JP2000256585A - Hardenable composition for lining at the time of production of shadow mask - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hardenable composition for lining at the time of production of a shadow mask, capable of providing a hardened membrane excellent in each of etching resistance, alkali-dissolvable and peelable properties, and pattern-forming properties even in the case of carrying out secondary etching at high temperature. SOLUTION: This hardenable composition for lining in a secondary etching step when producing a shadow mask comprises (a) a compound having one carboxyl group and one (meth)acryloyl group in the molecule, (b) a compound having five or more (meth)acryloyl groups and no alkylene oxide unit in the molecule, and (c) a compound having two or more (meth)acryloyl groups and the alkylene oxide unit in the molecule, and the hardened membrane has an alkali-dissolvable properties and an alkali-peelable properties.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of coating a metal plate having fine irregularities without causing air bubbles and curing it by heating or irradiating an active energy ray such as an ultraviolet ray or an electron beam. The cured film shows corrosion resistance to acid treatment and dissolves or peels off to alkali treatment (hereinafter referred to as "dissolution and peeling off"). It relates to a curable composition.

[0002]

2. Description of the Related Art A shadow mask has a function of causing electrons emitted from an electron gun in a cathode ray tube for a color television to collide with a light emitter of a predetermined color, and has a rectangular hole, a rectangular elongated hole (aperture). It is a thin metal plate in which a large number of fine holes such as grill type or circular holes are provided in a predetermined pattern by etching. These shadow masks used for CRTs of personal computers and the like have circular holes, and those used for high-resolution or high-brightness televisions have rectangular elongated holes (aperture grill type). There is a demand for higher precision holes. As a method for manufacturing such a shadow mask, a concave portion is provided by primary etching at a corresponding position on both the front and back surfaces of a metal plate, a cured film of the backing material composition is formed on one surface thereof, and then a further 2 steps are performed. A method of performing subsequent etching to connect the bottoms of the corresponding concave portions to each other is performed.

The manufacturing process of such a shadow mask will be described in more detail. First, a photosensitive resin is applied to the front and back surfaces of a thin metal plate made of iron or the like, and then a negative film on which a pattern is arranged is brought into close contact with the metal plate. Then, photographic printing is performed to cure the exposed portion of the photosensitive resin, and a non-photosensitive portion of the photosensitive resin film is removed by a developing process. Next, primary etching is performed with a corrosive liquid such as iron perchlorate to form fine hemispherical concave portions having a diameter of 100 to 200 μm that do not penetrate each other from both the front and back surfaces. The curable composition for a backing material is applied to only one side of the metal plate after the primary etching, and the composition is cured by irradiating active energy rays such as ultraviolet rays or heating, and the fine particles on one side of the metal plate are cured. A cured film is formed to fill the concave portions. After protecting one side in this way, secondary etching is again performed on the concave portion on the other side with a corrosive liquid,
The concave portion on one side and the concave portion on the other side are made to communicate with each other at the bottom by the primary etching, and then each cured film of the photosensitive resin for pattern formation and the curable composition for the backing material is removed by alkali treatment. And get a shadow mask.
Here, when a hole is formed only by the primary etching by performing the secondary etching using the curable composition for a backing material, an abnormally large hole or a distorted hole is formed, and the accuracy of the hole is reduced. The problem of lowering can be solved.

In such a method of manufacturing a shadow mask, a curable composition for a backing material applied after primary etching is required to satisfy the following characteristics. Hole-filling property: The property of uniformly wetting the surface of a material having a hemispherical concave part having a diameter of 50 to 200 μm or an elongated rectangular concave part having a width of 50 to 200 μm and a length of 10 to 200 cm, and filling the concave part without generating bubbles in the concave part. Surface smoothness: air bubbles caused by micro gas generated when the curable composition for backing material fills round holes or elongated rectangular recesses do not remain in the cured resin surface layer, and the surface of the cured film is smooth. Some nature. Curability: A property that cures uniformly to the bottom of the recess. Etching resistance: The property that the cured film has etching resistance against secondary etching by a corrosive liquid such as iron perchloride and protects the coated material surface. Alkali solubility: The property that the cured film easily dissolves and peels off by alkali treatment. Pattern forming property: The property of forming fine holes in a thin metal plate faithfully in accordance with the pattern (negative pattern) drawn on a negative film. For example, a narrow rectangular fine hole is formed while the long sides of the rectangle are parallel to each other. In the case of a large number of negative patterns provided at regular intervals, the long sides are straight, and the long sides of the adjacent holes are parallel to each other, and the distance between the long sides of the adjacent holes is constant. A characteristic of forming a hole in a metal plate by maintaining a regular shape peculiar to a negative pattern, and preventing a metal portion sandwiched between long sides of the elongated hole from twisting.

