JP2001279131A - Ultraviolet-curable resin composition for back coating and method for manufacturing shadow mask using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ultraviolet-curable resin composition for back coating contributable to efficient manufacture of a shadow mask of high quality and to provide a manufacturing method of a shadow mask using the same. SOLUTION: The formation of a back coating film of high strength having a three-dimensional network structure is rendered easy and foreign substances are prevented from adhering to or depositing on a part to be etched even when a secondary etching temperature after the formation of the back coating film is raised by employing a curable resin composition which comprises a polymerizable compound bearing at least one acid group and at least one acryloyl or methacryloyl group in one molecule and a polymeric polymerization initiator comprising a main chain and, bonded thereto, a plurality of radical- generating side chains and has a mass-average molecular weight of 500-5,000. The manufacturing method of the shadow mask comprises forming a back coating film 8 using the curable resin composition thereby to realize improvement of the quality and efficient manufacture of the shadow mask 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet curable resin composition for a back coat suitably used for producing a shadow mask, and a method for producing a shadow mask using the same. The present invention relates to an ultraviolet-curable resin composition for a backcoat that enables formation of a backcoat film that can contribute to the production of a high-quality shadow mask by a polymerization initiator, and a method for producing a shadow mask using the same.

[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 predetermined luminous body. It is a thin plate. The formation of the minute holes is performed by providing a large number of hemispherical or angular minute concave portions having different diameters at corresponding positions on the front and back surfaces of the thin metal plate, and communicating the bottoms of the corresponding concave portions.

[0003] As a manufacturing process of a shadow mask, first, a photosensitive resin coating film is applied and formed on both front and back surfaces of a thin metal plate made of an iron alloy or the like (a photosensitive resin coating film forming process), and then a predetermined exposure pattern is formed. A negative film having a film is brought into close contact with a metal plate, and is exposed to light to cure an exposed portion of the photosensitive resin coating film (photo printing step), and a non-photosensitive portion of the photosensitive resin coating film is removed by a developing process (non-photosensitive portion). Removal step). Then
After performing primary etching with an etching solution such as an aqueous solution of ferric chloride to form minute recesses that do not penetrate each other from one side or both sides (primary etching step), apply an ultraviolet-curable resin composition for back coating to only one side. To form a film that fills the minute recesses on one surface of the metal thin plate, and cures the curable resin composition by heating and / or irradiating ultraviolet rays to form a back coat film (back coat step). After protecting one side in this way, secondary etching is again performed on the micro-recess on the other surface with an etchant, and the micro-recess on the one surface and the micro-recess on the other surface formed by the primary etching are again performed. After communicating at the bottom (secondary etching step), the above-mentioned photosensitive resin coating film and back coat film are removed by dissolving with an aqueous alkali solution (dissolving and removing step), and a shadow mask is manufactured.

In a method of manufacturing a shadow mask, a conventional ultraviolet-curable resin composition for a back coat (hereinafter referred to as a “curable resin composition”) plays an important role in uniformly forming fine holes by etching. And a compound having one acid group and one acryloyl group or methacryloyl group, and a low molecular weight polymerization initiator. The curable resin composition is required to have a property related to quality improvement that can form a hole having a uniform size and a property related to production efficiency that enables efficient production. As for quality improvement, it can be filled to every corner of the minute recess formed by the primary etching, it can be dissolved without leaving with an alkaline aqueous solution, etc.
As regards the efficiency of production, it is easy to dissolve in an alkaline aqueous solution, easy to apply on a thin metal plate by a roll method, a spray method or other methods, easy to be cured safely and easily by hot air drying, etc. . Investigations regarding the curable resin composition have been actively carried out conventionally, for example, JP-A-10-306124 and JP-A-10-306124.
307390, JP-A-5-100423, JP-A-3-272538, JP-B-62-15082 and the like.

[0005]

In the secondary etching step after forming the back coat film using the above-mentioned conventional curable resin composition, it is necessary to raise the temperature of the etchant to improve the etching rate. It is observed that foreign matter is attached to the minute concave portion which is the portion to be etched. Such a foreign substance hinders the etching of the adhered portion, and thus causes a problem of causing unevenness of the hole in the shadow mask. Although the cause is not clear, the component of the foreign substance elutes from the backcoat film due to the increase in the etching temperature because the component of the foreign substance matches the component of the backcoat film, and is deposited and adhered to the portion to be etched. It is inferred. Therefore, the upper limit temperature at which etching can be performed without causing foreign matter to adhere is usually about 70 ° C., and it is difficult to manufacture a high quality shadow mask while increasing the etching temperature to improve the efficiency of the secondary etching process. there were.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problem, and has an ultraviolet curable resin composition for a back coat which can contribute to the efficient production of a high quality shadow mask.
And a method of manufacturing a shadow mask using the same.

[0007]

The ultraviolet-curable resin composition for a back coat according to the present invention comprises a polymerizable compound having one or more acid groups and one or more acryloyl or methacryloyl groups in one molecule; It is characterized in that the chain contains a high molecular weight polymerization initiator having a mass average molecular weight of 500 to 5,000 in which a plurality of side chains generating radicals are bonded.

According to the present invention, a mass average molecular weight of 500 to 5 in which a plurality of side chains generating radicals are bonded to the main chain.
000, a polymerizable initiator having one or more acid groups and one or more acryloyl groups or methacryloyl groups in one molecule acts as an initiator of a radical polymerization reaction on a polymerizable compound having a polymerizable A high-strength back coat film having a three-dimensional network structure is formed together with the compound. After the formation of the back coat film having such a three-dimensional network structure, even if the secondary etching temperature is increased, no foreign matter adheres or deposits on the portion to be etched. for that reason,
By increasing the etching rate, it is possible to perform efficient etching and manufacture of a shadow mask. Further, since the back coat film is formed by using a polymerizable compound having one or more acid groups, it has the same alkali solubility as before. Therefore, the ultraviolet-curable resin composition for a back coat of the present invention can contribute to more efficient and high-quality production of a shadow mask.

