JP2002012796A - Coating resin composition and photomask coated with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating resin composition which is curable even when a radical polymerization inhibit or is attached to the surface of a substrate and can provide a protective film having excellent antistatic ability, hardness, adhesion, UV transparency and water resistance. SOLUTION: The coating resin composition comprises a polymerizable acid phosphate of formula (I): CH2=C(R1)-C(O) [OCH2C(R2)H]n}mOP(O) (OH)3-m (wherein R1 is a methyl group or the like; R2 is hydrogen or the like; m is an integer of 1 or 2; and n is an integer of 1-8), a silane compound of formula (II): X-Si(Z)(Y)-Y (wherein X is a methacryloxyalkyl group or the like; Y is an alkoxy group; and Z is an alkoxy group or the like) (including, e.g. 3- methacryloxypropyltrimethoxysilane), a metal oxide, and a compound having two or more polymerizable unsaturated double bonds (including, e.g. pentaerythritol tetraacrylate).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating resin composition and a photomask having a cured product of the composition as a protective film, and more specifically, a substance which inhibits radical polymerization from adhering to a substrate. And has a sufficient antistatic ability, high hardness, good adhesion, high UV transmittance, and a resin composition for coating capable of providing a protective film having good water resistance. Related to a photomask.

[0002]

2. Description of the Related Art In a manufacturing process of a printed wiring board or a shadow mask, a photosensitive resin is irradiated with ultraviolet light (hereinafter referred to as "U") through a glass or polyethylene terephthalate photomask.
V ". ). In the exposure step, only the portion irradiated with UV is selectively insoluble or soluble in the developer, so that a resin pattern having a desired shape can be duplicated. Here, since the image of the photomask has a fine line width and interval of several tens to several hundreds of μm, if the image of the photomask is damaged, it appears as a shadow on the photosensitive resin, and the desired image is formed. Is not obtained, resulting in a defective product. Therefore, it is required that the surface of the photomask be covered with a protective film having scratch resistance to prevent the image from being damaged. This protective film needs to have high hardness in order to prevent scratching and high UV transmittance. In the case of a protective film having a low UV transmittance, the intensity is reduced before UV is absorbed by the protective film and reaches the photosensitive resin, so that it is necessary to lengthen the exposure time, which leads to a decrease in productivity.

Furthermore, if dust adheres to the photomask, it appears as a shadow on the photosensitive resin, so that a desired image cannot be obtained. For this reason, it is desired that the protective coating has an antistatic property in order to prevent the adhesion of dust, in addition to the high hardness. As a means for imparting the antistatic ability to the protective film, a method of adding and mixing a surfactant, a method of applying a partial hydrolyzate of a silicate compound, or a method of adding a conductive filler are conventionally known. . However, the addition of a surfactant has the disadvantage that the surfactant on the bleed-out surface drops off by washing with water or the like, and that the adhesion to the substrate is reduced. Silicon compound is applied on the protective film once formed,
A curing step is required. The addition of the conductive filler
Insufficient transparency and expensive. On the other hand, there has been reported a method of imparting an antistatic ability to a protective film by copolymerizing a monomer having an antistatic ability. For example, in JP-A-56-139516, polyalkylene glycol monomethacrylate is used as a monomer having an antistatic function. Since copolymerization is performed, the problem of falling off due to washing with water is solved, but polyalkylene glycol monomethacrylate has a low antistatic effect, requires a large amount of addition, and causes deterioration of other physical properties.