Heretofore, as a composition which satisfies the above-mentioned performance required for a curable composition for a backing material, a composition in which a resin forming a film soluble in an alkaline liquid is dissolved in an organic solvent has been used. After being applied by a method such as spraying, the organic solvent was evaporated by a hot air drying furnace or the like to form a resin coating. However, since the composition contains a large amount of an organic solvent, after applying the curable composition for a backing material, a drying furnace for evaporating the organic solvent and a device for collecting the evaporated solvent are necessary, and equipment costs are reduced. To rise. In addition, since a large amount of organic solvent evaporates during drying, there is a problem of toxicity and a risk of ignition and explosion. In addition, in order to reduce the danger of ignition, explosion and fire in the drying process, the use of flame-retardant chlorine-based solvents such as trichloroethylene has been studied, but these may cause problems such as air pollution in recent years. And their use is being regulated. A method of using a water-based ultraviolet curable composition as a curable composition for a backing material which solves these problems (Japanese Patent Laid-Open No. 1-261-261).
No. 410, JP-A-2-133404), a method using an essentially solvent-free ultraviolet curable composition (Japanese Patent Publication No. 6-79463), and the like.

On the other hand, in the manufacture of shadow masks in recent years, a secondary etching process at a high temperature has been studied for the purpose of reducing the manufacturing cost by shortening the process or controlling the shape of the hole by the etching temperature. Have been.

[0007]

However, a cured film obtained from a conventional curable composition for a backing material has a high degree of resistance to etching, alkali dissolution / peeling, and pattern formation in high temperature etching. There was nothing better. In other words, when the backing treatment is performed on the metal plate after the first etching using the conventional curable composition for a backing material and the second etching is performed at a high temperature, the surface of the metal plate is sufficiently protected from the corrosive liquid. In some cases, a large hole was opened in the metal plate. On the other hand, when an attempt is made to improve the etching resistance under such high-temperature etching treatment, the alkali solubility of the cured film is significantly deteriorated, and the cured film cannot be removed or the pattern formability is reduced. was there.

Accordingly, an object of the present invention is to solve the above-mentioned problems of the conventional curable composition for a backing material. Even when secondary etching is performed at a high temperature, the cured film has etching resistance, An object of the present invention is to provide a curable composition for a backing material at the time of manufacturing a shadow mask which is excellent in both alkali dissolving / peeling properties and pattern forming properties.

[0009]

Under these circumstances, the present inventors have conducted intensive studies and as a result, have found that a composition containing three types of compounds having specific functional groups can be used in a secondary etching step at a high temperature. The present invention was found to be excellent in both etching resistance, alkali dissolution and peeling properties, and also excellent in pattern forming properties, and completed the present invention.

That is, the present invention relates to a curable composition for a backing material in a secondary etching step in the production of a shadow mask, wherein (a) one carboxyl group and one (meth) A compound having an acryloyl group,
(B) a compound having 5 or more (meth) acryloyl groups in the molecule and not having an alkylene oxide unit, and (c) a compound having 2 or more (meth) acryloyl groups in the molecule. And a curable composition for a backing material at the time of manufacturing a shadow mask, wherein the curable composition comprises a compound having an alkylene oxide unit, and has a cured film having alkali solubility or alkali releasability.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, an acryloyl group or a methacryloyl group is called a (meth) acryloyl group,
Acrylate or methacrylate is called (meth) acrylate, and acrylic acid or methacrylic acid is called (meth) acrylic acid.

In the curable composition for a backing material during the production of the shadow mask of the present invention, the component (a) contains
It is a compound having one carboxyl group and one (meth) acryloyl group, and the cured film of the composition of the present invention has
It is a component that imparts dissolution / peelability by alkali treatment. Preferred examples of the component (a) include a reaction product of a dibasic acid or an acid anhydride thereof and a (meth) acrylate having a hydroxyl group at a terminal, and a reaction product of a lactone and a compound having a carboxyl group and a (meth) acryloyl group. Is mentioned.

