JP2002220422A - Active energy ray-hardenable composition and hardened film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hardened film excellent in both film strength and the alkali solubility as a resist and to provide an active energy ray-hardenable composition enabling the above properties. SOLUTION: The composition contains (A) a compound having at least one carboxyl group and at least one (meth)acryloyl group in a molecule, (B) a compound represented by the formula CH2=CHCONH-R-OH [R is a 2-6C alkyl group], (C) an ethylenically unsaturated compound other than (A) and (B) components and (D) a photopolymerization initiator. The hardening of the composition produces the film excellent in strength and elongation characteristics, etching resistance and solubility in an alkali.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate having fine irregularities such as a shadow mask and an aperture grill, which has excellent etching resistance by irradiating it with ultraviolet rays.
The present invention relates to a composition which forms a crosslinked cured coating film having high-performance alkali solubility and can be used as an etching resist. In particular, the present invention relates to a composition for forming an alkali-soluble protective film useful as a resin composition for a backing material in a secondary etching step in manufacturing a shadow mask and / or an aperture grill.

[0002]

2. Description of the Related Art Electronic materials such as printed wiring boards and semiconductor elements generally require sophisticated and delicate advanced processing techniques.
A method of forming a resist pattern by an ultraviolet exposure method has become mainstream. In response to demands for miniaturization of semiconductor element dimensions and improvement of processing accuracy, etching resists
Performance such as high sensitivity (response efficiency of a chemical reaction by light) and high resolution (especially low swelling during etching) is particularly required. Above all, in the case of a shadow mask or an aperture grill having a base material with precise and fine irregularities, an etching resist material that follows the base material, has good surface smoothness, and can be covered without generating bubbles is required.

[0003] A shadow mask has a thickness of about 0.1 cm and is attached at a position about 1 cm inside the screen of a color CRT.
It is a 5 mm steel plate and has many fine holes for irradiating the corresponding phosphor with an electron beam. In order to form such fine holes, a method is generally adopted in which etching is performed from both sides of the steel sheet at positions corresponding to the front and back surfaces thereof to penetrate.

[0004] Regarding the manufacturing process of this shadow mask,
An example will be described with reference to the cross-sectional view shown in FIG. First,
A photosensitive resin (primary resist) 12 is applied to both the front and back surfaces of a base material 10 such as a steel plate, and the coated surface is exposed to actinic rays through a patterned photomask. Remove. Next, an etching solution containing ferric chloride or the like is used to remove 1
Next etching is performed, and the etching is interrupted just before the hole penetrates. Then, masking is performed by applying and curing a UV-curable secondary resist 14 on one side of the base material.
After that, secondary etching is performed. In the secondary etching, the etching proceeds from the side not masked with the secondary resist using an etching solution containing ferric chloride or the like,
Etching is stopped when the secondary resist 14 is reached. Finally, the primary resist 12 and the secondary resist 14 are removed by an alkali treatment, and holes 16
The opened shadow mask is completed. In the aperture grill, the shape of the hole required is elongated, and the final shape is a steel plate in the form of a mat. The manufacturing process is basically the same as that of the above-mentioned shadow mask.

[0005] A secondary resist used in the production of a shadow mask or an aperture grill by such a method includes one carboxyl group as proposed in Japanese Patent Publication No. 4-82002 and Japanese Patent No. 2592733. And a compound having one (meth) acryloyl group is effective.

[0006]

However, in recent production lines for shadow masks and aperture grills, there is a tendency to increase the line speed in order to improve the productivity, and in order to increase the etching speed, a spray of an etching solution is required. Tends to increase pressure. For this reason, a large stress is applied to the resist film, and there is a problem in that the yield is reduced due to cracking or falling off of the film. Further, there is a problem that the alkali dissolution time has to be shortened for speeding up. In the prior art, there is a contradictory relationship that increasing the film strength of the secondary resist decreases the alkali solubility, and increasing the alkali solubility decreases the film strength, and a composition that satisfies this conflicting performance is required. Had been.

The present invention has been made in order to solve the above-mentioned problems, and has as its object a cured film excellent in both film strength and alkali solubility as a resist, and an active energy ray-curable composition enabling the cured film. It is assumed that.

