80% by weight).
It can be easily produced by copolymerizing the unsaturated monomer having an acid group with another unsaturated monomer copolymerizable (20 to 99% by weight) according to a known method. As the acid group, a carboxyl group is preferable, and as the unsaturated monomer having an acid group, well-known acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, maleic anhydride, or derivatives thereof For example, α-carboxy-polycaprolactone monoacrylate, monohydroxyethyl phthalate, acrylic acid dimer, JP-A-62-161742 and JP-A-63-161742.
The reactive acrylic monomer having a carboxyl group described in JP-A-137913 is exemplified. These may be used alone or in combination.

As one of the other unsaturated monomers copolymerizable with the above-mentioned unsaturated monomer having an acid group, a known unsaturated monomer having a hydroxyl group is preferably used. You. The hydroxyl group-containing unsaturated monomer is used, if necessary, in the range of 0 to 50% by weight, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl. Examples include acrylate, 4-hydroxybutyl methacrylate, lactone-modified hydroxyethyl acrylate, lactone-modified hydroxyethyl methacrylate, and derivatives thereof.

Other unsaturated monomers copolymerizable with the above unsaturated monomer having an acid group include conventionally known thermal crosslinks such as methylolated acrylamide compounds and N-methylolalkyletherified acrylamide compounds. Unsaturated monomers are also preferably used. These may be used within the range of 0 to 45% by weight, if necessary. For example, N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N- (n-butoxy) Examples include methylacrylamide, N- (n-butoxy) methylmethacrylamide, N- (isobutoxy) methylacrylamide, N- (isobutoxy) methylmethacrylamide, methylacrylamide glycolate methyl ether, and the like.

As the other copolymerizable unsaturated monomer, conventionally known unsaturated monomers can be used. Some examples thereof include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate and isopropyl acrylate. , Isopropyl methacrylate,
n-butyl acrylate, n-butyl methacrylate,
Isobutyl acrylate, isobutyl methacrylate,
t-butyl acrylate, t-butyl methacrylate,
Examples include n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, styrene, α-methylstyrene, vinyltoluene, vinyl acetate, acrylonitrile, and the like. These are used alone or in combination to obtain desired resin properties such as Tg and solubility (SP).

The acrylic resin composition has a number average molecular weight of 500 to 100,000, more preferably 1,000.
It is in the range of 0 to 50,000. Within this range, after heat curing, the light-shielding layer is excellent in alkali resistance and solvent resistance and easily flows by heating, so that the light-shielding pattern layer can be easily flattened by heat treatment. The acrylic resin may be used alone or in combination with another polymer resin having an ionic group.

As the light-shielding pigment to be added to the above-mentioned electrodeposition solution, those similar to those blended in the photopolymerizable composition such as carbon black, titanium black and nigrosine can be used. preferable. The light-shielding pigment (d) is used in an amount of usually 5 to 50% by weight, preferably 10 to 40% by weight, based on the total solid content excluding the pigment.

Next, a third manufacturing method will be described.
In this method, first, Cr, A is placed on a transparent substrate such as glass.
An opaque metal film is formed by sputtering a metal such as l, Cu or Ni, and a photosensitive resist layer is provided thereon. Here, it is preferable to apply the photopolymerizable composition described in the first production method to the photosensitive resist layer. Next, this resist layer is exposed and developed to form a resist pattern, and portions of the opaque metal film other than the pattern are removed by etching. According to this method, the light-shielding pattern and the convex region are integrated. Formed.

The fourth manufacturing method will be described. In this method, after removing the opaque metal film other than the resist pattern as in the third manufacturing method, the resist on the opaque metal film is removed to form a light-shielding pattern, and then on the opaque metal film. A light-shielding pattern and a height of 1 μm are formed by forming a photosensitive layer, and exposing and developing the photosensitive layer in a pattern.
This is a method of forming a convex region of m or more. According to this method, the light-shielding pattern and the convex region are formed at arbitrary positions, and the convex region is formed on the light-shielding pattern or separately from the light-shielding pattern.

