JP3509653B2 - Curable composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable composition which can be cured by irradiating an active energy ray such as an ultraviolet ray or an electron beam. More specifically, the obtained cured film has an alkaline composition. The present invention relates to a curable composition suitable as an etching resist material in a secondary etching step during the production of a shadow mask because it can be easily peeled from a substrate with an aqueous solution.

[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 grill type) or a thin metal plate provided with a large number of fine holes such as circular holes in a predetermined pattern by etching. Among these shadow masks, as a shadow mask for a CRT such as a personal computer,
The one having a circular hole is used, and the shadow mask for a high-resolution or high-brightness television has a rectangular elongated hole (aperture grill type).
These shadow masks are required to have fine holes with higher precision. In the production of such a shadow mask, recesses are formed by primary etching at corresponding positions on both front and back surfaces of a metal plate, and a cured film of the composition for backing material is formed on one surface of the recesses, and then the secondary mask is further formed. Etching is performed so that the bottoms of the corresponding recesses communicate with each other.

The outline of the manufacturing process of the shadow mask is as follows. First, a photosensitive resin is applied on both front and back surfaces of a thin metal plate made of iron or the like, and then a negative film having a pattern is adhered to the metal plate to adhere the photosensitive resin. Photographic printing is carried out to cure the exposed portion of, and the non-exposed portion of the photosensitive resin film is removed by development processing. Then, primary etching is performed with a corrosive solution such as iron perchloride to form fine recesses that do not penetrate each other from the front and back surfaces. The composition for the backing material is applied only to one side of the metal plate after the primary etching, and the composition is cured by irradiation with active energy rays such as ultraviolet rays or by heating to form fine recesses on one side of the metal plate. A cured film to be filled is formed. After protecting one surface in this way, again perform a secondary etching targeting the concave portion on the other surface with a corrosive solution, and connect the concave portion on one surface and the concave portion on the other surface by the primary etching to communicate at the bottom portion. From the above, each of the cured films of the photosensitive resin for pattern formation and the composition for backing material is removed by alkali treatment to obtain a shadow mask. By performing the secondary etching using the composition for the backing material here, which occurs when a hole is formed only by the primary etching, an abnormally large hole or a distorted hole is opened, and the accuracy of the hole is increased. It can solve the problem of deterioration. The composition for backing material is usually referred to as an etching resist composition.

In the above shadow mask manufacturing method,
The curable composition used for the purpose of the backing material after the primary etching, that is, the etching resist material must basically satisfy the following properties (1) and (2). Hole filling property: A property of uniformly wetting the surface of a material having a hemispherical recess having a diameter of 50 to 200 μm or an elongated rectangular recess having a width of 50 to 200 μm and a length of 10 to 200 cm, and filling the recess without generating bubbles in the recess. Surface smoothness: The property of the backing material composition that the surface of the cured film is smooth, with no bubbles remaining in the cured resin surface layer due to minute gas generated when filling a round hole or a long rectangular recess. . In addition to the above, it is required that the cured film satisfies the requirements in a certain degree of flexibility, etching resistance and alkali peeling property.

Recently, in the manufacture of shadow masks,
The etching temperature has been increased in order to shorten the etching time and because it is easy to obtain fine holes as designed. That is, the etching temperature of 40 to 55 ° C. has been mainly used in the past, but the etching temperature of 60 to 90 ° C. has been adopted recently. However, under such a high temperature condition, a resist film formed from a conventional curable composition for an etching resist has a problem that the resist performance cannot be maintained due to insufficient heat resistance. The present inventors have found that a curable composition that solves the above problems of the conventional backing material composition, that is, the cured film has etching resistance, alkali dissolution / peelability and The subject of the present invention was earnestly studied to provide a curable composition having excellent pattern formability.

