JP2003021899A - Curable composition for etching resist - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition for an etching resist giving a cured film excellent in etching resistance even in secondary etching at a high temperature and excellent also in suitability to subsequent alkali dissolution and removal and in pattern forming property and suitable for use as a backing material particularly in the manufacture of a shadow mask. SOLUTION: The curable composition contains (a) a compound having one carboxyl group and one (meth)acryloyl group in one molecule and (b) a compound having one or more carboxyl groups and two or more (meth)acryloyl groups in one molecule.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable composition for an etching resist, which can be cured by irradiating active energy rays such as ultraviolet rays or electron beams, and is obtained from the composition of the present invention. The cured film is
It is particularly suitable as an etching resist material in the secondary etching step during the production of a shadow mask because it can be easily peeled off from the substrate with an alkaline 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 characteristics (Japanese Patent Publication No. 7-
30270). 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. . Curability: The property that the composition for backing material is rapidly cured by irradiation with ultraviolet rays or active energy rays such as electron beams. Transportability: The property that the composition for backing material cured by irradiation with ultraviolet rays or active energy rays such as electron beams does not generate cracks or cracks during transport on the line in the shadow mask manufacturing process. Etching resistance: The property of the cured backing material composition having resistance to an etching solution for forming a desired precise hole in the shadow mask in the secondary etching step. Alkali releasability: A property that no peeling piece or foreign matter adheres to the shadow mask when the backing material composition after the second etching is peeled off with an alkali film removing liquid.

[0005]

Recently, in the production of shadow masks, studies have been made to increase the etching temperature in order to shorten the etching time and to easily 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 high temperature conditions, the resist film formed from the conventional curable composition for etching resist has a problem that the resist performance cannot be maintained because of insufficient etching resistance. Generally, in order to improve the etching resistance, it tends to increase the crosslink density of the cured product, but increasing the crosslink density of the cured product leads to a decrease in the alkali film peeling property, and when the film is peeled away Occurs and adheres to the shadow mask as a foreign substance, leading to a reduction in the product yield of the shadow mask. The present inventors have found that a curable composition that solves the above problems of conventional backing material compositions, that is, the cured film thereof has excellent etching resistance even in secondary etching under high temperature, and the subsequent alkali dissolution The present invention has been earnestly studied for the purpose of providing a curable composition excellent in both releasability and pattern formability.

[0006]

Means for Solving the Problems As a result of various investigations for solving the above problems, the present inventors have found that one carboxyl group and one (meth) acryloyl group are contained in one molecule. The present invention has been completed by finding that a composition in which a compound having one or more carboxyl groups and two or more (meth) acryloyl groups in one molecule is used in combination with the compound having the compound is effective. Hereinafter, the present invention will be described in detail. In addition, in this specification, an acryloyl group or a methacryloyl group is represented as a (meth) acryloyl group, an acrylate or a methacrylate is represented as a (meth) acrylate, and acrylic acid or methacrylic acid is represented as a (meth) acrylic acid.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION 1. (a) One carbo in one molecule
A compound having a xyl group and one (meth) acryloyl group
The component (a) is a compound having one carboxyl group and one (meth) acryloyl group in one molecule, and can be dissolved / released by an alkali treatment in a cured film obtained from the composition of the present invention. Is a component that imparts. As the component (a),
Various compounds can be used, and preferred are those having a dibasic acid or its acid anhydride and a hydroxyl group at the terminal (meth).
Examples thereof include a reaction product with an acrylate (half-ester compound), a reaction product with a lactone and a compound having a carboxyl group and a (meth) acryloyl group, and the like.

As the dibasic acid or its acid anhydride, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid,
Examples thereof include maleic acid, succinic acid, and acid anhydrides thereof. Examples of the (meth) acrylate having a hydroxyl group at the terminal include hydroxyalkyl (meth) s such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate. Acrylate etc. are mentioned.

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 end [ Aronix M-5300 manufactured by Toagosei Co., Ltd.].