The ultraviolet-curable resin composition for a back coat according to the present invention is characterized in that the high molecular polymerization initiator is represented by the following chemical formula 1. In the chemical formula 1, n is an integer of 3 to 5, R1 to R3 are H and / or an alkyl group, R4 is a phenyl group, a hydroxyalkyl group,
It is selected from a hydroxycyclohexyl group, a dialkoxy group or a derivative group thereof.

[0010]

Embedded image

In this case, a more preferred polymer polymerization initiator is 2-hydroxy-2-methyl-1- (4-
It is a polymer of (1-methylvinyl) phenyl) propanone.

Further, in the ultraviolet curable resin composition for a back coat according to the present invention, the polymer polymerization initiator is characterized by being represented by the following chemical formula 2. In this chemical formula 2, n is an integer of 1 to 6, m is an integer of 3 to 5, R
1 to R8 are selected from H and / or an alkyl group, and R9 is selected from an H and / or an alkyl group or a derivative thereof.

[0013]

Embedded image

In this case, a more preferred polymer polymerization initiator is [6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-.
Diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino] -1,6-hexanediyl [(2
2,6,6-tetramethyl-4-piperidinyl) imino].

In the ultraviolet curable resin composition for a back coat according to the present invention, the polymerizable compound is a compound having one or more acid groups and two or more acryloyl groups or methacryloyl groups in one molecule. Is preferred.

According to the present invention, since a polymerizable compound having two or more acryloyl groups or methacryloyl groups in one molecule is contained, a high-strength backcoat film having a three-dimensional network structure can be easily formed. As a result, even when the secondary etching temperature is increased, no foreign matter is adhered to the portion to be etched, and the etching rate can be increased to perform efficient etching and manufacture of a shadow mask.

The method for manufacturing a shadow mask according to the present invention comprises the steps of forming a photosensitive resin coating film on both surfaces of a thin metal plate, photographic printing the exposed portion of the photosensitive resin coating film, and exposing the photosensitive resin coating film to non-photosensitivity. Part removing step, primary etching step, back coating step of forming a back coat film on one side of the primary etched metal sheet, secondary etching step, and removing the photosensitive resin coating film and the back coat film by alkali treatment In the method for manufacturing a shadow mask, sequentially passing through the back coat step, the polymerizable compound having one or more acid groups and one or more acryloyl groups or methacryloyl groups in one molecule, and the main chain, a radical Weight average molecular weight of 50 or more side chains that generate
It is characterized by including a coating step of an ultraviolet-curable resin composition for a back coat containing 0 to 5000 high molecular polymerization initiator.

According to the present invention, as an ultraviolet-curable resin composition for a back coat, a polymerizable compound having one or more acid groups and one or more acryloyl groups or methacryloyl groups in one molecule; Since a polymer containing a polymer polymerization initiator having a mass average molecular weight of 500 to 5000 and having a plurality of side chains generating radicals bonded thereto is used, the polymer polymerization initiator is used as a polymerizable compound when forming the back coat film. After acting as an initiator of the radical polymerization reaction, a high-strength backcoat film having a three-dimensional network structure is formed together with the polymerizable compound. After the formation of the back coat film having such a three-dimensional network structure, even if the secondary etching temperature is increased, no foreign matter adheres or deposits on the portion to be etched. Therefore, the etching rate can be increased, and efficient etching and efficient and high-quality shadow mask production can be performed. Also, 3
Since a high-strength backcoat film with a three-dimensional network structure is formed, peeling and cracking do not occur even during operations such as transport, stabilizing the subsequent secondary etching process and stabilizing the quality of the shadow mask. It can also serve as a reinforcing material for the shadow mask during the manufacturing process.

In the method for producing a shadow mask of the present invention, it is preferable to use the polymer polymerization initiator represented by the above-mentioned chemical formula 1 or compound 2 as the polymer polymerization initiator.

In the method of manufacturing a shadow mask according to the present invention, in the step of applying the UV-curable resin composition for a back coat, the UV-curable resin composition for a back coat may have a dry film thickness of 10 to 60 μm. It is preferable to apply it.

According to the present invention, by forming the back coat film thinly, the back coat film can be efficiently dissolved and removed in a short time. Further, since the formed back coat film is reinforced by a three-dimensional network structure, even if it is a thin film, there is no occurrence of peeling or cracking even by operations such as conveyance, and the subsequent secondary etching step Can be performed stably, and a shadow mask with stable quality can be manufactured.

In the method of manufacturing a shadow mask according to the present invention, the secondary etching step may be performed in a range of 70 to 100.
It is preferably done with an acidic etchant at a temperature of ° C.

According to the present invention, even when secondary etching is performed with an acidic etching solution at a temperature of 70 to 100 ° C., no foreign matter adheres to the portion to be etched. Etching and shadow mask production can be performed.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an ultraviolet curable resin composition for a back coat according to the present invention and a method for producing a shadow mask using the same will be described in detail.

(1) UV-Curable Resin Composition for Backcoat The UV-curable resin composition for backcoat of the present invention (hereinafter referred to as “curable resin composition”) is used for backcoating during the manufacturing process of the shadow mask. A curable resin composition used in the forming step, a polymerizable compound having one or more acid groups and one or more acryloyl groups or methacryloyl groups in one molecule, and a side that generates radicals in the main chain. And a high molecular weight polymerization initiator having a mass average molecular weight of 500 to 5,000 in which a plurality of chains are bonded.