Examples using polymerizable acidic phosphoric acid esters are disclosed in JP-A-61-73709 and JP-A-61-788.
No. 07, No. 62-207358, and JP-A No. 64-62.
No. 316, JP-A-4-67731 and JP-A-4-30
No. 9568. Sufficient antistatic ability can be obtained with less addition of the polymerizable acidic phosphoric acid ester than the polyalkylene glycol monomethacrylate. However, the addition of such an amount that provides a sufficient antistatic ability deteriorates the water resistance of the protective coating. Conversely, the addition of a small amount has a problem that the antistatic ability becomes insufficient. Therefore, various devices have been devised so that a sufficient antistatic ability can be obtained by using a polymerizable acidic phosphate and another additive in combination. JP-A-57-
No. 65761, a nonionic surfactant is used in combination, JP-A-1-168771 uses a nonfunctional phosphate ester, and JP-A-50-109944 uses a sulfonic acid in combination. However, the addition of a non-functional nonionic surfactant, non-functional phosphate ester, or sulfonic acid not only tends to cause unevenness during curing, but also falls off the protective coating due to washing with water or the like, and has an antistatic property. In addition, there is a problem that the hardness is lowered.

As an attempt to improve the hardness, Japanese Patent Application Laid-Open
In -95951, a combined use of colloidal silica is proposed. According to this, the hardness of the protective film immediately after curing is high. However, in addition to the problem of adhesion, there is a problem that the resin becomes brittle when left under high humidity due to low water resistance. Furthermore, the above resin composition has no problem in adhesion to the substrate as long as it has a relatively low hardness, but when a high hardness film is formed, the adhesion to the substrate is insufficient. Was. Therefore, there has been a demand for a resin composition for coating capable of providing a protective film having sufficient antistatic ability, high hardness, good adhesion, high UV transmittance, and good water resistance. The authors disclosed in Japanese Patent Application Laid-Open No. 11-80.
594, comprising a resin composition for coating capable of providing a protective coating having sufficient antistatic ability, high hardness, good adhesion, high UV transmittance, and good water resistance, and the composition A photomask having a protective film has been proposed. However, if a substance that inhibits radical polymerization such as a dye component used for coloring or discriminating a substrate or hydroquinone used for developing a photographic plate adheres to the substrate surface, there is room for improvement in curability. there were.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances. Even when a substance that inhibits radical polymerization adheres to the surface of a substrate, it is sufficiently cured and has sufficient antistatic properties. A resin composition for coating capable of providing a protective film having high performance, high hardness, good adhesion, high UV transmittance, and good water resistance, and a photomask having the protective film. And

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to overcome various drawbacks as pointed out in the conventional resin compositions for coatings. By using a metal oxide dispersion in which a specific silane compound and a metal oxide having an average primary particle size of 8 to 100 nm are dispersed in an organic solvent, a substance that inhibits radical polymerization adheres to the substrate surface. Even if it does, it cures enough,
Sufficient antistatic ability, high hardness, good adhesion, high UV
The inventors have found that a protective film having a high transmittance and good water resistance and a photomask having the protective film can be easily obtained, thereby completing the present invention. That is, the coating resin composition of the first invention comprises a polymerizable acidic phosphate (A) represented by the formula (I), a silane compound (B) represented by the formula (II), and primary particles. Has an average particle size of 8 to 10
0 nm and a metal oxide (C) dispersed in an organic solvent, and an organic compound (D) having two or more polymerizable unsaturated double bonds in one molecule. Component (A) is 10 to 40% by weight, component (B) is 3 to 30% by weight, component (C) is 1.5 to 15% by weight, and component (D) is 25 to 82% by weight. There is a feature. The resin composition for coating of the second invention is characterized in that the metal oxide in the first invention is silica. The photomask of the third invention is characterized in that it is coated with a cured product of the coating resin composition of the first invention or the second invention.