In the manufacturing method described above, since the convex region is formed simultaneously with the formation of the light-shielding pattern, the process is not complicated and economical. Moreover, the obtained photoresist mask can shorten the evacuation time.

[0054]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Parts are parts by weight unless otherwise specified. (Example 1) 12 parts of benzyl methacrylate / methacrylic acid copolymer (molar ratio 70/30, number average molecular weight Mn 20,000) 15 parts of carbon black (MA-100) 20 parts of propylene glycol monomethyl ether acetate 20 parts Kneaded with a roll mill. To the obtained kneaded material, 50 parts of propylene glycol monomethyl ether acetate and 50 parts of ethyl 3-ethoxypropionate were added, and the mixture was dispersed with a dand grinder (Supermill: manufactured by Inoue Seisakusho) (primary dispersion). Next, using glass beads having an average particle diameter of 1 mm, the particles were similarly dispersed by Dynomill (manufactured by Shinmaru Enterprises) (secondary dispersion).

After dispersion, coarse particles such as fragments of glass beads were filtered with a filter having a pore size of 5 μm, and the following components were added to obtain a photopolymerizable composition. Dipentaerythritol pentaacrylate 42 parts 4- [o-bromo-p-N, N-di (ethoxycarbonyl) aminophenyl] 2,6-di (trichloromethyl) -s-triazine] 3 parts 7-[｛4- Chloro-6- (diethylamino) -s-triazin-2-yl {amino] -3-phenylcoumarin 2 parts Hydroquinone monomethyl ether 0.01 parts Propylene glycol monomethyl ether acetate 200 parts

The photopolymerizable composition is applied to a glass substrate for a mask used for exposing a resist for forming a shadow mask of a CRT by a spin coater, and dried at 100 ° C. for 15 minutes to form a uniform film having a thickness of 5 μm. A good coating film was obtained. An exposure light of 300 mj / cm ² was irradiated through a mask using an ultra-high pressure mercury lamp of 2.5 Kw. 0.2
It was developed by immersion in a 5% aqueous solution of sodium carbonate. After drying, it was baked at 230 ° C. for 30 minutes to prepare a photoresist mask of the present invention. The light-shielding pattern and the projection correspond to (A) shown in FIG.

The light-shielding pattern of the photoresist mask was an array of points corresponding to the holes of the shadow mask, and its height was 5 μm from the substrate surface. The mask was combined with a 32 × 42 inch size shadow mask substrate coated with a resist composed of a PVA-diazo photosensitive material, and exposed using a vacuum printer. The time required for the mask and the shadow mask substrate to sufficiently adhere to each other is 3
It was 0 seconds. Further, the obtained shadow mask was excellent in that the pattern was formed on the mask with an accuracy of ± 5 μm.

(Comparative Example 1) Instead of the mask prepared in Example 1, a commonly used silver salt dry plate mask (having no convex region) was used and exposed under the same conditions as in Example 1. did. The time required for evacuation was 150 seconds.

(Example 2) [Preparation of Colorant Dispersion] Deionized water 680 parts SMA-1440A 50 parts (partially esterified styrene / maleic acid copolymer, acid value 185, number average molecular weight Mn 2500, manufactured by Monsanto Co., Ltd.) After adding and stirring 18 parts of triethylamine and dissolving, 250 parts of carbon black was mixed and dispersed with a Dynomill to obtain a dispersion.