In a reaction product of a dibasic acid or an acid anhydride thereof and a (meth) acrylate having a hydroxyl group at a terminal,
Examples of the dibasic acid or its acid anhydride include phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, and succinic acid, and anhydrides of these dibasic acids. Examples of the acrylate include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate. Specific compounds include (meth) acryloyloxyethyl monophthalate (for example, trade name “Aronix M-5400” manufactured by Toagosei Co., Ltd.), (meth) acryloyloxypropyl monophthalate, and (meth) acryloyloxyethyl monotetrahydro. Phthalate, (meth) acryloyloxypropyl monotetrahydrophthalate, (meth) acryloyloxyethyl monohexahydrophthalate, (meth) acryloyloxypropyl monohexahydrophthalate, (meth) acryloyloxyethyl monosuccinate (trade name, manufactured by Toagosei Co., Ltd.) "Aronix M-5500 etc."), (meth) acryloyloxypropyl monosuccinate, (meth) acryloyloxyethyl monomalate and (meth) acryloyloxypropyl mono Mention may be made of the rate, and the like.

In the reaction product of a lactone and a compound having a carboxyl group and a (meth) acryloyl group, the lactone may include ε-caprolactone, and the compound having a carboxyl group and a (meth) acryloyl group. , (Meth) acrylic acid and the like. Specific examples of the compound include a compound having a carboxyl group at a molecular terminal (eg, “Aronix M-5300” manufactured by Toagosei Co., Ltd.), which is a reaction product of ε-caprolactone and (meth) acrylic acid. .

As the component (a), other than the above, compounds such as (meth) acrylic acid and dimers thereof (trade name “Aronix M-5600” manufactured by Toagosei Co., Ltd.) can be mentioned.

Among these components (a), acrylic acid dimer and (meth) acryloyloxyethyl monosuccinate themselves have a viscosity at 25 ° C. of 200-4.
Since the viscosity is relatively low at 00 cps, the composition of the present invention can be made low in viscosity, which is preferable.

The above component (a) can be used alone or in combination of two or more. Further, a preferable mixing ratio of the component (a) is a total amount of the component (a), the component (b), and the component (c), or the component (a), the component (b) described later.
When a component and a (meth) acrylate other than the component (c) are blended, 20 to 80% by weight (hereinafter, referred to as a “curable component”) based on the total amount thereof (hereinafter referred to as “curable component”) , “%” Means “% by weight”), and more preferably 30 to 70%. If the compounding ratio is less than 20%, the alkali dissolution and peeling properties of the cured film of the composition are not sufficient, and if it exceeds 80%, the corrosion resistance at the time of secondary etching may be insufficient.

In the present invention, the component (b) is a compound having five or more (meth) acryloyl groups in the molecule and having no alkylene oxide unit. Specifically, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tripentaerythritol polyvalent (meth)
Acrylate and the like. The component (b) is a component that imparts etching resistance to high-temperature etching to a cured film of the composition.

The above component (b) can be used alone or in combination of two or more. The preferred blending ratio of the component (b) is 1 to 30% based on the total amount of the curable component. If the compounding ratio is less than 1%, the etching resistance of the cured film of the composition may be reduced. On the other hand, if it exceeds 30%, the alkali dissolution and peelability of the cured film may be insufficient.

In the present invention, the component (c) is a compound having two or more (meth) acryloyl groups in the molecule and having an alkylene oxide unit, and has an etching resistant property on the cured film of the composition of the present invention. It is a component that imparts properties. Examples of the component (c) include polyol poly (meth) acrylate, polyester poly (meth) acrylate, and epoxy (meth) acrylate. Hereinafter, these components will be described.

Examples of the polyol poly (meth) acrylate include a reaction product of a polyhydric alcohol and (meth) acrylic acid. Specific examples of the compound include triethylene glycol di (meth) acrylate and tetraethylene glycol di ( (Meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, di (meth) acrylate of alkylene oxide adduct of hexanediol, alkylene oxide of neopentyl glycol (Meth) acrylate of an alkylene oxide adduct of bisphenol A, di (meth) acrylate of an alkylene oxide adduct of bisphenol F, hydrogenated bis Di (meth) acrylate of alkylene oxide adduct of phenol A, di (meth) acrylate of alkylene oxide adduct of hydrogenated bisphenol F, di (meth) acrylate of alkylene oxide adduct of tricyclodecanedimethanol, alkylene of glycerin Tri (meth) acrylate of oxide adduct, tri (meth) acrylate of alkylene oxide adduct of trimethylolpropane, tri- or tetra (meth) acrylate of alkylene oxide adduct of pentaerythritol, alkylene oxide adduct of ditrimethylolpropane Poly (meth) acrylates of polyols such as tri- or tetra (meth) acrylate and penta- or hexa- (meth) acrylate of alkylene oxide adduct of dipentaerythritol Mention may be made of the rate. Here, as the alkylene oxide,
Examples include ethylene oxide and propylene oxide.