A feature of the present invention is that a mass average molecular weight of 500 to 50 in which a plurality of side chains generating radicals are bonded to a main chain.
Is a point that the polymerizable polymerization initiator has a radical with respect to a polymerizable compound having one or more acid groups and one or more acryloyl groups or methacryloyl groups in one molecule. After acting as a polymerization reaction initiator, a high-strength backcoat film having a three-dimensional network structure is formed together with the polymerizable compound. After that, even if the etching temperature in the secondary etching step is increased, there is no adhesion or deposition of foreign matter on the portion to be etched, and the etching rate can be increased to perform efficient etching and manufacture of a shadow mask. It has the effect of being able to. This is understood to be due to the fact that the backcoat film has a strong three-dimensional network structure, and is presumed to be due to the fact that components causing foreign matter are eluted from the backcoat film. You.

First, the polymerizable compound will be described. In the following, acryloyl group or methacryloyl group is generally referred to as “(meth) acryloyl group”.

The polymerizable compound is a main essential component of the curable resin composition, and is polymerized by a radical polymerization reaction caused by irradiation with ultraviolet rays to form a back coat film.

This polymerizable compound is a compound having one or more acid groups and one or more (meth) acryloyl groups in one molecule. In the present invention, the polymerizable compound having one or more acid groups and one or more (meth) acryloyl groups in one molecule includes (i) one acid group and one (meth) acryloyl group in one molecule. Or a compound having one or more acid groups and two or more (meth) acryloyl groups in one molecule (hereinafter referred to as a “monoacid group monofunctional monomer”). Base polyfunctional monomer "). Furthermore, as other polymerizable compounds,
(Iii) a compound having two or more functional groups in the molecule (hereinafter referred to as “polyfunctional monomer”), (iv) a monofunctional acrylic monomer, and the like can be appropriately compounded. These various monomers are leveling agents that can be further compounded,
Along with additives such as extenders, the viscosity of the curable resin composition, surface tension, fluidity, filling properties, coating properties, UV curability, and the hardness, strength, and alkali dissolution of the formed back coat film Preferred types and amounts are set according to the characteristics required in the production process, such as properties, and the characteristics required for the obtained backcoat film.

The monofunctional monofunctional monomer will be described.

The monoacid monofunctional monomer is a compound having one acid group and one (meth) acryloyl group in one molecule, and a conventional type ultraviolet curable polymerizable compound can be used. The acid group has a function of easily dissolving the formed back coat film in alkali, and is particularly preferably a carboxyl group, but may be a substituent derived from the carboxyl group.

As the monofunctional monofunctional monomer, a monoester compound of a monomer having one hydroxyl group and one (meth) acryloyl group in a molecule and a dibasic acid anhydride can be used. For example, (meth) acryloyloxyethyl monophthalate, (meth) acryloyloxypropyl monophthalate, (meth) acryloyloxybutyl monophthalate, (meth) acryloyloxyethyl monotetrahydrophthalate, (meth)
Acryloyloxypropyl monotetrahydrophthalate, (meth) acryloyloxybutyl monotetrahydrophthalate, (meth) acryloyloxyethyl monohexahydrophthalate, (meth) acryloyloxypropyl monohexahydrophthalate, (meth) acryloyloxybutyl monohexahydrophthalate, (Meth) acryloyloxyethyl monosuccinate, (meth) acryloyloxypropyl monosuccinate,
Examples thereof include (meth) acryloyloxybutyl succinate, (meth) acryloyloxyethyl malate, and the like, and one or more of the above compounds can be used by mixing at any ratio.

The synthesis of a monofunctional monofunctional monomer is usually carried out by a ring-opening addition reaction between the monomer and an acid anhydride, but it can also be made by a usual esterification reaction. Monomers having one hydroxyl group and one (meth) acryloyl group in the molecule include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate,
Examples thereof include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, and polycaprolactam mono (meth) acrylate. Examples of dibasic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, propyltetrahydrophthalic anhydride, butyltetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Acid anhydride, methyl hexahydrophthalic anhydride, ethyl hexahydrophthalic anhydride, propyl hexahydrophthalic anhydride, isopropyl hexahydrophthalic anhydride, butyl hexahydrophthalic anhydride, maleic anhydride, succinic Acid anhydrides and the like can be exemplified. When a monofunctional monofunctional monomer is synthesized from such a monomer and an acid anhydride, a tertiary amine such as triethylamine, morpholine or triethanolamine or a quaternary ammonium salt thereof is used as a reaction accelerator. be able to. Further, in order to prevent polymerization from occurring during the reaction, a polymerization inhibitor such as hydroquinone, butylhydroquinone, butylcatechol, and phenothiazine may be used.

The monofunctional polyfunctional monomer will be described.

The monoacid group polyfunctional monomer is a compound having one or more acid groups and two or more (meth) acryloyl groups in one molecule, and is particularly preferably used in the present invention.
The monoacid group polyfunctional monomer has a plurality of (meth) acryloyl groups, the (meth) acryloyl group of the other monoacid group polyfunctional monomer, the (meth) acryloyl group of the above monoacid group monofunctional monomer, Reacts with the functional groups of other polymerizable compounds, and further with a polymer polymerization initiator described later, easily forms a three-dimensional network structure, and can form a strong backcoat film in which foreign substances do not elute. The preferred effect can be exhibited. Incidentally, the acid group has a function of easily dissolving the formed back coat film with alkali similarly to the above, and is particularly preferably a carboxyl group, but is preferably a substituent derived from the carboxyl group. There may be. Examples of the monofunctional group polyfunctional monomer include mono (2,2,2-tri-acryloyloxymethyl) ethyl phthalate represented by Chemical Formula 3 and “NK Oligo EA-1040” (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) represented by Chemical Formula 4. ) Can be preferably used. In the present invention, other compounds having the same action and effect as these compounds can also be preferably used.