[0008]

Means for Solving the Problems The present inventors have studied the cause of the film falling off during etching, which is the subject of the present invention, and as a result, have found that when the strength of the cured film is low, the frequency of cracking is high. The composition was studied for improving the strength.
As a result, by using a (meth) acrylic monomer containing a carboxyl group and a specific hydroxyalkylacrylamide, both of the etching resistance and the alkali solubility are excellent, and even in a high-speed production line, cracks may occur and fall off. It was found that an alkali-soluble protective film was obtained, and the present invention was completed.

That is, the active energy ray-curable composition of the present invention is characterized by containing the following components (A) to (D). (A) a compound having at least one carboxyl group and at least one (meth) acryloyl group in a molecule;
(B) a compound represented by the following general formula (I): CH ₂ ＣＨCHCONH—R—OH (I) (wherein, R represents an alkyl group having 2 to 6 carbon atoms). (A) and an ethylenically unsaturated compound other than the component (B), and (D) a photopolymerization initiator. Here, as the component (A), at least one carboxyl group and at least two (meth) acryloyl in the molecule. It is desirable to include a compound having a group. Further, it is preferable that the acrylic acid polymer multimer ester compounds represented by the following general formula (II) are contained as the component (C). _{[CH 2 = CHCOO- (CH 2 CH} 2 COO) p ] _{q -R- (OH) r ... (} II) ( wherein, p is an integer of from 1 to 10, q is an integer of from 2 to 6, r is 0 An integer of from 5 to 5, and R is a branched, cyclic, or linear hydrocarbon group having 2 to 15 carbon atoms, or a hydrocarbon group having an aromatic ring, and the structure may include an ester structure.) The cured film is a cured film obtained by curing the active energy ray-curable composition, and is an alkali-soluble protective film for producing a shadow mask or an aperture grill.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, each component will be described in detail. In the present invention, “(meth) acrylic acid” means “acrylic acid and / or methacrylic acid”, “(meth) acryloyl group” means “acryloyl group and / or methacryloyl group”, and “(meth) acrylate”
Means "methacrylate and / or acrylate", respectively. The component (A) in the active energy ray-curable composition of the present invention is a compound having at least one carboxyl group and at least one (meth) acryloyl group in a molecule. The component (A) is a component that imparts alkali solubility to the obtained cured film and at the same time develops good etching resistance. As a specific example of the component (A), for example, a compound having at least one acid anhydride group in a molecule and a compound having one hydroxyl group and at least one (meth) acryloyl group in a molecule are added. Product.

Specific examples of such components include dibasic anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and succinic anhydride. And polybasic anhydrides such as trimellitic anhydride, pyromellitic anhydride, ethylene glycol bisanhydrotrimellitate, glycerin bis (anhydrotrimellitate) monoacetate, and glycerin tris (anhydrotrimellitate) monoacetate Examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and cyclohexane Hydroxyalkyl (meth) acrylates such as methanol mono (meth) acrylate, and compounds obtained by adding ethylene oxide adducts, propylene oxide adducts, caprolactone adducts, and the like; trimethylolpropane di (meth) acrylate, glycerin di Compounds to which (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like are added. Among these compounds, since it is possible to increase the film strength while maintaining the alkali solubility of the obtained cured film, at least one carboxyl group and at least two (meth) acryloyl groups in the molecule It is preferable to use the compound (a1) having

[0012] In the active energy ray-curable composition of the present invention, the component (A) comprises a total amount of the components (A) to (C) of 1
The amount may be in the range of 20 to 70 parts by mass, particularly preferably in the range of 30 to 60 parts by mass.
When the amount of the component (A) is less than 20 parts by mass,
The alkali solubility of the cured film obtained therefrom tends to decrease. If the amount exceeds 70 parts by mass, the cured film obtained therefrom tends to be brittle.