Examples of the polyester poly (meth) acrylate include a reaction product of a polyester-type polyhydric alcohol and (meth) acrylic acid. Examples of polyester-type polyhydric alcohols include, for example, succinic acid, maleic acid, adipic acid, sebacic acid, phthalic acid, polybasic acids such as tetrahydrophthalic acid, hexahydrophthalic acid and trimellitic acid, and anhydrides thereof. Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
Examples include polyester alcohols obtained by reacting tripropylene glycol, polypropylene glycol, triol of an alkylene oxide adduct of trimethylolpropane, triol of an alkylene oxide adduct of glycerin, and tetraol of an alkylene oxide adduct of pentaerythritol. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

As the epoxy (meth) acrylate,
A compound obtained by reacting an epoxy group of an epoxy compound having an alkylene oxide unit such as ethylene oxide or propylene oxide in a molecule and having two or more epoxy groups with (meth) acrylic acid is exemplified.

The components (c) include diacrylate of ethylene oxide adduct of bisphenol A, triacrylate of ethylene oxide adduct of glycerin, triacrylate of ethylene oxide adduct of trimethylolpropane, and ethylene oxide adduct of pentaerythritol. And the like are preferred.

The above component (c) can be used alone or in combination of two or more. Further, a preferable blending ratio of the component (c) is 1 to 30% with respect to the total amount of the curable component. When this compounding ratio is less than 1%,
Etching resistance may be reduced. On the other hand, if it exceeds 30%, the alkali dissolution and peelability of the cured film may be insufficient.

The curable composition for a backing material of the present invention comprises 25
The viscosity at ℃ is preferably 10,000 cps or less,
It is more preferably 5,000 cps or less. If the viscosity of the composition at 25 ° C. exceeds 10,000 cps, it may be difficult to uniformly wet the surface of the metal material having the concave portions and fill the holes. The viscosity of the composition can be easily adjusted by appropriately selecting the types and amounts of the various components described above, or by mixing the following other components.

The curable composition for a backing material of the present invention may optionally contain, in addition to the above components (a), (b) and (c),
Chain transfer agent, leveling agent, polymerization initiator, (a),
It may contain (meth) acrylates other than the components (b) and (c) and other optional components. Less than,
These components will be described.

The curable composition for a backing material of the present invention preferably contains a chain transfer agent for the purpose of imparting alkali dissolving / peeling properties and pattern forming properties to a cured film of the composition. As the chain transfer agent, various compounds conventionally known can be used, and a monothiol compound is preferable. Monothiol compounds include mercaptans such as octylmercaptan, nonylmercaptan, decylmercaptan, dodecylmercaptan and cetylmercaptan; hydroxyl-substituted mercaptans such as monothioethylene glycol and α-monothioglycerin; thioglycolic acid, mercaptopropionic acid, -Mercaptocarboxylic acids such as mercaptopropionic acid, thiolactic acid and thiomalic acid.

The mixing ratio of the chain transfer agent is preferably 0.01 to 5 parts, more preferably 0.1 to 3 parts, per 100 parts of the total amount of the curable component. If the compounding ratio is less than 0.01 part, the dissolution / peelability of the cured film becomes insufficient, so that the distance between the holes formed in the metal plate becomes uneven or the metal part between adjacent holes is twisted. Sometimes. On the other hand, if it exceeds 5 parts, the stability of the composition will be reduced,
The viscosity of the composition may increase.

The curable composition for a backing material of the present invention preferably further contains a leveling agent for the purpose of improving the hole filling property of the composition and the surface smoothness of the cured film. As the leveling agent, a general surfactant can be used. Specific compounds include, for example, Florade FC-430, which is a nonionic fluorinated alkyl ester.
(Manufactured by Sumitomo 3M), Megafac F-177 (manufactured by Dainippon Ink and Chemicals) and Megafac F-179
(Manufactured by Dainippon Ink and Chemicals, Inc.), and NUC Silicone L7002 (manufactured by Nippon Unicar) and FZ-2165 (manufactured by Nippon Unicar) as silicone-based compounds. Of these, Megafac F-179 and NU
C silicone L7002 is preferable because it has low foaming properties and can easily obtain a resin coating film having excellent surface smoothness.

The compounding ratio of the leveling agent is 0.01 to 5 parts with respect to 100 parts by weight of the total amount of the curable component (hereinafter, “parts” means “parts by weight”). preferable. If the amount is less than 0.01 part, it may be difficult to impart the hole filling property and the surface smoothness characteristics to the composition of the present invention. If the amount exceeds 5 parts, the resin coating film may be liable to have defects. is there.