The above "polymerizable acidic phosphate" (A)
Has a coating resin composition of the present invention mainly has an antistatic ability.
It is intended to provide. Formula (I)
As a specific example, CH_Two= CHCOOCH_TwoCH_TwoOP
(O) (OH)_Two, CH_Two= C (CH_Three) COOCH_TwoCH
_TwoOP (O) (OH)_Two, CH_Two= C (CH_Three) COOCH
_TwoCH (CH_TwoCl) OP (O) (OH)_Two, (CH_Two= C
HCOOCH_TwoCH_TwoO)_TwoP (O) OH, (CH_Two= C
(CH_Three) COOCH_TwoCH _TwoO)_TwoP (O) OH, CH_Two
= C (CH_Three) CO (OCH_TwoCH_Two)_FourOP (O) O
H_Two, CH_Two= C (CH_Three) CO (OCH_TwoCH_Two)_FiveOP
(O) (OH)_Two, CH_Two= C (CH_Three) CO (OCH_TwoC
H (CH_Three))_FiveOP (O) (OH)_TwoAnd CH_Two= C (C
H_Three) CO (OCH_TwoCH (CH_Three))₆OP (O) (O
H)_TwoAnd the like, and these may be used for two or more kinds if desired.
Can be. Among them, CH_Two= C (C
H_Three) COOCH_TwoCH_TwoOP (O) (OH)_TwoAnd (CH
_Two= C (CH_Three) COOCH_TwoCH_TwoO)_TwoP (O) OH
It is preferable in terms of compatibility and hardness. In the present invention,
Mixing ratio of these polymerizable acidic phosphates in the composition
Is preferably 10 to 40% by weight, and 15 to 25% by weight
More preferred. If the content is less than 10% by weight, the protective film has an antistatic property.
The stopping ability tends to be insufficient, and an amount exceeding 40% by weight is added.
When added, coloring occurs with curing and UV transmittance decreases.
In addition, hardness and water resistance tend to decrease.
I don't.

The above-mentioned “silane compound” (B) is represented by the following formula (II) and improves the adhesion to a substrate,
At the same time, deterioration of water resistance due to the addition of the polymerizable acidic phosphate is improved, and the hardness of the cured coating film is further increased. X-Si (Z) (Y) -Y (II) (In the above formula, X represents an organic group having an ethylenically unsaturated double bond, Y represents an alkoxy group, and Z represents an alkoxy group or an alkyl group.) In the formula, “X” includes organic groups such as a methacryloxyalkyl group, an acryloxyalkyl group, and a vinyl group. In particular, the methacryloxyalkyl group and the acryloxyalkyl group have an alkyl group having 2 carbon atoms.
To 4 are preferable. The alkoxy group as “Y” preferably has 1 to 3 carbon atoms. The number of carbon atoms of each of the alkoxy group and the alkyl group as “Z” is preferably 1 to 3. Specifically, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane,
3-methacryloxypropylmethyldimethoxysilane,
Vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tris (2-methoxy ethoxy) silane and the like can be mentioned. Among these, 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane are preferred in terms of adhesion, water resistance, and hardness. The mixing ratio of these silane compounds in the composition of the present invention is 3 to 30% by weight, preferably 5 to 20% by weight. If the amount is less than 3% by weight, the effect of improving the adhesion to the substrate, improving the water resistance and the hardness is low, and is 30% by weight.
If the amount exceeds the above range, it is difficult to obtain a smooth coating film due to phase separation, and the antistatic ability is undesirably reduced.

[0010] The metal oxide contained in the above-mentioned "metal oxide dispersed in an organic solvent" (C) is used to sufficiently cure even if a substance inhibiting radical polymerization adheres to the substrate. Things. If the average particle size of the primary metal oxide particles is less than 8 nm, the aggregation between the metal oxide particles is so strong that it is difficult to obtain a uniform coating film. If the average particle size exceeds 100 nm, the transparency is undesirably reduced. In particular,
A metal oxide having an average particle size of primary particles of 8 to 100 nm is obtained by converting methanol, isopropyl alcohol, n-butanol,
Colloidal metal oxides dispersed in one or more organic solvents such as ethylene glycol, ethylene glycol mono n-propyl ether, methyl ethyl ketone, methyl isobutyl ketone, dimethylacetamide and xylene can be mentioned. Among these, a colloidal metal oxide dispersed in isopropyl alcohol, methyl ethyl ketone, or methyl isobutyl ketone is preferable because a uniform coating film is easily obtained. Preferred metal oxides are silica, alumina, zirconia, zinc oxide, antimony oxide, bismuth oxide and tin oxide, among which silica is particularly preferred. In the first invention, the mixing ratio of the metal oxide (C) in the composition is 1.5 to 1.5.
15% by weight, preferably 2 to 10% by weight, and 4 to 9%.
% Is more preferred. When the amount is less than 1.5% by weight, the effect of sufficiently hardening is low when the substance that inhibits radical polymerization is attached to the substrate, and when the amount exceeds 15% by weight, it is difficult to obtain a smooth coating film. It is not preferable because there is a tendency.