[Preparation of Electrodepositing Solution] Anionic acrylic resin * 1500 parts Hexamethoxymethylated melamine 125 parts Triethylamine 38 parts Deionized water 5000 parts is stirred and dissolved, and this is mixed with the above-mentioned dispersion liquid to form an electrodeposition coating composition. (Electrodeposition solution) was prepared. *: Copolymer of methyl methacrylate / lauryl methacrylate / 4-hydroxybutyl methacrylate / methacrylic acid = 33/28/29/10 (wt%)

Next, a positive resist (FH-213 manufactured by Fuji Film Ohlin Co., Ltd.) was applied to a glass substrate (manufactured by Geomatic) having an ITO film (indium-tin oxide) formed on the surface.
0) was applied to a thickness of 2.5 μm by a spinner. 2.
Using an ultra-high pressure mercury lamp of 5Kw, g-line sensitivity is 120mj
/ cm ^{2 was} exposed. Next, the film was developed with a positive resist developing solution FHPD of Fuji Film Ohlin Co., Ltd. to expose the ITO film in the electrodeposited area in a pattern.

The substrate was immersed in the above-mentioned electrodeposition coating composition bath adjusted to 23 ° C., and exposed without any pixels around the substrate.
Electric current was applied at 35 V for 10 seconds using the TO surface as an electrode contact. The substrate was immediately washed with water and dried at 150 ° C. for 15 minutes to form a 5 μm-thick black pattern. Subsequently, the entire surface was exposed to light at 500 mj / cm ² without using a mask, and then subjected to a development treatment to remove the remaining positive resist. After this 250
Baking for 2 hours at ℃, light-shielding pattern on substrate (convex area)
Had a film thickness of 4.5 μm. The light-shielding pattern and the projection correspond to (C) shown in FIG. Using this mask, a resist-coated substrate for a shadow mask was exposed under the same conditions as in Example 1. At this time, the time required for evacuation was 30 seconds. Further, the obtained shadow mask was excellent in that the pattern was formed on the mask with an accuracy of ± 5 μm.

Example 3 A positive resist FH-2 of Fuji Film Ohlin Co., Ltd. was formed on a Cr surface of a glass substrate sputtered with chromium (Cr) of 600 Å.
130 was applied using a roll coater to a dry film thickness of 2 μm and dried. This photosensitive layer was exposed for 50 seconds with a 2.5 Kw ultra-high pressure mercury lamp through a mask for exposing a resist for forming a shadow mask of a CRT. Next, after developing with a positive resist developing solution FHPD of Fuji Film Ohlin Co., Ltd. and washing with running water for 1 minute,
Post-baking was performed on a hot plate at 110 ° C. for 60 seconds. Next, it was immersed in the following etching solution for 1 minute and 30 seconds, rocked, and washed with running water for 1 minute to prepare a photoresist mask of the present invention. The height of the light-shielding pattern of this mask was 2 μm. Etching solution composition: ceric ammonium nitrate 16 parts by weight Ammonium nitrate 7 parts by weight 60% nitric acid 10 parts by weight Pure water 67 parts by weight The photoresist mask is a shadow mask substrate and a film coated with a resist made of PVA-diazo photosensitive material. The surfaces were aligned and exposed using a vacuum printer. 32 × 42
An inch size substrate was used. The time required for the mask and the shadow mask substrate to sufficiently adhere to each other was 50 seconds. Further, the obtained shadow mask was excellent in that the pattern was formed on the mask with an accuracy of ± 5 μm. The light-shielding pattern and the projection correspond to (d) shown in FIG.

Example 4 In Example 3, the entire surface of the developed substrate was exposed and then immersed in a developing solution to remove the resist.
A photosensitive layer having the following composition was applied to the surface of the Cr pattern of the substrate. The substrate was exposed to a 2.5 Kw ultra-high pressure mercury lamp for 30 seconds through an inverted mask for exposing a resist for forming a shadow mask of a CRT. Subsequently, development was performed using a solution obtained by diluting 1 part of a color mosaic developer CD of Fuji Film Ohlin Co., Ltd. with 4 parts of pure water. The height of the obtained transparent pattern was 3.5 μm. Exposure was performed under the same conditions as in Example 1. The time required for evacuation was 35 seconds. The light-shielding pattern and the projection correspond to (b) shown in FIG. [Composition of photosensitive layer] 36 parts of benzyl methacrylate / methacrylic acid copolymer (molar ratio 70/30, average molecular weight Mn 20,000) 36 parts of dithipentaerythritol pentaacrylate 4- [o-bromo-p-N, N-di (Ethoxycarbonyl) aminophenyl] 2,6-di (trichloromethyl) -s-triazine] 2.4 parts Hydroquinone monomethyl ether 0.01 parts Propylene glycol monomethyl ether acetate 136 parts The photoresist mask has a mask region of Cr. Membrane
Protrusions for improving the flow of air for evacuation were formed with a transparent resist pattern, but the same effect was confirmed. The method of this embodiment can be applied to patterns other than the shadow mask since the shape of the protrusion can be freely selected. For example, in the case of a lattice-shaped mask, in the first embodiment, air in the lattice is difficult to escape. In such a case, the method of this embodiment is effective.