[0036]

Embedded image

[0037]

Embedded image

The synthesis of a monofunctional polyfunctional monomer is usually carried out by
The reaction is carried out by an addition reaction between a monomer having one or more hydroxyl groups and two or more (meth) acryloyl groups in the molecule and a dibasic acid anhydride, but can also be synthesized by a usual esterification reaction. Examples of the monomer having one or more hydroxyl groups and two or more (meth) acryloyl groups in a molecule include EO-modified diacrylate of isocyanuric acid, pentaerythritol diacrylate, and pentaerythritol triacrylate.
As the dibasic acid anhydride, the same one as in the case of the monofunctional monofunctional monomer described above can be used. When synthesizing a monofunctional monofunctional monomer from such a monomer and an acid anhydride, it is possible to use a reaction accelerator or a polymerization inhibitor used when synthesizing the monofunctional monofunctional monomer described above as necessary. it can.

The polyfunctional monomer is a compound having two or more functional groups in the molecule, for example, a (meth) acryloyl group, and is used for adjusting the curing properties of the cured coating film and the strength of the back coat film. You. For example, a reaction product of a polyhydric alcohol and (meth) acrylic acid, a reaction product of a polybasic acid or its anhydride and (meth) acrylic acid, an epoxy compound having one or more epoxy groups in a molecule, and A) a reaction product of acrylic acid, a reaction product of an isocyanate compound having one or more isocyanate groups in a molecule and a hydroxyl group-containing (meth) acrylate, and the like. More specifically, di (meth) acrylates of alkyl diols such as 1,6-hexanediol di (meth) acrylate and 1,9-nonanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythritol-di, -tri or -tetra (meth) acrylate,
Dipentaerythritol-di, -tri, -tetra, -penta or -hexa (meth) acrylate, dimethylolpropane di (meth) acrylate, trimethylolpropane-di or -tri (meth) acrylate, Showa Kogyo Co., Ltd. Phenol novolak type epoxy (meth) acrylate such as Lipoxy SP-4010, cresol novolak type epoxy (meth) acrylate, and Kyoeisha Chemical Co., Ltd .: bisphenol A type epoxy-di (meth) acrylate such as epoxy ester 3000A, tri Glycidyl isocyanurate di- or tri (meth)
Acrylate, tetraphenylmethane type epoxy-di,
-Tri- or -tetra (meth) acrylate, trisphenylmethane type epoxy-di or -tri (meth) acrylate, glycerin diglycidyl ether di (meth)
Acrylate, isocyanuric acid di- or tri (meth) acrylate, melamine di or tri (meth)
Examples include acrylates, urethane (meth) acrylates, aminoalkyl (meth) acrylates, and polyfunctional compounds such as ethylene oxide adducts and propylene oxide adducts of the above compounds. One or more of the above compounds may be used at any ratio. Can be used by mixing.

The monofunctional acrylic monomer will be described.

The monofunctional acrylic monomer is a compound having one (meth) acryloyl group in the molecule, and is effective in adjusting the viscosity of the curable resin composition and the properties of the cured coating film. For example, alkyl (meth) acrylates such as propyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and the like Hydroxyalkyl (meth) acrylates, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, benzoyloxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, hydroxyphenoxypropyl (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate, isobonyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate Cyclic (meth) acrylates, aminoalkyl (meth) acrylates such as dialkylaminoethyl (meth) acrylate, cyanoethyl (meth) acrylate, ethoxyethyl (meth) acrylate, (meth) acryloxyethyl phosphate, fluoroalkyl ( (Meth) acrylate, sulfopropyl (meth) acrylate, glycidyl (meth) acrylates, urethane (meth) acrylates, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene Glycol mono (meth) acrylate, pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, dimethylol Pan mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, triglycidyl isocyanurate mono (meth) acrylate, tetraphenylmethane type epoxy-mono (meth) acrylate, trisphenylmethane type epoxy-mono (meth) acrylate, glycerin Diglycidyl ether mono (meth) acrylate,
Monofunctional compounds such as isocyanuric acid mono (meth) acrylate, melamine mono (meth) acrylate, and ethylene oxide adducts and propylene oxide adducts of the above compounds, and one or more of the above compounds may be mixed at any ratio. Can be used.

Next, the polymer polymerization initiator will be described.

The polymer polymerization initiator has a mass average molecular weight of 500 to 500 in which a plurality of side chains generating radicals are bonded to the main chain.
5000 polymerization initiators. This polymer polymerization initiator acts as a radical polymerization reaction initiator for the polymerizable compound having a monofunctional monofunctional monomer and / or a monofunctional polyfunctional monomer. That is, the side chain that generates radicals efficiently absorbs ultraviolet light and becomes an excited state, (i) the side chain is cleaved to generate a radical, or (ii) the side chain causes a hydrogen abstraction reaction. (Iii) a radical is generated by an electron transfer reaction between its side chain and a (meth) acryloyl group in the curable resin composition, thereby producing the above-described monofunctional monofunctional monomer. It induces a radical polymerization reaction based on the (meth) acryloyl group of the polyfunctional monomer or monoacid group. After the radical polymerization reaction, the high-molecular polymerization initiator forms a three-dimensional network structure with the above-mentioned polymerizable compound, and forms a part of the back coat film.

As the polymer polymerization initiator, those represented by the following chemical formula 1 can be preferably used.

[0045]

Embedded image

The main chain of the polymerized polymerization initiator represented by the chemical formula 1 is usually composed of repeating units of an alkylene group,
Is an integer of 3 to 5. The alkylene group has a side chain R1, R2, R3 such as an alkyl group in a range that does not inhibit the polymerization reaction (that is, a range inactive to the polymerization reaction or a range that does not adversely affect the polymerization reaction). May be. The side chains R1, R2 and R3 are usually H, C1 to C3 alkyl groups.