The above (D) “Polymerizable unsaturated double in one molecule”
Organic compound having two or more bonds ”(hereinafter referred to as“ organic compound
Also called "things." ) Is for higher hardness
It is. This “polymerizable unsaturated double bond” includes heavy
Although it is not particularly limited as long as it is compatible, acryloyl
Or a methacryloyl group. Also this sensuality
The number of groups per molecule is preferably about 3 to 6. Furthermore,
The molecular weight of this organic compound is preferably from 200 to 10,000.
And 200 to 5000 is more preferable. Heavy in one molecule
Examples of organic compounds having two compatible unsaturated double bonds
Is bisphenol A ethylene oxide-modified diacryle
Oxide, isocyanuric acid ethylene oxide modified oxide
Diacrylate, polyethylene glycol diacryle
Methacrylate and / or methacrylate
And / or methacrylate ”as“ (meth) acrylic
Rate. ), Polypropylene glycol di
(Meth) acrylate, hexamethylene glycol di
(Meth) acrylate, dimethylol tricyclodecane
Diacrylate, trimethylolpropane di (meth) a
Acrylate, pentaerythritol di (meth) acryle
Glycerin di (meth) acrylate, dipentae
Lithritol di (meth) acrylate, bisphenol
A-type epoxy resin with epoxy group and acrylic acid and / or
Or methacrylic acid (hereinafter referred to as “(meth) acrylic acid”)
You. ) Epoxy (meth) acrylate
Can be

On the other hand, examples of the organic compound having three or more polymerizable unsaturated double bonds in one molecule include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and glycerin tri (meth) acrylate. Acrylate, dipentaerythritol tri (meth) acrylate, tris (acryloxyethyl) isocyanurate and / or tris (methacryloxyethyl) isocyanurate (hereinafter “acryloxy and / or
Alternatively, “methacryloxy” is referred to as “(meth) acryloxy”. ), Pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, an epoxy resin epoxy group and (meth) acrylic acid Epoxy (meth) acrylates, epoxy (meth) acrylates composed of polyglycidyl ether of polyhydric alcohol and (meth) acrylic acid, urethane acrylate of polyhydric alcohol, and the like are included. Two or more of these can be used as desired. Among these, dipentaerythritol hexa (meth) acrylate or pentaerythritol tetra (meth) acrylate is preferred in terms of hardness.

As the organic compound (D) in the present invention,
It is preferable that an organic compound having two polymerizable unsaturated double bonds and an organic compound having three or more polymerizable unsaturated double bonds are used in combination. The cured product of the above composition has improved adhesion to a substrate. The compounding ratio of the organic compound (D) in the composition of the present invention is 25 to 82% by weight, preferably 30 to 70% by weight, and more preferably 30 to 55% by weight. If it is less than 25% by weight, the hardness of the coating tends to decrease, and if it exceeds 82% by weight, sufficient antistatic ability and adhesiveness tend not to be obtained, which is not preferable.

The composition of the present invention may contain, if desired, a reactive diluent, a polymerization initiator, a solvent, a leveling agent, an antifoaming agent or a thermal polymerization inhibitor, etc., to impart various properties to the coating resin composition of the present invention. It is also possible to add it within a range that does not significantly reduce it, and the present invention is not limited. The reactive diluent is
The purpose is to improve applicability and workability.
An organic compound having one polymerizable unsaturated double bond in the molecule. Specific examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, -(Meth) acryloyloxyethylhexahydrophthalic acid and N-vinylpyrrolidone.