The curable composition for a backing material of the present invention can be cured by irradiation with active energy rays such as ultraviolet rays, visible rays or electron beams, or by heating. When blended, the composition can be cured in a short time. When the composition is cured by irradiating ultraviolet rays or visible light, the following photopolymerization initiators and sensitizers that are commonly used are used in order to sufficiently exhibit the photocurability of the composition. use. Preferred photopolymerization initiators include 2-acetophenones.
Methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone (trade name “Irgacure 907” manufactured by Ciba Geigy), benzyl dimethyl ketal (trade name “Irgacure 65” manufactured by Ciba Geigy)
1)), 1-hydroxycyclohexyl phenyl ketone (trade name “Irgacure 184” manufactured by Ciba Geigy),
Diethoxyacetophenone (trade name "First Cure DEAP" manufactured by First Chemical Company), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name "Darocur 1173" manufactured by Ciba Geigy), 4
-(2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone (trade name “Irgacure 2959” manufactured by Ciba Geigy) and 2-benzyl-2-
Dimethylamino-1- (4-morpholinophenyl)-
Butanone (trade name "Irgacure 3" manufactured by Ciba Geigy)
69 ”). Benzoin ethers include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether. Benzophenones include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone,
Benzoyl-4'-methyl-diphenyl sulfide and 2,4,6-trimethylbenzophenone. The thioxanthones include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4
-Dichlorothioxanthone and 1-chloro-4-propoxythioxanthone. Examples of the acylphosphine oxide include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide. Other examples include camphorquinone. Preferred sensitizers include triethanolamine, methyldiethanolamine, triisopropanolamine,
Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4-dimethylaminobenzophenone and 4,4
-Diethylaminobenzophenone and the like.

Among these photopolymerization initiators, an acylphosphine oxide-based photopolymerization initiator or 1-hydroxycyclohexyl phenyl ketone improves the pattern forming property when manufacturing a shadow mask, and causes an abnormally large size on a metal plate. This is preferable in that the occurrence of a defect that a hole is opened can be prevented.

When the composition is to be cured mainly by a heat energy source such as a heating furnace, infrared rays and microwaves, it is preferable to add a thermal polymerization initiator. Suitable thermal polymerization initiators include, for example, azo compounds such as azoisobutyronitrile, ketone peroxides, hydroperoxides, alkyl peroxides, various organic peroxides such as acyl peroxides and peroxyesters, and And inorganic peroxides such as ammonium persulfate. When left at room temperature or heated at a relatively low temperature of 100 ° C. or less, it is preferable to mix a polymerization accelerator together with the thermal polymerization initiator. Preferred polymerization accelerators include, for example, cobalt,
Organic metal salts of metals such as iron and manganese with naphthenic acid, linoleic acid, acetylacetone and the like, reducing amines such as dimethyl paratoluidine and ascorbic acid, and other reducing substances. These polymerization accelerators are used in combination, for example, in combination of a hydroperoxide, ketone peroxide or peroxyester and an organic metal salt, or an acyl peroxide and a reducing amine.

The mixing ratio of the polymerization initiator is preferably 0.1 to 15 parts, more preferably 0.5 to 10 parts, based on 100 parts of the total amount of the curable component.
If the compounding ratio is less than 0.1 part, the effect of accelerating the initiation of polymerization becomes insufficient, and if it exceeds 15 parts, the components truly required for the cured film are reduced, and the target properties of the cured film deteriorate. There is fear.

As described above, the curable composition for a backing material of the present invention can be cured by either active energy ray or heating.
It is preferable in that curing can be performed with high energy efficiency and energy source equipment can be saved in space.

The curable composition for a backing material according to the present invention may have, if necessary, viscosity of the composition and alkali dissolution of the cured film.
For the purpose of adjusting the releasability, etc., the components (a) and (b)
A (meth) acrylate other than the component and the component (c) can be blended. Preferred (meth) acrylates having one (meth) acryloyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate (Meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; (meth) acrylates such as (meth) acrylamide, diacetone (meth) acrylamide and dimethyl (meth) acrylamide A) acrylamides; polyalkylene glycol monoalkyl (C1-9) ether mono (meth) acrylates such as polyethylene glycol and polypropylene glycol; Call mono (meth) acrylate and polypropylene glycol mono (meth) polyalkylene glycol mono acrylate (meth) acrylate; mono- phenol ethylene oxide or propylene oxide adduct (meth)
Mono (meth) acrylates of phenol alkylene oxide adducts such as mono (meth) acrylates of acrylates, ethylene oxide or propylene oxide adducts of nonylphenol, and mono (meth) acrylates of ethylene oxide or propylene oxide adducts of p-cumylphenol Benzyl (meth) acrylate; (meth) acryloylmorpholine; tetrahydrofurfuryl (meth) acrylate; N-vinylpyrrolidone; isobornyl (meth) acrylate; and the following formula (1);