On the other hand, the side chain that generates radicals efficiently absorbs ultraviolet light and easily enters an excited state.
Those having at least an aroyl group (aromatic acyl group) such as benzoyl are preferably used. Specifically, benzoin alkyl ethers such as benzoin isopropyl ether, acetophenones such as diethyl acetophenone, 2-hydroxy-2-methyl -1- (4- (1-
Examples thereof include propiophenones such as methylvinyl) phenyl) propanone, anthraquinones such as 2-ethylanthraquinone, thioxanthones such as isopropylthioxanthone, and ketals such as benzyldimethylketal. In the polymer polymerization initiator of the present invention, it is sufficient that one or more of the above-mentioned ones are bonded to the main chain as a side chain. In addition, the above-mentioned chemical formula 1
In the above, it is preferable that the functional group R4 in the side chain is selected from any of a phenyl group, a hydroxyalkyl group, a hydroxycyclohexyl group, a dialkoxy group and a derivative group thereof.

Of these, a more preferred polymer polymerization initiator is 2-hydroxy-2-methyl-1- (4- (1-
It is a polymer of methylvinyl) phenyl) propanone.

Further, as the polymer polymerization initiator, those represented by the following chemical formula 2 can also be preferably used.

[0050]

Embedded image

The main chain of the polymer polymerization initiator represented by the chemical formula 2 is composed of a repeating unit having an alkylene group, a piperidinyl imino group, and a triazine group, and n is 1 to 6.
And m is an integer of 3 to 5. The main chain may have a side chain such as an alkyl group as long as the polymerization reaction is not inhibited, as described above.

On the other hand, the functional groups R1 to R8 of the side chains that generate radicals are H and / or alkyl groups, and R9 is H and / or
Or an alkyl group or a derivative thereof.

Of these, a more preferred high molecular weight polymerization initiator is represented by the following chemical formula 5 wherein n is an integer of 1 to 6 and m is an integer of 3 to 5 [6-[(1,1,3,3 -Tetramethylbutyl) amino] -1,3,5-triazine-2,4-
Diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino] -1,6-hexanediyl [(2
2,6,6-tetramethyl-4-piperidinyl) imino].

[0054]

Embedded image

In the present invention, the weight average molecular weight of the high molecular weight polymerization initiator is preferably in the range of 500 to 5,000. In addition, both ends of the main chain portion of the polymer polymerization initiator,
Usually, a terminal terminating group such as H or an alkyl group is bonded.
Furthermore, in the curable resin composition of the present invention, a conventionally known low molecular weight polymerization initiator can be blended together with the above-mentioned high molecular weight polymerization initiator.

As the low molecular weight polymerization initiator, any known polymerization initiator can be appropriately selected and used. For example, benzoin alkyl ethers such as benzoin isopropyl ether, acetophenones such as diethyl acetophenone, propiophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, and anthraquinones such as 2-ethylanthraquinone And thioxanthones such as isopropylthioxanthone, and monomers such as ketals such as benzyldimethylketal. One or more of the above compounds can be used in a mixture at an arbitrary ratio. Of these, (i)
n is 3 to 5 2-hydroxy-2-methyl-1- (4-
A curable resin composition comprising a polymerization initiator obtained by mixing a polymer polymerization initiator composed of a polymer of (1-methylvinyl) phenyl) propanone and a low molecular weight polymerization initiator represented by the following chemical formula 6 in a ratio of 7: 3: (Ii) 2-hydroxy-2-methyl-1- (4) wherein n is 3 to 5 as described above.
A polymerization initiator obtained by mixing a high molecular weight polymerization initiator composed of a polymer of-(1-methylvinyl) phenyl) propanone and a low molecular weight polymerization initiator represented by the following chemical formula 7 in a ratio of 3: 7, It is preferable to include them in the composition. In Chemical Formula 7, R, R ′, and R ″ represent H,
Selected from the group consisting of CH _3.

[0057]

Embedded image

[0058]

Embedded image

The polymer polymerization initiator described above causes the polymerizable compound in the curable resin composition to undergo a radical polymerization reaction by its action, thereby curing the back coat film. On the other hand, the polymer polymerization initiator itself forms a three-dimensional network structure with the polymerizable compound and is included in the back coat film. When such a back coat film is formed, even if the etching temperature in the secondary etching step is increased, no adhesion or deposition of foreign matter is observed on the portion to be etched. This is because a strong back coat film having a three-dimensional network structure was formed by the action of the polymer polymerization initiator, and the polymer polymerization initiator and other components were easily restrained by the three-dimensional network structure. It is presumed to be based on the reason that it is difficult to elute into the water. In addition, even in the case of a low-molecular-weight polymerization initiator that can be blended with the high-molecular-weight polymerization initiator, considering that it is necessary to be in a state in which it is difficult to be eluted by being constrained by the three-dimensional network structure, The compounding amount is selected. Therefore, since the obtained back coat film is formed of a curable resin compound containing a high molecular weight polymerization initiator and a low molecular weight polymerization initiator added as needed, even if the etching rate is increased, the etching is performed without unevenness of the holes. it can. As a result, a remarkable effect is exhibited in that efficient etching can be performed and the manufacturing efficiency of the shadow mask can be improved.

The curable resin composition of the present invention may contain a leveling agent and other compounding materials as necessary. The leveling agent is a component that adjusts the filling property of the curable resin composition into the fine recesses, the surface smoothness of the cured coating film, the defoaming property of the composition, and the surface tension. The purpose can be sufficiently achieved by using a general antifoaming agent, surface smoothing agent, wetting and dispersing agent, and the like.