[0006]

The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, the present invention is a curable composition for an etching resist, which comprises the following compound (a) and compound (b) as main constituent components. (A) a compound having one carboxyl group and one (meth) acryloyl group in one molecule (b) a dihydric alcohol obtained by adding 2 to 3 alkylene oxide units per molecule of bisphenol A ( Di (meth) acrylate obtained by esterifying (meth) acrylic acid In the present invention, an acryloyl group or a methacryloyl group is referred to as a (meth) acryloyl group, and an acrylate or a methacrylate is referred to as a (meth) acrylate.
Acrylic acid or methacrylic acid is called (meth) acrylic acid. Hereinafter, the present invention will be described in detail.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The compound (a) in the present invention [hereinafter referred to as the component (a)] is a compound having one carboxyl group and one (meth) acryloyl group in one molecule. It is a component that imparts dissolution / peeling property by alkali treatment to the cured film obtained from the composition. Preferred component (a) is a reaction product of a dibasic acid or its acid anhydride with a (meth) acrylate having a hydroxyl group at the terminal (half-ester compound), a compound having a lactone and a carboxyl group and a (meth) acryloyl group. Reaction products with and the like can be mentioned. Examples of the dibasic acid or acid anhydride thereof include phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid and succinic acid, and acid anhydrides thereof, and the like, which has a hydroxyl group at the terminal (meth).
Examples of acrylates include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.

Specific compounds include (meth) acryloyloxyethyl monophthalate [as a commercial product,
Aronix M-5400 manufactured by Toagosei Co., Ltd. is available. The same applies in the following parentheses], (meth) acryloyloxypropyl monophthalate, (meth) acryloyloxyethyl monotetrahydrophthalate, (meth) acryloyloxypropyl monotetrahydrophthalate,
(Meth) acryloyloxyethyl monohexahydrophthalate, (meth) acryloyloxypropyl monohexahydrophthalate, (meth) acryloyloxyethyl monosuccinate [Toagosei Co., Ltd., Aronix M-5500, etc.], (meth) acryloyl Examples thereof include oxypropyl monosuccinate, (meth) acryloyloxyethyl monomerate and (meth) acryloyloxypropyl monomerate. A specific example of the reaction product of a lactone and a compound having a carboxyl group and a (meth) acryloyl group is a reaction product of ε-caprolactone and (meth) acrylic acid, which is a compound having a carboxyl group at the molecular terminal [Toagosei ( Aronix M-5300, etc.]. These can be used alone or in combination of two or more. In addition to the above compounds, as component (a), (meth) acrylic acid and its dimer [Aronix M-5600 manufactured by Toagosei Co., Ltd.]
Etc. can also be used.

The more preferred component (a) is (meth) acryloyloxyethyl monophthalate and (meth) acryloyloxyethyl monohexahydrophthalate in that the etching resistance and alkali solubility are well balanced. The preferable blending ratio of the component (a) is 10 parts by weight of the total amount of the polymerizable components among the components constituting the curable composition.
When 0 parts by weight (hereinafter, “parts” means “parts by weight”), it is 20 to 80 parts, and more preferably 30 to 70 parts. If this ratio is less than 20 parts, the alkali-dissolving / peeling property of the cured film of the composition may be insufficient, and if it is more than 80 parts, the corrosion resistance during secondary etching may be insufficient.

Next, the compound (b) [hereinafter referred to as the component (b)] is obtained by esterifying (meth) acrylic acid with a dihydric alcohol obtained by adding 2-3 alkylene oxide units per molecule of bisphenol A. It becomes (meta)
It is an acrylate, and specific examples thereof include di (meth) acrylate obtained by the esterification reaction of the following dihydric alcohol and (meth) acrylic acid. That is, as the dihydric alcohol, Nippon Oil & Fats Co., Ltd. Nissan Uniol DA-350F (dihydric alcohol in which two ethylene oxide units are added to bisphenol A on average), Nippon Emulsifier Co., Ltd.'s BA-3 glycol ( A dihydric alcohol obtained by adding three ethylene oxide units on average to bisphenol A), BAP- manufactured by Nippon Emulsifier Co., Ltd.
2 glycols (dihydric alcohol in which propylene oxide units are added to bisphenol A on average) and Nissan Uniall DB-400 (dihydric alcohol in which propylene oxide units are added to bisphenol A on average 3). ) And the like.

Conventionally, as a curable composition for etching resist, a di (meth) acrylate similar to the above-mentioned components (a) and (b), that is, 1 of bisphenol A has been used.
Although a composition containing a di (meth) acrylate of a dihydric alcohol in which four or more alkylene oxide units are added per molecule as a main constituent was known, such a known composition has a high heat resistance during etching. Inferior, it was difficult to use as an etching resist under high temperature, but di (meta)
This problem could be solved by using the specific compounds defined in the present invention as acrylates. The preferable mixing ratio of the component (b) is 1 to 60 parts based on 100 parts of the total amount of the polymerizable components. When this ratio is less than 1 part, the etching resistance of the cured film of the composition may be reduced, while when it is more than 60 parts, the alkali dissolution /
The peelability may be insufficient.