In addition to the above compounds, (meth) acrylic acid and its dimer [Aronix M-produced by Toagosei Co., Ltd.]
5600] etc. can also be used.

The more preferable component (a) is (meth) acryloyloxyethyl monophthalate and (meth) acryloyloxyethyl monohexahydrophthalate in that the etching resistance and alkali solubility are well balanced.

The component (a) can be used alone or in combination of two or more kinds.

The preferable blending ratio of the component (a) is such that the total amount of the polymerizable components among the components constituting the composition is 100 parts by mass (hereinafter, “part” means “part by mass”). When it does, it is 20-80 parts, More preferably, it is 30-
It is 70 copies. If this ratio is less than 20 parts, the cured film of the composition will not have sufficient alkali dissolution / peelability,
If it is larger than the area, the corrosion resistance at the time of secondary etching may be insufficient.

2. (b) more than one carboxy in one molecule
Compound having two or more (meth) acryloyl groups
Object component (b), one or more carboxyl groups in one molecule and 2
It is a compound having at least one (meth) acryloyl group and is a component that imparts etching resistance and dissolution / peeling property by alkali treatment to the cured film obtained from the composition of the present invention.

As the component (b), various compounds can be used, and a compound having two or more (meth) acryloyl groups and a hydroxyl group [hereinafter referred to as a hydroxyl group-containing polyvalent (meth) acrylate] and a polybasic acid or an acid thereof. Esterification reaction products with anhydrides are preferred. As the hydroxyl group-containing poly (meth) acrylate, a partial (meth) acrylate compound of a polyhydric alcohol selected from pentaerythritol, dipentaerythritol and ditrimethylolpropane is preferable.
Specific examples include tri (meth) acrylate of pentaerythritol, penta (meth) acrylate of dipentaerythritol, and tri (meth) acrylate of ditrimethylolpropane. Examples of the polybasic acid or its acid anhydride include phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid, trimellitic acid, pyromellitic acid, dodecenyl succinic acid, ethylene glycol bis trimellitate, glycerol tris trimellitate. Examples thereof include tate, maleated methylcyclohexene tetrabasic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid and the like, and anhydrides thereof.

Specific examples of the component (b) include pentaerythritol tri (meth) acrylate monophthalate, pentaerythritol tri (meth) acrylate monotetrahydrophthalate, and pentaerythritol tri (meth) acrylate monohexahydro. Phthalate, pentaerythritol tri (meth) acrylate monosuccinate, dipentaerythritol penta (meth) acrylate monophthalate, dipentaerythritol penta (meth) acrylate monotetrahydrophthalate, dipentaerythritol penta (meth) Acrylate monohexahydrophthalate,
Dipentaerythritol penta (meth) acrylate monosuccinate, ditrimethylolpropane tri (meth) acrylate monophthalate, ditrimethylolpropane tri (meth) acrylate monotetrahydrophthalate, ditrimethylolpropane tri (meth) acrylate And monohexahydrophthalate and tri (meth) acrylate monosuccinate of ditrimethylolpropane.

The component (b) can be used alone or in combination of two or more kinds.

The preferable mixing ratio of the component (b) is 1 to 60 parts, when the total amount of the polymerizable components is 100 parts.
It is more preferably 5 to 40 parts. If this ratio is less than 1 part, the cured film of the composition may have insufficient corrosion resistance during secondary etching, and if it is more than 60 parts, the cured film of the composition may not have sufficient flexibility.

Conventionally, as a curable composition for etching resist, a polyvalent (meth) acrylate similar to the above-mentioned component (b), that is, tri- or tetra- (meth) acrylate of pentaerythritol, penta- or hexa- of dipentaerythritol ( Although a composition containing (meth) acrylate and tri- or tetra (meth) acrylate of ditrimethylolpropane as a main constituent has been known, such a known composition has excellent heat resistance during etching, but a cured film. It was difficult to use because the alkali dissolution / peelability of was extremely poor, but this problem could be solved by using the component (b).