[0038]

Embedded image

(Wherein R ₁ is a hydrogen atom or a methyl group) and the following formula (2):

[0040]

Embedded image

(Wherein R ₂ is a hydrogen atom or a methyl group), and one or more of these compounds can be used.

Preferred (meth) acrylates having two or more (meth) acryloyl groups include, for example, butanediol di (meth) acrylate, pentanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl Glycol di (meta)
Di (meth) acrylates of diols such as acrylate, nonanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, and di (meth) acrylate of esterified diol of hydroxypivalic acid and neopentyl glycol; polyethylene glycol; Di (meth) acrylates of polyether glycols such as di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate; polyols such as dipentaerythritol penta or hexa (meth) acrylate Poly (meth) acrylate can be mentioned.

Further, a reaction product of a compound obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to a polyhydric alcohol and (meth) acrylic acid can also be mentioned. Specific compounds include di (meth) acrylate of an alkylene oxide adduct of hexanediol, di (meth) acrylate of an alkylene oxide adduct of neopentyl glycol, di (meth) acrylate of an alkylene oxide adduct of bisphenol A, Di (meth) acrylate of an alkylene oxide adduct of bisphenol F, di (meth) acrylate of an alkylene oxide adduct of hydrogenated bisphenol A,
Di (meth) acrylate of an alkylene oxide adduct of hydrogenated bisphenol F and di (meth) acrylate of an alkylene oxide adduct of tricyclodecanedimethanol can be used. In addition, poly (meth) acrylate phosphate or the like can be used.

These (meth) acrylates can be used alone or in combination of two or more. Also,
The preferred compounding ratio of these (meth) acrylates is
0 to 40 parts with respect to 100 parts of the total amount of the curable component.

In order to lower the viscosity of the curable composition for a backing material of the present invention, water or an organic solvent can be appropriately blended. As the organic solvent, alcohols such as methanol, ethanol, butanol and isopropyl alcohol, butyl cellosolve, cellosolve such as methyl cellosolve and ethyl cellosolve, methyl cellosolve acetate, cellosolve acetate of ethyl cellosolve acetate and butyl cellosolve acetate, propylene glycol monomethyl ether, toluene, and Xylene and the like can be mentioned. A preferable mixing ratio of the organic solvent is 0 to 10 parts with respect to 100 parts of the total amount of the curable component. In order to alleviate distortion during curing, a polymer having a molecular weight of 1,000 to 10,000 which is dissolved in the curable component and a particulate filler which is insoluble in the curable component can be added.

In order to obtain the curable composition for a backing material of the present invention, the above-mentioned components may be uniformly mixed by a usual mixing method, and the order of mixing the components, the mixing apparatus and the like are not particularly limited. However, when mixing solid components at room temperature, it is preferable to mix by heating to a temperature at which the components melt or disperse.

In the curable composition for a backing material of the present invention, a cured film having alkali solubility or alkali releasability means that the cured film after the secondary etching step in the production of a shadow mask has a concentration of 5 to 20%. When completely immersed in an aqueous solution of caustic soda or caustic potash at 50 to 90 ° C. for 1 minute, it completely dissolves, peels off, or does not completely dissolve, but peels off.