In the curable composition of the present invention, in addition to the components (a) and (b), a monofunctional vinyl monomer other than the component (a) as a polymerizable component [hereinafter referred to as the component (c)].
Is preferably blended. When the component (c) is added to the curable composition of the present invention, the resulting cured film has excellent flexibility. The preferable mixing ratio of the component (c) is 1 to 30 parts based on 100 parts of the total amount of the polymerizable components. If this ratio is less than 1 part, the cured coating film lacks flexibility, and the coating film may crack during transportation. On the other hand, if the amount is more than 30 parts, the etching resistance may decrease.
Specific examples of the component (c) include methyl (meth) acrylate, ethyl (meth) acrylate and propyl (meth).
Alkyl (meth) acrylates such as acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate, hydroxyethyl (meth) acrylate, and hydroxypropyl (meth) Hydroxyalkyl (meth) acrylates such as acrylates, polyalkylene glycol monoalkyl (C1-18) ether mono (meth) acrylates such as polyethylene glycol and polypropylene glycol, polyethylene glycol mono (meth) acrylates and polypropylene glycol Polyalkylene glycol mono (meth) such as mono (meth) acrylate
Acrylate, mono (meth) acrylate of ethylene oxide or propylene oxide adduct of phenol, mono (meth) acrylate of ethylene oxide or propylene oxide adduct of nonylphenol, and mono (meth) acrylate of p-cumylphenol adduct of ethylene oxide or propylene oxide Mono (meth) of phenol alkylene oxide adduct such as (meth) acrylate
Examples thereof include acrylate, benzyl (meth) acrylate, (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, and isobornyl (meth) acrylate.

Further, as the polymerizable component in the curable composition of the present invention, in addition to the components (a), (b) and (c), for example, polyol poly (meth) acrylate, polyester poly (meth) acrylate. Optionally containing a polyfunctional (meth) acryloyl compound other than the component (b) such as a reaction product of a polyepoxy compound and (meth) acrylic acid or urethane poly (meth) acrylate [hereinafter referred to as component (d)]. Is also good. Such (d)
The components are used for adjusting the viscosity of the composition of the present invention, the etching resistance, the alkali dissolution / peeling property of the cured film, and the like, and the preferable blending ratio is 100 parts by weight of the total amount of the polymerizable components. With respect to 0 to 40 parts. Specific examples of the polyol poly (meth) acrylate, the polyester poly (meth) acrylate, the reaction product of the polyvalent epoxy compound and (meth) acrylic acid, and the urethane poly (meth) acrylate are described in various publicly known documents related to curable compositions. Although described (for example, Japanese Patent Publication No. 7-3027)
No. 0), some examples are as follows.

Polyol Poly (meth) acrylate A reaction product of a polyhydric alcohol and (meth) acrylic acid, and specific compounds include butanediol di (meth) acrylate, pentanediol di (meth) acrylate and hexanediol. Di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, and di (meth) esterified diol of hydroxypivalic acid and neopentyl glycol. Di (meth) acrylate of diol such as acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri- or tetra (meth) acrylate, tri- or tetra (meth) acryle of pentaerythritol DOO, poly (meth) acrylate of polyols such as penta or hexa (meth) acrylate of dipentaerythritol.

Polyester poly (meth) acrylate A reaction product of polyester type polyhydric alcohol and (meth) acrylic acid can be mentioned. As the polyester-type polyhydric alcohol, for example, polybasic acids such as succinic acid, maleic acid, adipic acid, sebacic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and trimellitic acid, and their anhydrides are used. it can. The alcohol component, ethylene glycol, butanediol, hexanediol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylolpropane, pentaerythritol, ethylene oxide of trimethylolpropane, or triol of propylene oxide adduct, ethylene oxide of glycerin, Or propylene oxide adduct triol, and pentaerythritol ethylene oxide,
Alternatively, a polyester alcohol obtained by reacting propylene oxide adduct tetraol or the like may be used.