(Embodiment 5) Height 5 created in Embodiment 1
A solution having the following composition was spin-coated on a photoresist mask having a black pattern of μm to form a protective film (1 μm thick).
m) was formed. When the mask was used repeatedly, the damage to the pattern edge was reduced, and the friction between the mask and the photosensitive layer was reduced when the vacuum was drawn together with the photosensitive layer, so that the durability of the mask was improved. The pattern accuracy did not deteriorate at all even after 800 exposures. [Solution composition] GR 908 (silicone oligomer: manufactured by Showa Denko KK) 100 parts Propylene glycol monomethyl ether acetate 900 parts

[0066]

By using the photoresist mask of the present invention, the time required for evacuation during exposure can be reduced to about 1/5 and the throughput can be improved without impairing the shape of the obtained resist. Conventionally, it was necessary to install a plurality of exposure machines because the evacuation time was long in the lithography process. However, this is no longer necessary, and investment and installation space can be reduced. Absent.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram showing the shape of a convex region.

FIG. 2 is a schematic sectional view of a convex region of a photoresist mask.

Claims (7)

[Claims] 1. A photoresist mask, wherein a light-shielding pattern and a convex region having a height of 1 μm or more are formed on a surface of a transparent substrate. 2. The photoresist mask according to claim 1, wherein the convex region forms the light-shielding pattern. 3. The height of the projection in the projection region is 1 to 3
The photoresist mask according to claim 1, wherein the thickness is 0 μm. (1) (a) at least one kind of a photopolymerizable monomer having at least one terminal ethylenic group and having a boiling point of 100 ° C. or more under normal pressure, (b) a photopolymerization initiator,
(C) applying a photopolymerizable composition containing a binder and (d) a light-shielding pigment to the surface of a transparent substrate to form a photosensitive layer, and (2) exposing and developing the photosensitive layer. Forming a light-shielding pattern and a convex region having a height of 1 μm or more. 5. A step of (1) providing a conductive pattern layer on the surface of a transparent substrate, and (2) forming a light-shielding pattern and a convex region having a height of 1 μm or more on the conductive pattern layer by an electrodeposition method. A method for manufacturing a photoresist mask, comprising: 6. A step of (1) forming an opaque metal film by sputtering metal on the surface of a transparent substrate; (2)
Providing a photosensitive resist layer on the opaque metal film,
(3) exposing the photosensitive resist layer in a pattern, forming a resist pattern by developing, and
(4) By removing the opaque metal film other than the resist pattern by etching, a light-shielding pattern and a height of 1
forming a protruding region having a thickness of at least μm. 7. A step of forming an opaque metal film by sputtering metal on the surface of a transparent substrate.
Providing a photosensitive resist layer on the opaque metal film,
(3) exposing the photosensitive resist layer in a pattern, forming a resist pattern by developing, and
(4) a step of removing the opaque metal film other than the resist pattern by etching, (5) a step of removing the resist on the opaque metal film to form a light-shielding pattern, and (6) a photosensitive layer on the opaque metal film. Forming a light-shielding pattern and a convex region having a height of 1 μm or more by patternwise exposing and developing the photosensitive layer.