3. Other Polymerizable Components In addition to the components (a) and (b), the composition of the present invention has (c) an alkylene oxide unit having 2 to 4 carbon atoms in one molecule as a polymerizable component, A compound having two or more (meth) acryloyl groups, a compound having one ethylenically unsaturated group other than the components (d) and (a), and two or more other than the components (e), (b) and (c). A compound having an ethylenically unsaturated group of
It can be blended as needed. The components (c) to (e) will be described below.

3-1. (C) Alky having 2 to 4 carbon atoms in one molecule
It has a lenoxide unit and contains two or more (meth) acryls.
Compound Having Royl Group In the composition of the present invention , a compound having an alkylene oxide unit having 2 to 4 carbon atoms in one molecule and having two or more (meth) acryloyl groups is added as a polymerizable component. It is preferable. By blending the component (c), the resulting cured film has excellent flexibility.

Specific examples of the component (c) include triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate. Examples thereof include polyalkylene glycol di (meth) acrylates such as acrylate, di (meth) acrylate of polypropylene glycol, di (meth) acrylate of tritetramethylene glycol and polytetramethylene glycol di (meth) acrylate. In addition, poly (meth) acrylates of alkylene oxide adducts of polyhydric alcohols and the like can be mentioned. In this case, the polyhydric alcohol includes butanediol, pentanediol, hexanediol, nonanediol, bisphenol A, bisphenol F, trimethylolpropane, pentaerythritol and glycerin, and the alkylene oxides include ethylene oxide and propylene oxide. And butylene oxide.

The preferable mixing ratio of the component (c) is 1 to 40 parts based on 100 parts of the total amount of the polymerizable components. If this ratio is less than 1 part, the cured film lacks flexibility, and the coating film may crack during transportation. On the other hand, if it is more than 40 parts, the etching resistance may be reduced.

3-2. One ethylenic non-component other than (d) (a) component
Compound Having Saturated Group It is preferable to add a compound having one ethylenically unsaturated group other than the component (a) as a polymerizable component to the composition of the present invention. When the component (d) is blended in the curable composition of the present invention, the resulting cured film has excellent flexibility. The preferable mixing ratio of the component (d) 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 film lacks flexibility, and the cured 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 (d) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate. And alkyl (meth) acrylates such as stearyl (meth) acrylate; hydroxyalkyl (meth) such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate
Acrylate; Polyalkylene glycol monoalkyl (C1-18) ether mono (meth) acrylate such as polyethylene glycol and polypropylene glycol; Polyalkylene glycol such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate Mono (meth) 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 p-
Mono (meth) acrylate of phenol alkylene oxide adduct such as mono (meth) acrylate of cumylphenol ethylene oxide or propylene oxide adduct; benzyl (meth) acrylate; (meth) acryloylmorpholine; tetrahydrofurfuryl (meth) Acrylate; N-vinylpyrrolidone; and isobornyl (meth) acrylate.

3-3. Two or more components other than the components (e), (b) and (c)
Compound Having Ethylenically Unsaturated Group In the composition of the present invention, as the polymerizable component, for example, polyol poly (meth) acrylate, polyester poly (meth) acrylate, epoxy (meth) acrylate, urethane poly (meth) acrylate, etc. (b) and
If desired, a compound having two or more ethylenically unsaturated groups other than the component (c) may be contained. The component (e) is used for adjusting the viscosity of the composition of the present invention, the etching resistance, or the alkali dissolution / peeling property of the cured film, and the like, and the preferable blending ratio thereof is that of the polymerizable component. It is 0 to 40 parts with respect to the total amount of 100 parts. The above polyol poly (meth) acrylate, polyester poly (meth) acrylate, polyvalent epoxy compound and (meth)
Specific examples of the reaction product of acrylic acid and urethane poly (meth) acrylate are described in various publicly known documents relating to curable compositions (for example, Japanese Patent Publication No. 7-30270), but some examples will be given. It is as follows.