The component (B) in the active energy ray-curable composition of the present invention is a hydroxyalkylacrylamide compound represented by the following general formula (I). CH ₂ ＣＨCHCONH—R—OH (I) (wherein, R represents an alkyl group having 2 to 6 carbon atoms.) This is because the amide group in the molecule imparts good strength to the obtained cured film. In addition, since the amide group and hydroxy group in the molecule have high hydrophilicity, it is a component capable of improving the alkali solubility of the cured film obtained. By blending the compound, it is possible to improve the strength of the cured film and the alkali solubility, which were impossible with the conventional composition. In the general formula (I), when R is an alkyl group having 1 carbon atom, that is, in the case of N-methylolacrylamide, the compound is in the form of a crystal at room temperature and has a solubility in the components (A) to (D). Extremely bad, and even if it is dissolved, crystallization occurs at low temperature, so that it is phase-separated from the composition and cannot be used practically. Further, when the carbon number of R exceeds 6, not only the strength of the cured film to be obtained is reduced due to a decrease in the amide group concentration, but also the hydrophilicity is reduced, so that the alkali solubility cannot be improved. Specific examples of the component (B) include 2-hydroxyethyl acrylamide, 2-hydroxypropyl acrylamide, 3-hydroxypropyl acrylamide, 4-hydroxybutyl acrylamide, hydroxypivalyl acrylamide, 5-hydroxypentyl acrylamide, and 6-hydroxyhexyl acrylamide. And the like, and one or more of these can be used. In the active energy ray-curable composition of the present invention, the component (B) may be blended in an amount of 5 to 40 parts by mass, and particularly preferably 100 parts by mass of the total amount of the components (A) to (C). It is in the range of 10 to 35 parts by mass. When the amount of the component (B) is less than 5 parts by mass, the strength of the obtained cured film tends to decrease. On the other hand, when the amount exceeds 40 parts by mass, the resulting cured film has too high a hydrophilicity, and thus the etching resistance tends to decrease.

The component (C) in the active energy ray-curable composition of the present invention is an ethylenically unsaturated compound other than the components (A) and (B), and gives a good curability to the composition. It is. Specific examples of the ethylenically unsaturated compound include, for example, N-vinylformamide, N-
Vinylacetamide, N-vinyl-2-pyrrolidone, N
-Vinyl ester monomers such as vinyl caprolactam and divinyl adipate; vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether; acrylamide, N-methoxymethylacrylamide, N-butoxymethylacrylamide, Nt-butylacrylamide, acryloylmorpholine, methylenebis Acrylamides other than the component (B) such as acrylamide; (meth) acrylic acid, methyl (meth) acrylate, (meth)
Ethyl acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid 2-ethylhexyl, lauryl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) 4-hydroxybutyl acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate,
Diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, allyl (meth) acrylate, (meth) acryl 2-ethoxyethyl acid, (meth)
Isobornyl acrylate, phenyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, di ( Polyethylene glycol (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, di (meth) acrylate 1,9-nonanediol acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate
Acrylic ester, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene di (meth) acrylate Glycol,
Poly (tetramethylene glycol) di (meth) acrylate,
Polyethoxylated bisphenol A di (meth) acrylate, polyethoxylated bisphenol F
Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate,
Propoxylated trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, ditrimethylolpropanetetra (meth) ) Acrylates, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. ) Acrylates; polybasic acids such as phthalic acid and adipic acid, ethylene glycol, neopentyl glycol, 1,6-hexanediol, polyethylene glycol, polytetra Polyester (meth) acrylates obtained by reaction with a polyhydric alcohol such as methylene glycol and (meth) acrylic acid or a derivative thereof;
Isocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, norbornane diisocyanate, and polyethylene glycol, propylene glycol, and polytetraethylene Methylene glycol, bisphenol A
A polyol compound such as ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, polyester polyol and polycarbonate diol;
(Meth) acrylates having a hydroxyl group such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate Urethane di (meth) acrylates reacted with: isocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, norbornane diisocyanate, etc. -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , 4-hydroxybutyl (meth)
Urethane poly (meth) acrylates to which (meth) acrylates having hydroxyl groups such as acrylates and their caprolactone adducts have been added; phenol novolak epoxy resins, cresol novolak epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins Epoxy poly (meth) acrylates obtained by reacting (meth) acrylic acid or a derivative thereof with a glycidyl ether compound such as the above. Further, acrylic acid polymer ester compounds (c1) represented by the following general formula (II) can also be used. _{[CH 2 = CHCOO- (CH 2 CH} 2 COO) p ] _{q -R- (OH) r ... (} II) ( wherein, p is an integer of from 1 to 10, q is an integer of from 2 to 6, r is 0 And R is a branched, cyclic or linear hydrocarbon group having 2 to 15 carbon atoms, or a hydrocarbon group having an aromatic ring, which may have an ester structure in the structure. These can be used alone or in combination of two or more.