As described above, the curable resin composition of the present invention has been described. As a method for applying the curable resin composition, conventional methods such as a roll coating method, a spray coating method, a flow coating method, and a dip coating method are used. A coating method can be used. By heating the curable resin composition to a temperature equal to or higher than room temperature, the filling property of the fine concave portions can be further improved by lowering the viscosity of the composition. The curable resin composition of the present invention is obtained by a normal method using a high-pressure mercury lamp,
It can be cured by irradiating ultraviolet rays with a metal halide lamp, a xenon lamp or the like.

Since the back coat film is firmly formed by the curable resin composition of the present invention, the back coat film is unlikely to be cracked or peeled even during transportation and handling during the shadow mask manufacturing process. Further, the shadow mask can also serve as a reinforcing material for the metal sheet. Therefore, it is possible to perform etching of the minute concave portion at the time of the secondary etching step with high accuracy, and it is extremely effective in manufacturing a high-accuracy and high-quality shadow mask.

(2) Method of Manufacturing Shadow Mask FIG. 1 is a process chart showing an example of a method of manufacturing a shadow mask of the present invention.

The shadow mask 1 uses a thin metal plate 2 made of an invar material (Fe-36 mass% Ni alloy) or the like which has been subjected to alkali degreasing or water washing in advance as a base material. A photosensitive resin coating film is formed (a step of forming a photosensitive resin coating film). The photosensitive resin film is a thin metal plate 2.
It is applied to a predetermined thickness on the top and dried to form. As the photosensitive resin, a resin composition composed of casein or modified PVA (polyvinyl alcohol) and a dichromate is usually used, and as a coating method, a dipping method or a kiss coater method is used.

Next, the photosensitive resin coating film 3 is photographic printed in a predetermined pattern (photo printing step). Photo printing is performed by forming a photomask in which a pattern corresponding to a small hole on the electron gun side of a shadow mask is formed on a photosensitive resin coating film 3 formed on both surfaces of a metal thin plate 2 and a large mask on a fluorescent surface side of the shadow mask. This is performed by closely adhering a pair of photomasks including a photomask on which a pattern corresponding to the hole is formed, irradiating ultraviolet light or the like, and curing the photomask according to the pattern of each photomask.

Next, the non-photosensitive portion of the photosensitive resin coating film 3 is removed (step of removing the non-photosensitive portion). The non-photosensitive portion not irradiated with the ultraviolet rays can be developed with a predetermined developing solution and easily removed. Thereafter, drying and hardening (baking) are performed to form a resist pattern corresponding to the pair of photomask patterns described above, as shown in FIG.

Next, primary etching is performed with an acidic etching solution such as an aqueous ferric chloride solution (primary etching step). The primary etching step is, as shown in FIG. 1 (b), a step of forming minute recesses 6, 7 which do not penetrate each other on both the front and back surfaces of the metal sheet 2, and (i) from both sides of the small hole side and the large hole side. (Ii) First, an etching resistance material or a protection film is provided on one surface and the other surface is etched, and then an etching resistance material or a protection film is provided on the etched surface and the other is etched. It can be performed by a method of etching the surface, or the like. As the etching solution, an acidic etching solution represented by an aqueous ferric chloride solution is used. After the etching, it is usually washed by alkali neutralization treatment and multi-stage water washing.

Next, a back coat film 8 is formed in one of the minute concave portions 6 (back coat step). In the back coat step, as shown in FIG. 1 (c), by forming a back coat film 8 filling one of the minute concave portions 6, the holes of the finally manufactured shadow mask 1 can be uniformly and accurately formed. Done to form. Normally, as shown in FIG. 1 (c), the above-described ultraviolet curable resin composition for back coat (curable resin composition) of the present invention is applied to the small concave portion 6 on the small hole side, and the corners are formed. The back coat film 8 is formed by sufficiently filling and then curing by irradiating ultraviolet rays.

Next, the micro concave portion 7 on the side where the back coat film 8 is not formed is etched again (secondary etching step). In the secondary etching, as shown in FIG. 1 (d), the small concave portion 7 on the large hole side where the back coat film 8 is not formed is etched with the same etching solution made of an aqueous ferric chloride solution as in the first etching. The small concave portion 6 on the small hole side on which the back coat film 8 is formed
This is a step of penetrating (communicating) through the holes. After the etching, as in the case of the first etching, cleaning is performed by alkali neutralization treatment and multi-stage water washing.

Finally, the back coat film 8 and the photosensitive resin coating film 3 are dissolved and removed (dissolution removing step). An alkaline aqueous solution such as an aqueous sodium hydroxide solution is used for dissolution and removal, and as shown in FIG. 1E, the shadow mask 1 having predetermined holes is manufactured by dissolution and removal. Since the manufactured shadow mask 1 can control the opening diameter (the opening diameter of the communicating portion between the small hole and the large hole) by adjusting the etching amount on the small hole side in the primary etching, the shadow mask 1 has high definition and high quality. .

A feature of the method for producing a shadow mask of the present invention is that, in the step of applying the curable resin composition during the back coat step, the above-mentioned curable resin composition, that is, one or more acid groups in one molecule is used. A polymerizable compound containing the above (meth) acryloyl group and a mass average molecular weight of 500 to 500 in which a plurality of side chains generating radicals are bonded to the main chain.
A curable resin composition containing a high molecular weight polymerization initiator is used. When the back coat film 8 is formed using the above-described curable resin composition of the present invention, the temperature of the etchant is set to 70 to 70 in the subsequent secondary etching step.
Even at a high temperature of 100 ° C., preferably 80 ° C. to 90 ° C., the phenomenon that no foreign matter is deposited or adhered to the minute concave portion 7 which is the portion to be etched as in the related art is observed. For this reason, the etching rate can be increased by increasing the etching temperature as compared with the related art, so that the process efficiency of the secondary etching and the manufacturing efficiency of the shadow mask can be improved. The reason why the deposition or adhesion of the foreign matter does not occur is as described above.