The curable composition for a backing material of the present invention is applicable to both the production of a shadow mask having a large number of round holes and the production of a shadow mask having a large number of elongated holes. Can be preferably used for manufacturing a shadow mask having a long and narrow hole. Hereinafter, a method of manufacturing the shadow mask will be described. First, a photosensitive resin such as casein and polyvinyl alcohol is applied to the front and back surfaces of a thin metal plate made of iron or the like, and then a negative film on which a pattern is arranged is brought into close contact with the metal plate to cure the exposed portion of the photosensitive resin. Photolithography is performed, and a non-photosensitive portion of the photosensitive resin film is removed by a developing process. Next, primary etching is performed with a corrosive liquid such as iron perchlorate,
Fine concave portions that do not penetrate each other are formed from both sides.
A curable composition for a backing agent is applied to one surface of the metal plate after the primary etching, and the composition is cured by irradiation with active energy rays such as ultraviolet rays or heating. In this case, as a method of applying the composition, a normal application method such as spray, flow coat, roll coat, die coat, and dip coat may be adopted. After the curing process of the curable composition for a backing material, a corrosive liquid is supplied to the metal plate to perform a secondary etching on the concave portion on the other surface, and the concave portion on one surface by the primary etching and the other surface. The upper recess is communicated at the bottom. The temperature in the secondary etching is 40 to 90.
Although it is in the range of ° C., as described above, the composition of the present invention has both etching resistance and alkali dissolution / peeling property in high-temperature secondary etching, and therefore can be preferably applied even at a high temperature of 70 to 90 ° C. Things. An alkali solution is supplied to the obtained metal plate having a large number of holes, and the cured film of the photosensitive resin film and the curable composition for a backing material is peeled from the metal plate. In this case, as the alkaline solution, a solution obtained by heating an aqueous solution of caustic soda or caustic potash having a concentration of 5 to 20% to 50 to 90 ° C is used.

[0049]

Next, the present invention will be described more specifically with reference to examples and comparative examples. Examples 1 to 4 The components shown in Table 1 were dissolved and mixed to produce an active energy ray-curable composition for a backing material. Next, the composition obtained was applied to a test iron plate so as to have a thickness of 30 μm. The coating film was irradiated with ultraviolet rays using an 80 w / cm condensing metal halide lamp, and it was confirmed that the resin was cured because there was no tack on the coating film surface. The properties of the obtained cured film were evaluated according to the methods described below to evaluate the hole filling property, surface smoothness, etching resistance, alkali dissolution / peeling property, and pattern forming property. Table 1 shows the results.

(Hole-filling property) An iron plate having a negative pattern formed of a casein-based photosensitive resin film and having a large number of elongated rectangular recesses formed by primary etching (hereinafter simply referred to as “test iron plate”)
The composition of the present invention was applied to one side of the sample, and the state of hole filling was visually determined based on the following evaluation criteria. The dimensions of the test iron plate are shown in FIG. In the figure,
Reference numeral 1 denotes a test iron plate, and reference numeral 2 denotes an elongated rectangular recess formed in the test iron plate 1. The width of the concave portion is increased in the figure for easy understanding. L _{1 to} L ₆
Indicates a length dimension, L ₁ = 15 cm, L ₂ = L ₃ = 20 cm, L ₄ = 40c
m, L ₅ = L ₆ = 200 μm. ：: There are no bubbles at all. Δ: Air bubbles are present in some holes. ×: Bubbles are present on the entire surface.

(Surface Smoothness) The composition of the present invention is cured by irradiating ultraviolet rays to the iron plate after the hole filling property has been evaluated, and the surface condition of the cured film is visually determined based on the following evaluation criteria. did. ：: No cissing. Δ: Repelling was partially observed. ×: Many repelling occurred.

(Etching Resistance) The iron plate after the evaluation of the surface smoothness was placed in a 43% aqueous solution of FeCl ₃ at 90 ° C. for 2 hours.
After immersion for 0 minutes, the surface state of the cured film was visually determined based on the following evaluation criteria. ：: No change at all. Δ: Colored. X: Swelling or peeling occurred.

(Alkali dissolution / peelability) The iron plate after the evaluation of the etching resistance was placed in a 20% aqueous NaOH solution for 8 hours.
It was immersed at 0 ° C. for 1 minute, and the solubility or releasability of the cured film was visually determined based on the following evaluation criteria. A: Completely dissolved and peeled. ：: Not completely dissolved but peeled. Δ: Some of the peeled ones remained on the metal plate. X: It did not peel.

(Pattern-forming property) The iron plate after evaluating the alkali dissolution / peelability was washed with water and dried, and illuminated from the back of the iron plate, so that the shape of the elongated rectangular hole formed in the iron plate was transmitted. And the uniformity of the brightness of the transmitted light, the size of the holes, the distance between the holes, and the linearity of the long side of the rectangle were determined based on the following evaluation criteria. ：: The size of the hole and the interval between the holes are completely constant, and the long side of the rectangle is a straight line. ：: Approximately one out of every 100 products has a defect. Δ: Approximately 1 out of 3 to 9 defects out of 100 products. ×: One or more defects were found in 10 or more out of 100 products.

Comparative Examples 1 to 3 An active energy ray-curable composition for a backing material was produced in the same manner as in Example 1 except that the components were changed as shown in Table 1. Using the obtained composition, evaluation was performed in the same manner as in the examples. Table 1 shows the results.