Among these, the compounds (c1) are preferable in that they can impart excellent etching resistance and alkali solubility, and the compound (c1) contains at least 40 of the compounds (c1) in the component (C). It is particularly preferred that the content be contained by mass%. Specific examples of the compounds (c1) include, for example, 1,4-butanediol diacryl dimer acid ester, 1,6-hexanediol diacryl dimer acid ester, neopentyl glycol diacryl dimer acid ester, and diethylene glycol dimer ester. Acrylic dimer acid ester, tetraethylene glycol diacryl dimer acid ester, tripropylene glycol diacryl dimer acid ester, polyoxyethylene bisphenol A diacryl dimer acid ester, trimethylolpropane triacryl dimer acid ester, glycerol triacryl dimer acid ester, Pentaerythritol triacrylic dimer ester, pentaerythritol tetraacrylic dimer ester, ditrimethylolpropane tetraac Rudaima esters, dipentaerythritol penta acrylate dimer acid ester, dipentaerythritol hexa acrylate dimer acid ester. Among the above, trimethylolpropane triacrylic dimer acid ester, glycerol triacrylic dimer acid ester, pentaerythritol triacrylic dimer acid ester, pentaerythritol tetraacrylic dimer acid ester, ditrimethylolpropane tetraacrylic acid because of good curability Dimer acid esters are particularly preferred.

In the active energy ray-curable composition of the present invention, the component (C) comprises a total amount of the components (A) to (C) of 1
The amount may be in the range of 25 to 75 parts by mass, particularly preferably in the range of 30 to 70 parts by mass.
When the amount of the component (C) is less than 25 parts by mass,
The curability of the composition tends to decrease, and the etching resistance of the obtained cured film tends to decrease. Also,
If the amount exceeds 75 parts by mass, the alkali solubility of the cured coating film obtained therefrom tends to decrease.

The active energy ray-curable composition of the present invention contains a photopolymerization initiator (D) as an essential component in order to impart practical ultraviolet curability. Specific examples of the component (D) include, for example, benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methylorthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, Ethyl anthraquinone, 2,4-diethylthioxanthone, isopropylthioxanthone,
Thioxanthones such as 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-
Methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2
-Dimethylamino-1- (4-morpholinophenyl)-
Acetophenones such as butanone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2 Acylphosphine oxides such as 4,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, methylbenzoyl formate,
1,7-bisacridinyl heptane, 9-phenylacridine and the like. These photopolymerization initiators can be used alone or in combination of two or more.

In the active energy ray-curable composition of the present invention, the component (D) is composed of a total amount of the components (A) to (C) of 1
It may be added in the range of 0.01 to 10 parts by mass with respect to 00 parts by mass, and particularly preferably in the range of 0.1 to 8 parts by mass. When the amount of the component (D) is less than 0.01 part by mass, the curing rate required for industrial production tends not to be obtained, and when it exceeds 10 parts by mass, the curing speed is not obtained. When the cured film is used as an etching resist, the photopolymerization initiator residue in the cured film is eluted into the etchant, which tends to adversely affect the product yield.

The active energy ray-curable composition of the present invention may contain, if necessary, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate,
A known photosensitizer such as ethyl-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, and 4-dimethylaminoacetophenone can also be added. Further, the active energy ray-curable composition of the present invention may contain a leveling agent, a radical polymerization chain transfer agent, a slip agent, a plasticizer, an antifoaming agent, an anti-repellent agent, a wetting agent, an anti-settling agent, Various additives such as an inhibitor, a light stabilizer, an ultraviolet absorber, an antioxidant, a polymerization inhibitor, a filler, a chelating agent, and a coupling agent can be contained. Of these, the addition of a radical polymerization chain transfer agent is preferable to improve the alkali solubility of the cured film, and the addition of a non-thiol chain transfer agent is more preferable from the viewpoint of storage stability of the obtained composition. In the thiol-based chain transfer agent, an ene-thiol reaction occurs between the double bond and the thiol contained in the components (A) to (C) in the present invention. It is not preferable because it tends to cause the formation. Specific examples of the most preferable non-thiol chain transfer agent include α-methylstyrene dimer and terpinolene. In the present invention, when a chain transfer agent is used, the total amount of the components (A) to (C) is 10%.
It can be added in the range of 0.01 to 10 parts by mass, preferably in the range of 0.1 to 5 parts by mass with respect to 0 parts by mass. If the amount is less than 0.01 part by mass, the alkali dissolution time cannot be shortened. If the amount exceeds 10 parts by mass, the curability of the composition decreases and the strength of the cured film tends to decrease. is there.