The obtained back coat film is formed in a three-dimensional network structure by the polymer polymerization initiator and the polymerizable compound contained in the curable resin composition. Since the back coat film having such a structure is formed uniformly with high strength,
There is no occurrence of peeling or cracking even by a work such as transportation, and the subsequent secondary etching step can be performed stably to produce a shadow mask of stable quality.
Further, it can also serve as a reinforcing material for the shadow mask. Further, even when the reinforced back coat film is formed in a dry thickness of 10 to 60 μm, preferably 10 to 25 μm, it can sufficiently function as a back coat film and as a reinforcing material for a shadow mask. Can demonstrate. Reducing the thickness of the back coat film is convenient because the subsequent dissolution and removal with an aqueous alkali solution can be performed in a short time.

As described above, the method of manufacturing a shadow mask according to the present invention is effective for manufacturing a more efficient and high quality shadow mask.

[0074]

The present invention will be described more specifically with reference to the following examples and comparative examples. In the following, "%" means% by mass, and "part" means part by mass.

(Example 1) Biscoat # 2100 (trade name, manufactured by Osaka Organic Chemicals) 6 as a monofunctional acrylic monomer
0 parts, mono (2,2,2-tri-acryloyloxymethyl) ethyl phthalate of the above formula 3 (trade name: CBX-1, manufactured by Shin-Nakamura Chemical Co., Ltd.)
5 parts, 2-hydroxy-2-methyl-1 having a weight average molecular weight of about 500 to 2,000 with n = 3 to 5 as a photopolymerization initiator
KIP-150 (trade name, lambe) comprising a polymer of-(4- (1-methylvinyl) phenyl) propanone
rti chemical specialties
Was dissolved and mixed to prepare a curable resin composition of Example 1.

Example 2 As a photopolymerization initiator, [6-[(1,1,3,3-tetramethylbutyl) amino] -1,1 having a mass average molecular weight of about 2000 to 3300 represented by the above chemical formula 5 was used. 3,5-triazine-2,4-diyl]
[(2,2,6,6-tetramethyl-4-piperidinyl) imino] -1,6-hexanediyl [(2,2,6
6,6-Tetramethyl-4-piperidinyl) imino] (DOUBLE BOND CHEMICAL)
IND., CO., LTD.) Was used in the same manner as in Example 1 except that 5 parts of the curable resin composition of Example 2 was prepared.

Example 3 The procedure of Example 1 was repeated, except that 35 parts of NK oligo EA-1040 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) of the above formula 4 was used as the monofunctional polyfunctional monomer. The curable resin composition of Example 3 was prepared.

Comparative Example 1 Biscoat # 2100 (trade name, manufactured by Osaka Organic Chemicals) 6 as a monofunctional acrylic monomer
5 parts of M- represented by the following chemical formula 8 as a polyfunctional monomer:
315 (trade name, manufactured by Toagosei Co., Ltd.), 30 parts, Irgacure 184 which is a low molecular weight polymerization initiator as a photopolymerization initiator
Dissolve 5 parts (Ciba Specialty Chemicals)
By mixing, a curable resin composition of Comparative Example 1 was prepared.

[0079]

Embedded image

Comparative Example 2 Biscoat # 2100 (trade name, manufactured by Osaka Organic Chemical) 6 as a monofunctional acrylic monomer
5 parts, M- represented by the following chemical formula 9 as a polyfunctional monomer:
215 (trade name, manufactured by Toagosei Co., Ltd.), 30 parts, Irgacure 184 which is a low molecular weight polymerization initiator as a photopolymerization initiator
Dissolve 5 parts (Ciba Specialty Chemicals)
By mixing, a curable resin composition of Comparative Example 2 was prepared.

[0081]

Embedded image

(Test at 90 ° C. Etching Precipitation) Example 1
Each of the curable resin compositions of Comparative Examples 1 to 3 and Comparative Examples 1 and 2 was applied on an Invar alloy thin plate so that the film thickness after curing became 30 μm. The coating film was irradiated with ultraviolet light of 1000 mJ / cm ² using a 240 W high-pressure mercury lamp. The absence of tack on the coating film surface confirmed the curing of the coating film, and the irradiation was terminated.

From the obtained cured film, 50 g was collected, and 45 °
Be (Bome) FeCl ₂ aqueous solution: 500 g, HC
1 (36%): 2.8 g, and the mixture was heated and refluxed at 90 ° C. for 4 hours while air bubbling. The cured film after treatment is removed by filtration,
The filtrate was left at room temperature for 15 hours. Remove the filtrate after standing
Filter through a μm filter, dry the resulting precipitate,
The mass of the precipitate was measured. The evaluation criteria for the 90 ° C. etching deposition test were as follows: 析出: the deposition amount was less than 0.5 g;
Δ: The amount of precipitation was 0.5 g or more to less than 1.0 g, and X: The amount of precipitation was 1.0 g or more. The results are shown in Table 1.

(Alkali dissolution / peelability test) A casein resist-based photosensitive resin coating film was formed on an amber alloy thin plate, and then a negative pattern was formed through a photographic printing process and a non-photosensitive portion removing process. Next, a test thin plate having a large number of minute concave portions was manufactured by a primary etching process. Examples 1 to 3 and Comparative Examples 1 and 2 were placed on one side of the test thin plate.
Each of the curable resin compositions was applied and then cured by ultraviolet irradiation to form a back coat film.

A test sample on which a back coat film composed of each curable resin composition was formed was poured into a 20% aqueous sodium hydroxide solution at 90 ° C., and the time required for the back coat film to completely peel off from the test thin plate was measured. did. The evaluation criteria for the alkali dissolution / peelability test were as follows: ： １: less than 1 minute, 以上: 1 minute or more to less than 2 minutes, Δ: 2 minutes to less than 3 minutes, ×: 3 minutes or more. The results are shown in Table 1.