3-3-1. Polyol Poly (meth) acrylate
It is a reaction product of polyhydric alcohol and (meth) acrylic acid, and specific compounds include butanediol di (meth) acrylate, pentanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl. Di (meth) acrylates such as glycol di (meth) acrylate, nonanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate and esterification diol di (meth) acrylate of hydroxypivalic acid and neopentyl glycol. ) Acrylate; and trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri- or tetra (meth) acrylate, pentaerythritol tri- or tetra (meth) acrylate and dipentaerythritol penta or Examples include poly (meth) acrylates of polyols such as hexa (meth) acrylate.

3-3-2. Polyester poly (meth) acrylate
Examples include reaction products of polyester-type polyhydric alcohols and (meth) acrylic acid. 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, trimethylol propane, pentaerythritol, ethylene oxide of trimethylol propane, or triol of propylene oxide adduct, ethylene oxide of glycerin, Or a propylene oxide adduct triol,
And a polyester alcohol obtained by reacting pentaerythritol with ethylene oxide or a propylene oxide adduct such as tetraol.

3-3-3. 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.

3-3-4. Urethane (meth) acrylate A reaction product of a polyhydric alcohol, a polyisocyanate 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, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate can be used.

4. Curable Composition for Etching Resist The composition of the present invention has a viscosity at 25 ° C. of 10,000.
It is preferably 0 cps or less, more preferably 5,0
It is less than 00 cps. When 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 recesses 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. A chain transfer agent, a leveling agent and / or a polymerization initiator is preferably added to the composition of the present invention. Each component will be described below.

4-1. 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 mercaptans such as octyl mercaptan, nonyl mercaptan, decyl mercaptan, dodecyl mercaptan and cetyl mercaptan; hydroxyl-substituted mercaptans such as monothioethylene glycol and α-monothioglycerin; and thioglycolic acid, mercaptopropionic acid, 2 -Mercaptocarboxylic acids such as mercaptopropionic acid, thiolactic acid and thiomalic acid. As the compounding ratio of the chain transfer agent, the total amount of the polymerizable 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.

4-2. 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 polymerizable 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 coating film may be likely to occur. .

4-3. 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. When the components are blended, 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.

Specific examples of preferable photopolymerization initiators include:
As the 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 Co., Ltd.], 1-hydroxy Cyclohexyl phenyl ketone [Irgacure 184 manufactured by Ciba-Geigy Co., Ltd.], diethoxyacetophenone [First Cure Co., Ltd. Fast Cure DEAP], 2-hydroxy-2-methyl-1-phenylpropan-1-one [Ciba-Geigy Co., Ltd. Darocur 1173] ], 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl)
Ketone [Ciba Geigy Co., Ltd. Irgacure 2959]
And 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone [Ciba Geigy Corp.
Irgacure 369] and the like. Examples of the benzoin ether type include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether. Examples of the benzophenone system include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, and 2,4,6-trimethylbenzophenone. As the thioxanthone type, 2-
Examples include isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.
Examples of acylphosphine oxide-based compounds include 2,4,6
-Trimethylbenzoyldiphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,
4,4-trimethylpentylphosphine oxide and the like can be mentioned. Other examples include camphor quinone.

Among these photopolymerization initiators, acyl can be used in the production of shadow masks in terms of improving pattern formability and preventing the occurrence of defects such as abnormally large holes in the metal plate. It is preferable to add a phosphine oxide photopolymerization initiator and / or 1-hydroxycyclohexyl phenyl ketone.

As the sensitizer used in combination with the above photopolymerization initiator, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate,
Isoamyl 4-dimethylaminobenzoate, 4,4-dimethylaminobenzophenone and 4,4-diethylaminobenzophenone are preferred.

When the composition is 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, 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 if it exceeds 15 parts, the components truly required for the cured film may be reduced, and the target properties of the cured film may be deteriorated. .

4-4. 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 in total of the polymerizable components.
It is 0 to 10 parts with respect to parts. In addition, in order to alleviate the strain during curing, it dissolves in the polymerizable component and has a molecular weight of 10
It is also possible to add a polymer of 00 to 100,000 or a particulate filler insoluble in the polymerizable 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.