The thermal polymerization initiator or the photopolymerization initiator is added for applying the resin composition of the present invention to the surface of a substrate and crosslinking and curing the composition to form a film.
Specific examples of the thermal polymerization initiator include (1) benzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, cumene hydroperoxide, and terpolymer.
peroxides such as t-butyl peroxyisopropyl monocarbonate; (2) azobisisobutyronitrile;
An azo compound such as 2-azobis (2,4-dimethylvaleronitrile) is exemplified. Specific examples of the photopolymerization initiator include (1) 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1- (4-isopropylphenyl)
-2-hydroxy-2-methyl-1-propanone, 2-
Acetophenones such as methyl-1- (4- (methylthio) phenyl) -2-morpholino-1-propanone, 1-hydroxycyclohexylphenylketone, and benzyldimethylketal; (2) diketones such as phenylmethoxydiketone; 3) Combined use of isopropylthioxanthone and ethyl p-dimethylaminobenzoate, 2,4
Thioxanthone systems such as a combination of diethylthioxanthone and ethyl p-dimethylaminobenzoate. The amount of these polymerization initiators added to the coating resin composition of the present invention is 0.1 to 20% by weight, preferably 1 to 10% by weight. Further, a thermal polymerization initiator and a photopolymerization initiator can be used in combination. Apart from this, it is also possible to carry out curing with an electron beam. In this case, these polymerization initiators are unnecessary.

The coating resin composition of the present invention is diluted with a solvent, if necessary, in order to improve coating properties, improve workability, and adjust the thickness of the protective coating. In particular, when importance is placed on the transmittance of the protective film in order to shorten the exposure time when using a photomask, it is preferable to dilute with a solvent and adjust the thickness of the protective film to be thin. Specific examples of such a solvent include:
(1) alcohols such as ethanol, isopropanol, normal propanol, isobutyl alcohol, normal butyl alcohol, methyl cellosolve, and propylene glycol monomethyl ether; (2) aromatic hydrocarbons such as toluene and xylene; (3) acetone and methyl ethyl ketone; Ketones such as methyl isobutyl ketone and cyclohexanone; (4) ethers such as dioxane;
(5) Esters such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate. However, depending on the type of the base material, the solvent may damage the base material. Therefore, it is preferable to use the solvent appropriately selected depending on the type of the base material. The coating resin composition used in the present invention can be easily prepared by mixing the above components.

The thickness of the protective film formed in the present invention is usually 0.5 to 10 μm, preferably 0.7 to 5 μm,
More preferably, it is 1 to 3 μm. If the thickness is less than 0.5 μm, it is difficult to obtain sufficient antistatic ability and abrasion resistance, and if the thickness exceeds 10 μm, the transmittance tends to decrease, which is not preferable. The thickness of the protective coating can be arbitrarily changed by adjusting the solid content concentration of the resin composition.