It is preferable to add a leveling agent to the active energy ray-curable composition of the present invention in order to improve the surface smoothness at the time of coating. For example, a well-known silicone-based leveling agent and a fluorine-based leveling agent can be used. Agents and the like can be used. In particular, when the active energy ray-curable composition of the present invention is used for a shadow mask or an aperture grill, a silicone leveling agent that does not leave fluorine residue on the product is preferred. Specific examples of the silicone leveling agent include, for example, L manufactured by Nippon Unicar Co., Ltd.
7604, L720; SH28PA manufactured by Dow Corning Toray Silicone Co., Ltd .; KF351, K manufactured by Shin-Etsu Chemical Co., Ltd.
F354A, KF355A, KP341; and the like. In the present invention, when a leveling agent is used, it is in the range of 0.01 to 5 parts by mass, preferably 0.1 to 1 part by mass, based on 100 parts by mass of the total of components (A) to (C). Can be added. When the amount is less than 0.01 part by mass, it is difficult to obtain a smooth cured coating film. When the amount is more than 5 parts by mass, bubbles tend to be hardly eliminated when bubbles are generated during application of the composition.

The active energy ray-curable composition of the present invention can be cured by an active energy ray alone or in combination with an active energy ray and heat. The active energy ray-curable composition of the present invention can be applied to various substrates, but can be suitably used particularly for a secondary resist such as a shadow mask and / or an aperture grill. In addition, it can be used as an etching resist for printed wiring boards, lead frames, TAB tapes, and the like, and can also be applied as a paint, molding material, or casting material. Examples of the substrate on which the active energy ray-curable composition of the present invention can be cured to form a film include, for example, inorganic substances such as a glass plate, an iron plate, a tin plate, a galvanized plate, an aluminum plate, and a zinc steel plate, wood, paper, and plastics. And organic substances such as organic paint films, but are not particularly limited. In particular, in order to manufacture a shadow mask or an aperture grill, a known substrate for a shadow mask or an aperture grill, such as an amber alloy or pure iron, may be used.

The method for applying the composition to a substrate is as follows.
For example, spray coating, curtain flow coating,
Examples include a roll coating method, a bar coating method, a dipping coating method, a spin coating method, a gravure coating method, and a screen coating method, but are not particularly limited. In addition, as the coating amount, the thickness of the cured coating film is 1 to 50.
It may be applied in a range of 0 μm, preferably in a range of 5 to 300 μm.

As a means for curing the film applied to the substrate, a known method of irradiating active energy rays such as X-rays, ultraviolet rays, visible rays, etc. can be used. It is preferable to use ultraviolet rays as a means for curing the composition. As a source of ultraviolet light, an ultraviolet lamp is generally used in terms of practicality and economy. Specific examples include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a gallium lamp, and a metal halide lamp. Further, the atmosphere at the time of exposure of the composition used in the present invention,
Any of an inert gas such as air, nitrogen, or argon may be used.

[0024]