Epoxy (meth) acrylate. An addition reaction product of a polyvalent epoxy compound and (meth) acrylic acid can be used. As the polyhydric epoxy compound, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, triglyceride. Methylolpropane diglycidyl ether or triglycidyl ether, glycerin diglycidyl ether or triglycidyl ether, pentaerythritol triglycidyl ether or tetraglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, phenol novolac poly Glycidyl ether, cresol novolac polyglycidyl ether, etc. And the like.

A reaction product of a urethane (meth) acrylate polyhydric alcohol, a polyvalent isocyanate compound, and a hydroxyl group-containing (meth) acrylate can be used.
As the polyhydric alcohol, polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and polyester diols such as ethylene glycol adipate, butanediol adipate, butanediol phthalate and hexanediol phthalate can be used. As the polyvalent isocyanate compound, tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate,
Hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate and the like can be used. As the hydroxyl group-containing (meth) acrylate, hydroxyethyl (meth)
Acrylates and hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate can be used.

The curable composition of the present invention preferably has a viscosity at 25 ° C. of 10,000 cps or less, more preferably 5,000 cps or less. 25
When the viscosity of the composition at 10,000 ° C. exceeds 10,000 cps, it may be difficult to uniformly wet the surface of the metal material having the depressions to fill the holes. The viscosity of the composition can be easily adjusted by appropriately selecting the type and blending amount of the above various components, or blending the following other components.

The curable composition of the present invention includes a chain transfer agent,
It is preferable to add a leveling agent and / or a polymerization initiator. -Chain transfer agent In the composition of the present invention, it is preferable to add a chain transfer agent to the cured film of the composition for the purpose of imparting alkali dissolution / peeling property and pattern formability. As the chain transfer agent, various conventionally known compounds can be used, and a monothiol compound is preferable. Examples of the monothiol compound include octyl mercaptan, nonyl mercaptan, decyl mercaptan, mercaptans such as dodecyl mercaptan and cetyl mercaptan, and hydroxyl-substituted mercaptans such as monothioethylene glycol and α-monothioglycerin, thioglycolic acid, and mercaptopropionic acid. , 2-mercaptopropionic acid, mercaptocarboxylic acids such as thiolactic acid and thiomalic acid, and the like. As the compounding ratio of the chain transfer agent, the total amount of the curable components is 100
The amount is preferably 0.01 to 5 parts, and more preferably 0.1 to 3 parts. If the ratio is less than 0.01 part, the cured film may have insufficient dissolution / peelability, resulting in non-uniform spacing of holes formed in the metal plate or twisting of metal parts between adjacent holes. I have something to do. On the other hand, if it exceeds 5 parts, the stability of the composition may be lowered and the viscosity of the composition may be increased.

Leveling Agent The composition 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, Florard FC-430 (manufactured by Sumitomo 3M Limited), which is a nonionic fluorinated alkyl ester, and Megafac F-177 [Dainippon Ink and Chemicals, Inc.].
], Megafac F-179 [manufactured by Dainippon Ink and Chemicals, Inc.], and NU as a silicone compound.
C silicone L7002 [manufactured by Nippon Unicar Co., Ltd.] and FZ-2165 [manufactured by Nippon Unicar Co., Ltd.]. Among the above compounds, Megafac F-179 and N
UC silicone L7002 and the like having a low foaming property are preferable because a resin coating film having excellent surface smoothness can be easily obtained. As the mixing ratio of the leveling agent,
0.01 to 5 parts is preferable for 100 parts of the total amount of the curable components. If it is less than 0.01 part, it may be difficult to impart the properties of hole filling and surface smoothness to the composition of the present invention, and if it exceeds 5 parts, defects of the resin coating film may easily occur. is there.