[Action] Obtained from the coating resin composition of the present invention
Protective film and photomask having the protective film
Blends a specific polymerizable acidic phosphate (A)
It has excellent antistatic ability. Specific silane compounds
Since (B) is blended, it has excellent water resistance and hardness. Ma
The primary particles have an average particle size of 8 to 100 nm and have
Contains metal oxide (C) dispersed in organic solvent
Therefore, substances that inhibit radical polymerization
However, it can be sufficiently cured. Furthermore, in one molecule
Having two or more polymerizable unsaturated double bonds
Because (D) is blended, higher hardness can be obtained.
Can be. Hydrate with phenolic hydroxyl group
If roquinone or a compound that becomes a dye adheres to the substrate
If so, it acts as an inhibitor of radical polymerization,
Radical polymerization of polymerizable unsaturated double bonds does not progress
That was the way of thinking so far. However, the present invention
In addition, the components (A), (B), (C) and (D)
By blending at a characteristic ratio, coating can be performed only by reaction of metal oxide.
Instead of curing the film, the polymerizable unsaturated double bond
It was found that the dical polymerization also proceeded and was cured.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the coating resin composition of the present invention and a photomask coated with the same will be specifically described with reference to Examples and Comparative Examples. The specification of the materials used in each example and each comparative example is shown below. (A) Polymerizable acidic phosphoric acid ester “Phosmer M”: manufactured by Unichemical Corporation, 2-methacryloyloxyethyl acid phosphate “KAYAMER PM-2”: manufactured by Nippon Kayaku Co., Ltd., 2-methacryloyloxyethyl acid Phosphate "Phosmer PE": manufactured by Unichemical Co., Ltd., acid phosphooxypolyoxyethylene glycol monomethacrylate "Light Ester PA": manufactured by Kyoeisha Chemical Co., Ltd., 2
-Acryloyloxyethyl acid phosphate (B) silane compound "KBM-503": manufactured by Shin-Etsu Chemical Co., Ltd., 3-
Methacryloxypropyltrimethoxysilane “KBE-503”: manufactured by Shin-Etsu Chemical Co., Ltd., 3-
Methacryloxypropyltriethoxysilane "KBM-1003": Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane "A-174": Nippon Unicar Co., Ltd., 3-methacryloxypropyltrimethoxysilane (C) silica dispersion MIBK-ST ": Nissan Chemical Industries, Ltd., methyl isobutyl ketone dispersion containing primary particles 10 to 20 nm in diameter and 30 wt% as silica" IPA-ST ": Nissan Chemical Industries, primary particle diameter 10 Isopropyl alcohol dispersion containing 30 to 20 nm as silica and 30 wt% as silica "MEK-ST": Nissan Chemical Industries, Ltd., methyl ethyl ketone dispersion as primary particles having a particle size of 10 to 20 nm and containing 30 wt% as silica (D) Polymerization in one molecule Three or more unsaturated double bonds (
-) Or an organic compound having two () "Aronix M-450": manufactured by Toagosei Co., Ltd.
Pentaerythritol tetraacrylate "Aronix M-400": manufactured by Toagosei Co., Ltd.
Mixture of dipentaerythritol penta and hexaacrylate “Aronix M-305”: manufactured by Toagosei Co., Ltd.
Pentaerythritol triacrylate “Lipoxy SP-1509”: Bisphenol A type epoxy acrylate (E) and others (thermal polymerization initiator) manufactured by Showa Polymer Co., Ltd. “Park Mill D”: Dicumyl peroxide “Niiper BMT” manufactured by NOF Corporation ": Benzoyl peroxide (solvent, etc.) manufactured by NOF Corporation" PGM ": propylene glycol monomethyl ether" PGMAc ": propylene glycol monomethyl ether acetate" MEK ": methyl ethyl ketone

Example 1 (1) Preparation of Resin Composition for Coating and Evaluation of Performance of Protective Coating As shown in Table 1 below, 20 parts of polymerizable acidic phosphoric acid ester “phosmer M” and silane compound “KBM” -503 "1
0 parts, 25 parts of a silica dispersion “MIBK-ST”, 45 parts of an organic compound “Aronix M-450” having four polymerizable unsaturated double bonds in one molecule, and 5 parts of a thermal polymerization initiator “Parkmill D” , A solvent "PGMAc" (900 parts) and a fluorine-based leveling agent (1 part) were mixed to prepare a coating resin composition. The numbers in parentheses in the column of “Silica dispersion” in Table 1 indicate the amount of silica solids. The same applies to Table 3 (Comparative Examples 1 to 7). On the other hand, a solution of hydroquinone was dropped on a part of a glass substrate having a thickness of 2 mm and dried to prepare a glass substrate to which hydroquinone was attached. A coating resin composition was applied on the glass substrate by a spin coater so that the thickness of the protective film became 2 μm, and the coating was maintained at 180 ° C. for 15 minutes to obtain a protective film. The curability of this protective coating,
In order to examine the antistatic ability, hardness, adhesion, water resistance and transparency, the following methods are used for appearance, surface resistance, pencil hardness,
The Goban test, the water resistance test, and the evaluation of the UV transmittance were performed, and the evaluation results are shown in Table 2.