The present invention will be described below in more detail with reference to examples. The evaluation method in the present example is as follows. <Measurement of Breaking Strength and Breaking Elongation> Preparation of Sample for Measuring Tensile Strength
Is coated on a glass substrate so that the peak illuminance is 350 m using a high-pressure mercury lamp with a monitor of 320 to 390 nm.
Curing was performed under ultraviolet irradiation conditions of w / cm ² and an integrated light quantity of 600 mj / cm ² . The obtained glass substrate sample having a cured coating film was cut into a strip having a width of 15 mm and a length of 50 mm with a cutter, and the cured coating film was separated from the glass substrate to obtain a sample for measuring tensile strength. Test method for tensile strength Tensilon universal tester RTC manufactured by Orientec Co., Ltd.
A sample was attached to a sample holder using -1250A, and held at an ambient temperature of 90 ° C. for 3 minutes.
A tensile strength test was performed under the following conditions. Breaking strength 10M
Pa or more and elongation at break of 5% or more were judged to be good. <Etching resistance> A negative pattern of the same shape aligned on both sides with a casein-based photosensitive resin film (primary resist) was formed on both sides of a 0.15 mm thick steel plate. A base material having 100 non-penetrating rectangular holes (recesses) of 20 mm was prepared. On one surface of the substrate, the composition prepared in each Example was applied on the casein-based photosensitive resin film by a bar coater so that the cured film thickness became 20 μm, and then 320 to 3 using a high-pressure mercury lamp.
The composition was cured under the ultraviolet irradiation conditions of a peak illuminance of 350 mw / cm ² and an integrated light quantity of 600 mj / cm ^{2 on} a 90 nm monitor, and a sample having a cured coating film of the composition prepared in each example was prepared. This sample was subjected to an etching resistance test for 20 minutes at a temperature of 90 ° C. and a spray pressure of 3.5 kg / cm ² using a 43% aqueous FeCl ₃ solution as an etching solution. After the etching resistance test was completed, the sample was washed with water and dried, and then the cured coating film was visually observed. The criteria for determining the etching resistance are as follows. A: All 100 rectangular holes (recesses) were not broken, cracked or dropped. B: Among 100 rectangular holes (recesses), tearing into 1 to 19
Cracks or shedding occur. C: 20 to 79 or more out of 100 rectangular holes (recesses), cracks or falling off. D: Torn into 80 or more of 100 rectangular holes (recesses),
Cracks or shedding occur. <Alkali solubility> The composition prepared in each Example was applied on a steel sheet by a room temperature bar coater so as to have a cured film thickness of 25 μm, and was subjected to 320 to 390 nm using a high-pressure mercury lamp.
Monitor peak illuminance 350mw / cm ² , integrated light amount 6
Curing was performed under ultraviolet irradiation conditions of 00 mj / cm ² . Then, it is immersed in a 75 ° C., 20% aqueous sodium hydroxide solution,
The time for complete dissolution of the membrane was measured. The criteria for determining alkali solubility are as follows. A: good (90 seconds or less) B: insufficient (90-110 seconds) C: bad (110 seconds or more)

Synthesis Example 1 (Synthesis of Compound A-1) In a 2 L flask equipped with a stirrer, a thermometer and a condenser, 590.4 g of ethylene glycol bis (anhydrotrimellitate) and 2-hydroxyethyl acrylate were added. 381.2 g, 9.6 g of diethylaminoethyl methacrylate as a reaction catalyst, and 0.48 g of hydroquinone monomethyl ether as a polymerization inhibitor were charged. next,
The temperature was gradually increased with stirring, and when the temperature reached 95 ° C., the temperature was maintained for 2 hours, followed by cooling to obtain Compound A-1.

Example 1 30 parts by mass of compound A-1
30 parts by mass of 2-hydroxyethylacrylamide, trimethylolpropane triacrylic dimer acid ester 4
0 parts by weight, 5 parts by weight of 1-hydroxycyclohexyl-phenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals), 1 part by weight of α-methylstyrene dimer as a photopolymerization initiator, leveling agent L-720 manufactured by Nippon Unicar Co., Ltd. Was mixed at room temperature until the whole became uniform to obtain an active energy ray-curable composition. This composition was evaluated by the above-described methods. Table 1 shows the evaluation results. [Example 2, Comparative Examples 1-4] Except for using each component shown in Table 1, compounding was carried out in the same manner as in Example 1 to prepare an active energy ray-curable composition. A cured coating film was formed from each of the obtained compositions in the same manner as in Example 1, and the cured coating film was evaluated. The evaluation results are shown in Table 1.

[0027]

[Table 1]

The symbols / abbreviations in Table 1 mean the following compounds, respectively. A-1: Compound obtained in Synthesis Example 1 above A-2: Addition reaction product of tetrahydrophthalic anhydride and pentaerythritol triacrylate (Biscoat # 2480 manufactured by Osaka Organic Chemical Industry Co., Ltd.) A-3: Anhydrous Addition reaction product of phthalic acid and 2-hydroxyethyl acrylate (Viscort # 2000 manufactured by Osaka Organic Chemical Industry Co., Ltd.) B-1: 2-hydroxyethyl acrylamide B-2: 2-hydroxypropyl acrylamide C-1: tri Methylolpropane triacrylic dimer acid ester (this corresponds to the acrylic acid polymer ester compounds (c1) represented by the above general formula (II)) C-2: 2-hydroxyethyl acrylate C-3: N -Methylol acrylamide Irgacure 184: 1-hydroxycyclohexyl-
Phenyl ketone MSD: α-methylstyrene dimer (NOF Corporation)
Nofmer MSD) Leveling agent: L-720 manufactured by Nippon Unicar Co., Ltd.