5. Method for producing shadow mask The curable composition of the present invention can be preferably used as a composition for a backing material at the time of secondary etching in producing a shadow mask. Hereinafter, a method for manufacturing the shadow mask will be described. First, on both front and back sides of a thin metal plate made of iron,
Photosensitive printing is performed by applying a photosensitive resin such as casein and polyvinyl alcohol, and then sticking a negative film on which a pattern is placed to a metal plate to cure the exposed portion of the photosensitive resin, and then performing a development process to remove the non-existence of the photosensitive resin film. Remove the exposed areas. 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 is, for example, 40 to 90 ° C., and the composition of the present invention has both etching resistance and alkali dissolution / peeling property in the high temperature secondary etching as described above.
It is also preferably applicable to secondary etching at a high temperature of up 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.

[0043]

EXAMPLES The present invention will be described more specifically below with reference to Examples and Comparative Examples. In each example, "%" means mass%.

Examples 1 to 6 The components shown in Table 1 were mixed to produce an active energy ray-curable composition for a backing material for producing a shadow mask. Using the obtained composition, the viscosity, hole filling property, surface smoothness, etching resistance, alkali dissolution / peelability and pattern formability were evaluated according to the methods described below.
The results are shown in Table 2.

<Hole filling property> A test iron plate (for shadow mask, 27 cm × 20 cm × 0.1 mm) having a large number of elongated rectangular recesses formed by primary etching in which a negative pattern is formed with a casein type photosensitive resin film. , 200
Using a bar coater on one side of an aperture grill type shadow mask iron plate (hereinafter simply referred to as a test iron plate) consisting of a repeating pattern of concave portions and flat portions alternately provided at μ intervals so that the film thickness becomes 30 μm. The obtained composition was applied to. The state of hole filling at this time was visually determined. ◯: There are no bubbles. Δ: Air bubbles are present in some holes. ×:
There are bubbles on the entire surface.

<Surface smoothness> After the hole filling property was evaluated, the iron plate was coated with 80 w / cm high pressure mercury lamp, height 10 cm,
The composition was cured by irradiating with ultraviolet rays under the condition of 5 m / min. Since there was no tack on the surface of the cured film, it was confirmed that the composition was cured. The surface condition of the cured film was visually determined. ○: No repelling. Δ: Some repelling occurred. X: Many repelling occurred.

<Etching resistance> After the surface smoothness was evaluated, the iron plate was immersed in an aqueous 43% FeCl ₃ solution at 90 ° C. for 2 hours.
After soaking for 0 minute, the surface condition of the cured film was visually evaluated. ○: No change at all Δ: Colored. X: Swelling or peeling occurred.

<Alkali Dissolution / Removability> The iron plate after the etching resistance was evaluated was immersed in a 20% concentration aqueous solution of NaOH for 8 hours.
It was immersed at 0 ° C. for 1 minute, and the solubility or releasability 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> The iron plate after the alkali dissolution / peeling property is evaluated is washed with water and dried, and light is applied from the back surface of the iron plate so that the shape of the elongated rectangular hole formed in the iron plate is transmitted light. Then, the size of the holes, the distance between the holes, and the linearity of the long side of the rectangle were judged 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.

[0050]

[Table 1]