Polymerization Initiator The composition 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, and the following components are blended depending on the curing means. Then, the composition can be cured in a short time. When the composition is cured by irradiation with 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. As a preferable photopolymerization initiator, specifically, as an acetophenone type, 2-methyl- [4-
(Methylthio) phenyl] -2-morpholino-1-propanone (Irgacure 907 manufactured by Ciba Geigy), benzyl dimethyl ketal (Irgacure 651 manufactured by Ciba Geigy), 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba Geigy), diethoxyacetophenone ( First Cure First Cure DEAP), 2-hydroxy-2-methyl-1
-Phenylpropan-1-one (Darocur 1173 manufactured by Ciba-Geigy), 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone (Irgacure 2959 manufactured by Ciba-Geigy) and 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butanone (Ciba Geigy Irgacure 36
9) and the like. As benzoin ether type,
Examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether. Examples of the benzophenone type include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, and 2,4,6-trimethylbenzophenone. Examples of the thioxanthone system include 2-isopropylthioxanthone, 2,4-diethylthioxanthone and 2,4.
-Dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like. Examples of the acylphosphine oxide system include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide. Other examples include camphor quinone. Among these photopolymerization initiators, acylphosphine oxide is advantageous in that it can improve pattern formability and prevent the occurrence of defects such as formation of abnormally large holes in a metal plate when producing a shadow mask. It is preferable to add a photopolymerization initiator and / or 1-hydroxycyclohexyl phenyl ketone. As the sensitizer used in combination with the photopolymerization initiator, triethanolamine, methyldiethanolamine, triisopropanolamine, 4-
Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4-dimethylaminobenzophenone and 4,4
-Diethylaminobenzophenone and the like are preferable.

When the composition is cured mainly by a heating energy source such as a heating furnace and infrared rays and microwaves, it is preferable to add a thermal polymerization initiator, and the thermal polymerization initiator preferably used is, for example, azoiso There are various organic peroxides such as azo compounds such as butyronitrile, ketone peroxides, hydroperoxides, alkyl peroxides, acyl peroxides and peroxyesters, and inorganic peroxides such as ammonium persulfate. When left at room temperature or heated at a relatively low temperature of 100 ° C. or lower, it is preferable to add a polymerization accelerator together with the above thermal polymerization initiator. As a preferable polymerization accelerator, for example, cobalt,
There are organic metal salts of metals such as iron and manganese with naphthenic acid, linoleic acid and acetylacetone, reducing amines such as dimethylparatoluidine and ascorbic acid, and other reducing substances. These polymerization accelerators are used in combination, for example, in the combination of hydroperoxide, ketone peroxide or peroxy ester with an organic metal salt, or acyl peroxide with a reducing amine. The mixing ratio of the polymerization initiator is preferably 0.1 to 15 parts, and more preferably 0.5 to 10 parts, based on 100 parts of the total amount of the polymerizable components. If it is less than 0.1 part, the effect of accelerating the initiation of polymerization becomes insufficient, and 1
If it exceeds 5 parts, the components that are truly necessary for the cured film will be reduced,
The target properties of the cured film may deteriorate.

Other components In addition to the above components, water or an organic solvent may be appropriately added in order to reduce the viscosity of the composition of the present invention. Examples of the organic solvent include 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 etc. are mentioned. The preferable mixing ratio of the organic solvent is 100, which is the total amount of the curable components.
It is 0 to 10 parts with respect to parts. In addition, in order to reduce strain during curing, it dissolves in a curable component and has a molecular weight of 10
It is also possible to add a polymer of 0-100,000 or a particulate filler insoluble in the curable component. In order to obtain the composition of the present invention, it is sufficient to uniformly mix the above-mentioned components by a usual mixing method, and there is no particular limitation on the order of mixing the components, the mixing device and the like. However, when a solid component is mixed at room temperature, it is possible to heat the mixture to a temperature at which the component melts or disperses to perform the mixing.

The curable composition of the present invention can be preferably used for forming a resist film during secondary etching in producing a shadow mask. Hereinafter, a method for manufacturing the shadow mask will be described. First, a thin metal plate made of iron or the like is coated with a photosensitive resin such as casein and polyvinyl alcohol on both front and back surfaces, and then a negative film having a pattern is adhered to the metal plate to cure the exposed portion of the photosensitive resin. Photographic printing is performed, and a non-exposed portion of the photosensitive resin film is removed by development processing. Next, primary etching is performed with a corrosive solution such as iron perchloride to form fine recesses that do not penetrate each other from the front and back surfaces. The composition for backing material 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 usual application method such as spraying, flow coating, bar coating, roll coating, die coating and dip coating may be adopted. After the step of curing the backing material composition, a corrosive liquid is supplied to the metal plate to perform a secondary etching targeting the concave portion on the other surface, and a concave portion on one surface and a concave portion on the other surface by the primary etching. Communicate at the bottom. The temperature in the secondary etching includes 40 to 90 ° C., and the composition of the present invention has a high temperature in the secondary etching as described above.
Since it has both etching resistance and alkali dissolution / peelability, it is preferably applicable to secondary etching at a high temperature of 70 to 90 ° C. An alkaline solution is supplied to the obtained metal plate having a large number of holes to separate the photosensitive resin film and the cured film of the curable composition for backing material from the metal plate. In this case, examples of the alkaline solution include aqueous solutions of NaOH and KOH.