In Example 1, in the tensile strength test, the breaking strength was 15 MPa and the breaking elongation was 20%. Regarding the etching resistance, it was confirmed that the cured coating film remained in each of the 100 rectangular holes (concave portions), and the etching resistance was sufficiently good (determination: A). The alkali solubility was 70 seconds, which was good (determination:
A). On the other hand, in Comparative Example 1 containing no component (B), all of the breaking strength, the breaking elongation, the etching resistance, and the alkali solubility were low. In Comparative Example 2, compound C
-3 did not dissolve and subsequent evaluation was not possible.
In Comparative Example 3 having no component (C), the etching resistance was poor.
In Comparative Example 4 containing no component (A), both the etching resistance and the alkali solubility were low.

[0030]

The active energy ray-curable composition of the present invention is capable of forming a cured coating film having excellent strength and elongation properties, excellent etching resistance and alkali solubility, and is suitable for high-speed production lines. Since the resin composition can sufficiently cope with such a situation, it has great industrial applicability as a resin composition for a backing material in an etching step. In addition, the cured film of the present invention satisfies the performance required when manufacturing a shadow mask, an aperture grill, a printed wiring board, a lead frame, a TAB tape, a metal mask, and the like, and is used as an alkali-soluble protective film. Useful. Further, by containing a compound having at least one carboxyl group and at least two (meth) acryloyl groups in the molecule as the component (A), the film strength can be maintained while maintaining the alkali solubility of the obtained cured film. Can be raised more. Furthermore,
By containing the acrylic acid polymer ester compound represented by the above (II) as the component (C), the etching resistance and the alkali solubility can be both improved.

[Brief description of the drawings]

FIG. 1 is a process diagram showing a manufacturing example of a shadow mask in a sectional view.

[Explanation of symbols]

 10 Base material 12 Primary resist 14 Secondary resist

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 4/02 C09D 4/02 5/00 5/00 Z H01J 9/14 H01J 9/14 G F term ( (Reference) 4J011 QA03 QA06 QA12 QA15 QA22 QA23 QA24 QB14 QB20 QB22 QB24 SA06 SA21 SA24 SA25 SA36 SA51 SA54 SA63 SA64 UA00 UA01 UA04 WA02 4J027 AB23 AB25 AB26 AC03 AC04 AC06 AE02 AE03 AG01 BA07 BA13 BA01 FA08 FA082 FA091 FA092 FA141 FA142 FA151 FA152 FA231 FA232 FA251 FA252 FA261 FA262 FA281 FA282 GA03 GA06 KA03 NA04 NA11 PA17 PB08 PB09 4J100 AE04R AG63R AJ02R AL03R AL04R AL05R AL08P AL09R AL62R AL63R AM15R BA17R13A08A13A08 BA16P BA21R BA39R BC04P BC43P CA05 JA01 5C027 HH11

Claims (4)

[Claims] (A) a compound having at least one carboxyl group and at least one (meth) acryloyl group in a molecule, (B) a compound represented by the following general formula (I), and CH ₂ ＣＨCHCONH —R—OH (I) (wherein, R represents an alkyl group having 2 to 6 carbon atoms.) (C) an ethylenically unsaturated compound other than the above components (A) and (B), and (D) An active energy ray-curable composition comprising a photopolymerization initiator. 2. The active energy ray-curable composition according to claim 1, wherein the component (A) contains a compound having at least one carboxyl group and at least two (meth) acryloyl groups in the molecule. Composition. 3. The active energy ray-curable composition according to claim 1, wherein the component (C) comprises an acrylic acid polymer ester compound represented by the following general formula (II). _{[CH 2 = CHCOO- (CH 2 CH} 2 COO) p ] _{q -R- (OH) r ... (} II) ( wherein, p is an integer of from 1 to 10, q is an integer of from 2 to 6, r is 0 An integer of from 5 to 5, and R is a branched, cyclic, or linear hydrocarbon group having 2 to 15 carbon atoms, or a hydrocarbon group having an aromatic ring, which may include an ester structure in the structure.) 4. A cured film obtained by curing the active energy ray-curable composition according to claim 1, which is an alkali-soluble protective film for producing a shadow mask or an aperture grill. Characterized cured film.