[0021]

[Table 1]

[0022]

[Table 2]

(Appearance) The appearance of the protective film was visually evaluated. In addition, in the evaluation of the appearance, those with severe irregularities were not subjected to other performance evaluations. (Surface resistance value) JISK691
The measurement was performed in an environment of 25 ± 2 ° C. and 65 ± 5% according to 1. (Pencil Hardness) The pencil hardness of the protective film was measured using Mitsubishi Pencil Uni according to JIS K5400. (Goban eye test) Evaluation of adhesion of protective film by JISK
The test was performed according to the 5400 Goban test. Judgment is 10
It shows how many of the zero goban were adhered. (Water resistance) The water resistance of the protective coating was evaluated by observing the appearance after immersing the protective coating in water for 1 hour. (UV transmittance) The UV transmittance of the protective film was measured by measuring the transmittance of the substrate on which the protective film was formed using UV light (wavelength: 365 nm) and setting the transmittance of the substrate alone to 100%. Evaluation was made by obtaining a converted value.

(2) Photoresist patterning A chromium thin film layer is formed on a glass substrate, and is further subjected to resist formation, patterning, etching and resist peeling.
A glass substrate on which a chromium thin film pattern was formed was formed.
A hydroquinone solution was dropped on this part and dried to prepare a photomask to which hydroquinone was attached. On this, the coating resin composition was applied by a spin coater so that the protective film became 2 μm, and kept at 180 ° C. for 15 minutes to obtain a photomask having the protective film. Negative photoresist “PERM” is applied to copper-clad laminate
N-HC40 "(manufactured by Toagosei Co., Ltd.) was applied using a bar coater, and dried at 90 ° C. for 5 minutes.
A μm resist film was obtained. Next, using a photoresist double-side baking machine “HTE-106S” (manufactured by Hitec Co., Ltd.), the above-described photomask was vacuum-adhered on the above-mentioned resist film, and exposed with a 5 kW ultra-high pressure mercury lamp. The exposure amount was 200 mJ / cm2, and the exposed portion was cured. Using a conveyor type spray developing machine (manufactured by Kimura Etching Laboratories Co., Ltd.), the unexposed portions of the thus obtained resist film were dissolved and removed with a 1% aqueous sodium carbonate solution. Evaluation was made by observing the appearance of the photomask used and the appearance of the resist film on which the pattern was formed, and the results are also shown in Table 2.

Examples 2 to 4 Polymerizable acidic phosphate, silane compound and primary particles having an average particle size of 8 to 100 n
m, silica dispersed in an organic solvent, an organic compound having two or more polymerizable unsaturated double bonds in one molecule, and those described in Table 1 as other components. The resin composition was prepared so as to have the ratio shown in Table 1. Next, this composition was applied on a substrate in the same manner as in Example 1 to obtain a protective film. This protective film was evaluated in the same manner as in Example 1, and a photoresist was patterned in the same manner as in Example 1 using a photomask coated with the present protective film. The evaluation results are also shown in Table 2.

(Comparative Examples 1 to 7) The average particle size of the polymerizable acidic phosphate, silane compound and primary particles is 8 to 100 n.
m, silica dispersed in an organic solvent, silica, an organic compound having two or more polymerizable unsaturated double bonds in one molecule, and those described in Table 3 below as other components,
Each of Comparative Examples 1 to 7 was blended so as to have a ratio shown in Table 3.
Was prepared. Next, each of the compositions was applied on a substrate in the same manner as in Example 1 to obtain a protective film. This protective film was evaluated in the same manner as in Example 1, and a photoresist was patterned in the same manner as in Example 1 using a photomask coated with the present protective film. The evaluation results are also shown in Table 2. still,
The parentheses in the column of “(C) silica dispersion” in Table 3 are the solid content of silica. “*” In Table 2 indicates a component that is not included in the scope of the present invention.