The present invention will be more specifically described below with reference to Examples and Comparative Examples. In each example, "%"
Means% by weight.

Example 1 The following components were mixed to obtain a curable composition for etching resist. Aronix M-5400 (acryloyloxyethyl monophthalate) manufactured by Toagosei Co., Ltd.-50 parts Diacrylate of dihydric alcohol formed by adding two ethylene oxide units per molecule of bisphenol A --40 parts lauryl acrylate 10 parts Mercaptopropionic acid 2 parts NUC Silicone L7002 manufactured by Nippon Unicar Co., Ltd. 0.2 parts IRGACURE 184 manufactured by Ciba-Geigy 5 parts The obtained composition was used as a test iron plate (shadow mask). For, 27
cm × 20 cm × 0.1 mm) so as to have a film thickness of 30 μm. The coating film was irradiated with ultraviolet rays using a 80 w / cm concentrating metal halide lamp, and it was confirmed that the resin was cured because there was no tack on the coating film surface.
According to the method shown below the characteristics of the obtained cured film, the viscosity,
The hole filling property, surface smoothness, flexibility, etching resistance, alkali dissolution / peelability, and pattern formability were evaluated. The results are shown in Table 1.

<Hole filling property> A test iron plate (200) having a negative pattern formed of a casein type photosensitive resin film and having a large number of elongated rectangular recesses formed by primary etching.
An aperture grill type shadow mask iron plate comprising a repeating pattern of concave portions and flat portions alternately provided at μ intervals; hereinafter, referred to simply as a test iron plate). One side is filled with holes when the composition of the present invention is applied. The state was visually determined. ◯: There are no bubbles. Δ: Air bubbles are present in some holes. ×:
There are bubbles on the entire surface. <Surface smoothness> The composition of the present invention was cured by irradiating the iron plate after evaluating the hole filling property with ultraviolet rays, and the surface state of the cured film was visually determined. ○: No repelling. Δ: Some repelling occurred. X: Many repelling occurred. <Flexibility> The cured coating film was bent and the crack of the coating film was observed. ◯: The coating film is not broken. X: The coating film is broken.

<Etching resistance> After the surface smoothness was evaluated, the iron plate was immersed in an aqueous 43% FeCl ₃ solution at 90 ° C. for 20 minutes, and the surface state of the cured film was visually determined. ○: No change at all Δ: Colored. X: Swelling or peeling occurred. <Alkali Dissolution / Peelability> The iron plate after the etching resistance was evaluated was immersed in a 20% aqueous NaOH solution at 80 ° C. for 1 minute, and the solubility or peelability of the cured film was visually determined. A: Completely melted and peeled. ◯: It did not completely dissolve, but peeled off. Δ: Some of the peeled off remained on the metal plate. X: It did not peel off. <Pattern formability> By washing and drying the iron plate after evaluating the alkali dissolution / peeling property, and shining light from the back surface of the iron plate, the shape of the elongated rectangular hole formed in the iron plate can be visually observed with transmitted light. In this way, the size of the holes, the distance between the holes, and the linearity of the long side of the rectangle were determined by the uniformity of the brightness of the transmitted light. ⊚: The size of the holes and the distance between the holes are completely constant, and the long side of the rectangle is a straight line. ◯: There is a defect in one of about two out of 100 products. B: About 3 to 9 out of 100 products have defects at one place. X: There are 1 to 2 or more defects in 10 or more out of 100 products.