[0086]

[Table 1]

[0087]

As described above, according to the ultraviolet curable resin composition for a back coat of the present invention, a high-strength back coat film having a three-dimensional network structure can be easily formed and further contained. The polymeric polymerization initiator forms a three-dimensional network with the polymerizable compound. By forming such a back coat film, no foreign matter adheres or deposits on the etched portion even when the subsequent secondary etching temperature is increased. Therefore, the etching rate can be increased, and efficient etching and manufacture of a shadow mask can be performed. Furthermore, it has the same alkali solubility as before.

According to the shadow mask manufacturing method of the present invention, the back coat film is formed by the curable resin composition containing the polymerizable compound and the polymer polymerization initiator.
Even when the secondary etching temperature after the formation of the back coat film is increased, no foreign matter adheres or deposits on the etched portion. Therefore, the etching rate can be increased, and efficient etching and manufacture of a shadow mask can be performed.
In addition, since a high-strength backcoat film having a three-dimensional network structure is formed, peeling or cracking does not occur even during operations such as conveyance, and the subsequent secondary etching process is performed stably to ensure quality. A stable shadow mask can be manufactured, and can also serve as a reinforcing material for the shadow mask. Further, since a thin back coat film can be formed, the back coat film can be efficiently dissolved and removed.

[Brief description of the drawings]

FIG. 1 is a process chart showing an example of a method for manufacturing a shadow mask of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Shadow mask 2 Thin metal plate 3 Photosensitive resin coating film 4 Small hole side 5 Large hole side 6, 7 Fine recess 8 Back coat film

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA09 AA10 AA13 AB14 AB20 AC01 AD01 BC13 BC42 CA01 CA03 CA28 4J011 AA05 DA02 FB01 QA03 QA12 QA22 QA35 RA10 SA61 SA78 SA89 UA01 VA01 WA01 4J038 FA151 GA02 GA03 GA03 PA03 PB09 PC02 5C027 HH11

Claims (11)

[Claims] 1. A polymerizable compound having one or more acid groups and one or more acryloyl groups or methacryloyl groups in one molecule, and a mass average molecular weight of 500 to 500 in which a plurality of side chains generating radicals are bonded to a main chain. An ultraviolet-curable resin composition for a back coat, comprising 5,000 of a polymer polymerization initiator. 2. The ultraviolet curable resin composition for a back coat according to claim 1, wherein the polymer polymerization initiator is represented by the following chemical formula 1. In the chemical formula 1, n is an integer of 3 to 5, R1 to R3 are H and / or an alkyl group, and R4 is a phenyl group, a hydroxyalkyl group, a hydroxycyclohexyl group, a dialkoxy group, or a derivative thereof. It is. Embedded image 3. The method according to claim 2, wherein the polymer polymerization initiator is a polymer of 2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone. UV curable resin composition for back coat. 4. The ultraviolet curable resin composition for a back coat according to claim 1, wherein the polymer polymerization initiator is represented by the following chemical formula 2. In the chemical formula 2, n is an integer of 1 to 6, m is an integer of 3 to 5, R1 to R8
Is H and / or an alkyl group, and R9 is selected from H and / or an alkyl group or a derivative thereof. Embedded image 5. The method according to claim 1, wherein the polymer polymerization initiator is [6-
[(1,1,3,3-tetramethylbutyl) amino]-
1,3,5-triazine-2,4-diyl] [(2,
2,6,6-tetramethyl-4-piperidinyl) imino] -1,6-hexanediyl [(2,2,6,6-tetramethyl-4-piperidinyl) imino]. The ultraviolet curable resin composition for a back coat according to claim 4. 6. The compound according to claim 1, wherein the polymerizable compound is a compound having one or more acid groups and two or more acryloyl groups or methacryloyl groups in one molecule. 3. The ultraviolet-curable resin composition for a back coat according to 1.). 7. A step of forming a photosensitive resin coating film on both sides of a metal thin plate, a step of photographic printing of an exposed portion of the photosensitive resin coating film, a step of removing a non-photosensitive portion of the photosensitive resin coating film, and a primary etching step A shadow mask comprising a back coat step of forming a back coat film on one side of a primarily etched metal sheet, a secondary etching step, and a step of removing the photosensitive resin coating film and the back coat film by an alkali treatment. In the manufacturing method, the back coat step, a polymerizable compound having one or more acid groups and one or more acryloyl groups or methacryloyl groups in one molecule, and a main chain, a plurality of side chains that generate radicals bonded And an application step of an ultraviolet-curable resin composition for a back coat containing a polymerized polymerization initiator having a mass average molecular weight of 500 to 5,000. Method of manufacturing a shadow mask to butterflies. 8. The method of claim 7, wherein the polymer polymerization initiator is represented by the following Chemical Formula 1. In the chemical formula 1, n is 3 to
An integer of 5, R1 to R3 are H and / or an alkyl group, R4
Is selected from phenyl, hydroxyalkyl, hydroxycyclohexyl, dialkoxy and their derivatives. Embedded image 9. The method of claim 7, wherein the polymer polymerization initiator is represented by the following Chemical Formula 2. In the chemical formula 2, n is 1 to
An integer of 6, m is an integer of 3 to 5, R1 to R8 are H and / or an alkyl group, and R9 is selected from an H and / or an alkyl group or a derivative thereof. Embedded image 10. The method of applying an ultraviolet-curable resin composition for a back coat, wherein the ultraviolet-curable resin composition for a back coat is applied to a dry film thickness of 10 to 60 μm. A method for manufacturing a shadow mask according to any one of claims 7 to 9. 11. The method according to claim 11, wherein the secondary etching step is performed at 70 to 1
11. The method of manufacturing a shadow mask according to claim 7, wherein the method is performed with an acidic etching solution at a temperature of 00.degree.