The abbreviations in Table 1 have the following meanings. a-1: acryloyloxyethyl monophthalate, manufactured by Toagosei Co., Ltd. Aronix M-5400 a-2: hexahydrophthalic anhydride adduct of hydroxyethyl acrylate b-1: succinic anhydride adduct of triacrylate of pentaerythritol b-2: Hexahydrophthalic anhydride adduct of triacrylate of pentaerythritol b-3: Succinic anhydride adduct of triacrylate of ditrimethylolpropane c-1: Tripropylene glycol diacrylate, Aronix manufactured by Toagosei Co., Ltd. M-220 c-2: tritetramethylene glycol diacrylate, Kyoeisha Chemical Co., Ltd. light acrylate PTMGA-
250 c-3: trimethylolpropane propylene oxide 6 mol modified triacrylate, Toagosei Co., Ltd. Aronix M-320 d-1: lauryl acrylate, Kyoeisha Chemical Co., Ltd. light acrylate L-A d-2: nonylphenol ethylene Oxide modified acrylate, Toagosei Co., Ltd. Aronix M-111 e-1: Bisphenol A ethylene oxide 4 mol modified diacrylate, Toagosei Co., Ltd. Aronix M-2
10 e-2: pentaerythritol triacrylate, Toagosei Co., Ltd. Aronix M-305 F-177: leveling agent, Dainippon Ink and Chemicals, Inc.
Megafac F-177 L-7002: Leveling agent, UC manufactured by Nippon Unicar Co., Ltd.
Silicone L-7002 Lucillin TPO: photopolymerization initiator, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, BA
SF's Lucillin TPO Irgacure 184: photopolymerization initiator, 1-hydroxycyclohexyl-phenylketone, Ciba Specialty Chemicals Co., Ltd. Irgacure 184 Irgacure 651: photopolymerization initiator, benzyl dimethyl ketal, Ciba Specialty Chemicals (corp.) ) Irgacure 651

[0052]

[Table 2]

Comparative Examples 1 to 4 The components shown in Table 1 were mixed to prepare an active energy ray-curable composition for a backing material at the time of manufacturing a shadow mask. The obtained composition was evaluated in the same manner as in the examples. The results are shown in Table 2.

[0054]

INDUSTRIAL APPLICABILITY The curable composition for etching resists of the present invention is particularly useful as a curable composition for a backing material in the production of a shadow mask, and can be easily and quickly irradiated with active energy rays or heated. Hardened, 2 at high temperature
Even in the case of subsequent etching, the cured film has excellent etching resistance, alkali dissolution / peeling property, and pattern formability. Further, since the composition of the present invention does not require an organic solvent, there is no need for a drying furnace for evaporating the organic solvent and a solvent recovery device, and there is no need to worry about the toxicity of the organic solvent when handling raw materials. Also, 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.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Ichiro Igarashi             1 Toago, 1 Funami-cho, Minato-ku, Nagoya-shi, Aichi             Synthetic Co., Ltd. F-term (reference) 2H025 AA07 AA10 AA16 AB17 AC01                       AC06 AD01 BC14 BC42 BC85                       CA02 CA35 FA17                 4J011 QA03 QA13 QA14 QA15 QA18                       QA23 QA33 QA35 QA46 SA61                       SA84 UA01 WA01 WA02                 4J100 AL08P AL66Q AL66R AL67Q                       AL67R BA08 BA15 BA16                       BC04 BC43 JA46

Claims (7)

[Claims] (A) One carboxyl group and one in one molecule
Having one (meth) acryloyl group and (b) 1
A curable composition for an etching resist, which comprises a compound having one or more carboxyl groups and two or more (meth) acryloyl groups in the molecule. 2. The etching resist according to claim 1, wherein the component (b) is an esterification reaction product of a compound having two or more (meth) acryloyl groups and hydroxyl groups with a polybasic acid or an acid anhydride thereof. Curable composition. 3. The compound having two or more (meth) acryloyl groups and hydroxyl groups is a partial (meth) acrylate compound of a polyhydric alcohol selected from pentaerythritol, dipentaerythritol and ditrimethylolpropane. A curable composition for an etching resist as described above. 4. The method according to claim 1, further comprising a compound having an alkylene oxide unit having 2 to 4 carbon atoms in one molecule and having 2 or more (meth) acryloyl groups. A curable composition for an etching resist as described above. 5. The curable composition for etching resist according to claim 1, further comprising a compound having one ethylenically unsaturated group other than the component (a). 6. The curable composition for an etching resist according to claim 1, further comprising an acylphosphine oxide photoinitiator or 1-hydroxycyclohexyl phenyl ketone. 7. A curable composition for a backing material at the time of producing a shadow mask, which comprises the composition according to any one of claims 1 to 6.