[0028]

Example 2 The following components were mixed to obtain a curable composition for etching resist. Toagosei Co., Ltd. Aronix M-5400 (acryloyloxyethyl monophthalate) ───50 parts Aronix M-5600 (acrylic acid dimer) ───10 parts Two propylene oxide units per bisphenol A molecule. Diacrylate of dihydric alcohol added ───20 parts Toagosei Co., Ltd. Aronix M-350 (triacrylate of ethylene oxide 3 mol addition to trimethylolpropane) ───20 parts Dodecyl mercaptan ── -2 parts Megafac F-177 (fluorine-containing oligomer) manufactured by Dainippon Ink and Chemicals, Inc. --- 0.2 parts BASF Lucillin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) --- ─ 5 copies

[0029]

Example 3 The following components were mixed to obtain a curable composition for etching resist. Toagosei Co., Ltd. Aronix M-5400 (acryloyloxyethyl monophthalate) ──60 parts Dihydric alcohol diacrylate formed by adding three ethylene oxide units per molecule of bisphenol A ───30 parts Toagosei Aronix M-111 (monoacrylate of ethylene oxide 1 mol adduct to nonylphenol) ─── 10 parts mercaptopropionic acid ─── 1 part NUC Silicone L7002 manufactured by Nippon Unicar KK ─── 0.2 Part Ciba Geigy Irgacure 651 ─── 5 parts

[0030]

Comparative Example 1 Toagosei Co., Ltd. was used instead of the diacrylate of a dihydric alcohol obtained by adding two ethylene oxide units per molecule of bisphenol A in Example 1.
Except that Aronix M-350 (triacrylate of ethylene oxide 3 mol addition to trimethylolpropane) was used, all the same compounds as in Example 1 were mixed in the same amounts to obtain a curable composition for etching resist. Obtained.

[0031]

Comparative Example 2 1 of bisphenol A in Example 2
Instead of 20 parts of diacrylate of dihydric alcohol formed by adding two propylene oxide units per molecule and 20 parts of Aronix M-350 manufactured by Toagosei Co., Ltd., 10 parts of lauryl acrylate and Aronix manufactured by Toagosei Co., Ltd. Except that 30 parts of M-210 (diacrylate of 4 mol ethylene oxide adduct to bisphenol A) was used, the same compounds as in Example 2 were all mixed in the same amounts to obtain a curable composition for etching resist. .

[0032]

Comparative Example 3 Toagosei Co., Ltd. was used instead of the diacrylate of a dihydric alcohol obtained by adding two ethylene oxide units per molecule of bisphenol A in Example 1.
A curable composition for etching resists was obtained by mixing the same amounts of the same compounds as in Example 1 except that Aronix M-305 (triacrylate of pentaerythritol) manufactured by Aronix was used. Table 1 shows the evaluation results of the performance of the curable compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 as etching resists.

[0033]

[Table 1]

[0034]

EFFECT OF THE INVENTION The curable composition for a backing material during the production of a shadow mask of the present invention is easily and quickly cured by irradiation with active energy rays or heating, and is cured even when secondary etching is performed at a high temperature. The film is excellent in etching resistance, alkali dissolution / peeling property, and pattern formability. Further, since the composition 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, and there is no need to worry about the toxicity of the organic solvent when handling the raw materials. The danger of ignition and explosion during drying can be prevented. Moreover, it can be cured for a short time without the need for a drying step involving the evaporation of an organic solvent, and it is useful in that energy costs can be reduced and fires can be prevented, and existing steps can be used for improvement. The industrial value is extremely large.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI // H01J 9/14 H01J 9/14 G (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03F ^7/ 004- 7/18

Claims (4)

(57) [Claims] 1. A curable composition for an etching resist, which comprises the following compounds (a) and (b) as main constituent components. (A) a compound having one carboxyl group and one (meth) acryloyl group in one molecule (b) a dihydric alcohol obtained by adding 2 to 3 alkylene oxide units per molecule of bisphenol A ( Di (meth) acrylate formed by esterification of (meth) acrylic acid 2. The curable composition for an etching resist according to claim 1, which contains a monofunctional vinyl monomer other than the compound (a). 3. The curable composition for an etching resist according to claim 1, which contains an acylphosphine oxide photoinitiator or 1-hydroxycyclohexyl phenyl ketone. 4. A method for producing a shadow mask, which comprises using the curable composition according to claim 1, 2 or 3 as a backing material in a secondary etching step in producing a shadow mask.