[0056]

[Table 1]

The abbreviations in Table 1 have the following meanings.・ M-5400: Trade name “Aronix M-540” manufactured by Toagosei Co., Ltd.
0 ", acryloyloxyethyl monophthalate ・ M-5600: Toagosei Co., Ltd. product name“ Aronix M-560
0 '', acrylic acid dimerM-400: Alonix M-400, trade name, manufactured by Toagosei Co., Ltd.
A mixture of about 30 parts of pentaacrylate of dipentaerythritol and about 70 parts of hexaacrylate. • M-210: “Aronix M-210” manufactured by Toagosei Co., Ltd.
, Diacrylate of ethylene oxide 4 mol adduct of bisphenol A ・ M-360: trade name “Aronix M-360” manufactured by Toagosei Co., Ltd.
], Ethylene oxide 6 of trimethylolpropane
Triacrylate of molar adducts ・ M-320: trade name “Aronix M-320” manufactured by Toagosei Co., Ltd.
Triacrylate of 6 mol of propylene oxide adduct of trimethylolpropane ・ TO-1811: trade name “Aronix TO-181” manufactured by Toagosei Co., Ltd.
1), tetraacrylate of 4 moles of ethylene oxide adduct of pentaerythritol. • M-305: trade name “Aronix M-305” manufactured by Toagosei Co., Ltd.
・ Triacrylate of pentaerythritol ・ ACMO: Kojinsha, acryloylmorpholine ・ MegaFac F-177: Leveling agent, Dainippon Ink and Chemicals, fluorine-containing oligomer ・ NUC Silicone L7002: Leveling agent, Nippon Unicar -Silicone polymer -Lucirin TPO: Photopolymerization initiator, manufactured by BASF, 2,4,6-trimethylbenzoyldiphenylphosphine oxide -Irgacure 184: Photopolymerization initiator, manufactured by Ciba Geigy, 1-hydroxycyclohexylphenyl ketone・ Irgacure 651: Photopolymerization initiator, Ciba-Geigy, benzyl dimethyl ketal

[0058]

The curable composition for a backing material at the time of manufacturing a shadow mask according to the present invention is easily and quickly cured by irradiation with active energy rays or heating. The cured film is excellent in all of etching resistance, alkali dissolving / peeling properties and pattern forming properties. Further, since the curable composition for a backing material of the present invention does not require an organic solvent, a drying furnace for evaporating the organic solvent and a solvent recovery device are not required.
Furthermore, there is no need to worry about the toxicity of the organic solvent when handling the raw materials, and it is possible to prevent the danger of ignition and explosion during drying. Moreover, it is possible to cure for a short time without the need for a drying step involving the evaporation of the organic solvent, to achieve a reduction in energy costs and prevention of fire, and to be useful in that it can be improved by utilizing existing processes. The industrial value is extremely large.

[Brief description of the drawings]

FIG. 1 is a schematic plan view of a test iron plate used in an example.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C23F 1/00 C23F 1/00 CF term (Reference) 4J027 AB01 AB06 AB15 AB16 AB17 AB18 AB19 AB23 AB24 AB25 AB26 AC02 AC03 AC04 AC06 AE01 BA07 BA08 BA13 BA14 BA17 BA19 BA23 CA25 CA26 CA27 CA29 CB02 CB04 CB06 CB07 CB09 CB10 CD08 4J038 FA012 FA081 FA111 FA272 GA01 GA06 JA33 KA04 NA04 PA17 PA19 PB08 PB09 PC02 4K057 WA11 WG04

Claims (3)

[Claims] 1. A curable composition for a backing material in a secondary etching step in the production of a shadow mask, comprising: (a)
A compound having one carboxyl group and one (meth) acryloyl group in the molecule, (b) having five or more (meth) acryloyl groups in the molecule and having no alkylene oxide unit In the compound, and (c) the molecule:
A backing material for producing a shadow mask, comprising a compound having two or more (meth) acryloyl groups and having an alkylene oxide unit, and having a cured film having alkali solubility or alkali releasability. Curable composition. 2. A mixture of one or more selected from the group consisting of a chain transfer agent, a leveling agent, a polymerization initiator and a (meth) acrylate other than the components (a), (b) and (C). A curable composition for a backing material during production of a shadow mask according to claim 1. 3. The curable composition according to claim 2, wherein the polymerization initiator is an acylphosphine oxide-based photoinitiator or 1-hydroxycyclohexyl phenyl ketone.