[0027]

[Table 3]

(Effects of Examples) According to the results in Table 2, in Comparative Example 1 in which no polymerizable acidic phosphate was blended, the surface resistance was high and the antistatic ability was low. vice versa,
In Comparative Example 2 in which the content of the phosphate ester was as large as 50 parts, the surface resistance was low and the antistatic ability was excellent, but the appearance was colored yellow, the hardness was low, and the UV transmittance was as low as 83%. And the photomask is scratched. In Comparative Example 3 in which the silane compound was not blended, the adhesiveness was 0/100 in the Goban test and the water resistance was low. Conversely, in Comparative Example 4 in which the blending amount of the silane compound was as large as 40 parts, phase separation occurred, a smooth coating film was not obtained, and the appearance was uneven. In Comparative Example 5 in which the silica dispersion was not blended, there were some uncured parts in appearance. Conversely, in Comparative Example 6 in which the blending amount of the silica dispersion was as large as 60 parts, a smooth coating film was not obtained, and the appearance was uneven. In Comparative Example 7 in which the amount of the organic compound having two or more polymerizable unsaturated double bonds was as small as 10 parts, the hardness was low and the photomask was scratched. On the other hand, in all of Examples 1 to 4, the appearance was good and cured sufficiently,
Since the surface resistance is as low as 2 × 10 ¹² Ω to 3 × 10 ¹² Ω, it shows excellent antistatic ability, and the Goban test is also 100%.
/ 100, excellent adhesion, good water resistance, high UV transmittance of 90 to 92 (%), no scratches on the photomask appearance, and good resist appearance . From the above, it can be seen that the coating resin compositions of Examples 1 to 4 and the photomasks coated with the coating resin compositions have a very excellent performance balance.

[0029]

The resin composition for coating of the present invention and the photomask coated with the same can be prepared by blending a specific polymerizable acidic phosphate, a specific silane compound and a metal oxide dispersion. Even if a substance that inhibits radical polymerization adheres to the surface of the material, it can be sufficiently cured. Furthermore,
According to the present invention, a coating resin composition having sufficient antistatic ability, high hardness, good adhesion, high UV transmittance, and excellent water resistance, and a protective coating comprising the composition are provided. A photomask having the same can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/00 C09D 5/00 Z G03F 1/14 G03F 1/14 EF term (Reference) 2H095 BB30 BC20 4J011 AA05 PA13 PB22 PC02 PC08 WA01 4J027 AC03 AC04 AC06 AC09 AE02 AJ02 AJ08 BA04 BA19 BA26 BA28 CA18 CA36 CB03 CB09 CB10 CD08 4J038 FA012 FA112 FA211 HA216 HA446 4J100 AL08P AL08Q AL62R AL63R AL66R BA08PBA BCBC

Claims (3)

[Claims] 1. A polymerizable acidic phosphorus represented by the following formula (I):
Acid ester (A), silanization represented by the following formula (II)
Compound (B), the average particle size of the primary particles is 8 to 100 nm
And a metal oxide (C) dispersed in an organic solvent, and
Organic having two or more polymerizable unsaturated double bonds in one molecule
It consists of compound (D), and each compounding ratio is above (A)
The component is 10 to 40% by weight, and the component (B) is 3 to 30% by weight.
%, The component (C) is 1.5 to 15% by weight, and
(D) Component is 25 to 82% by weight.
Resin composition for coating. (CH_Two= C (R₁) -C (O) (OCH_TwoC (R_Two) H)_n)_mOP (O) (OH) _3-m (I) (where R is₁Is hydrogen or a methyl group, R_TwoIs hydrogen, methyl
A group or a halogenated methyl group, m is an integer of 1 or 2, n is
Shows an integer of 1 to 8. X-Si (Z) (Y) -Y (II) (where X is an organic compound having an ethylenically unsaturated double bond)
Group, Y is an alkoxy group, Z is an alkoxy group or alkyl
Represents a group. ) 2. The coating resin composition according to claim 1, wherein the metal oxide is silica. 3. A photomask coated with a cured product of the resin composition for coating according to claim 1 or 2.