JP2002069108A - Active energy ray curable composition - Google Patents

Abstract

(57) [Problem] Active energy ray curing that exhibits excellent etching resistance and alkali solubility, does not cause corrosion even when baked, and can thermally decompose a residue by the calcination. Composition. A composition comprising a compound (A) having at least one carboxyl group and at least one (meth) acryloyl group in a molecule, wherein the halogen element content of the composition is less than 100 ppm. . It is excellent in etching resistance and alkali solubility and has a low halogen content, so that it does not cause corrosion, particularly for applications requiring firing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to cross-linking and curing of a substrate having fine irregularities, such as a shadow mask and an aperture grill, having excellent etching resistance and high-performance alkali solubility by irradiating ultraviolet rays. It forms a coating film 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 these fine holes, a method is generally adopted in which etching is performed from both sides of the steel plate at positions corresponding to the front and back surfaces thereof to penetrate the steel plate.
An example of the manufacturing process of the shadow mask will be described with reference to the cross-sectional view of 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 applied surface is exposed to actinic rays through a patterned photomask to develop a primary resist in a non-photosensitive portion. Removed by processing. Next, primary etching is performed from both the front and back surfaces of the base material using an etching solution containing ferric chloride or the like, and the etching is interrupted before the holes penetrate. 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, and the secondary resist 1
Etching is interrupted when it reaches the fourth side. Finally, the primary resist 12 and the secondary resist 14 are removed by an alkali treatment, and a shadow mask having holes 16 at predetermined positions 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.

A secondary resist used for manufacturing a shadow mask or an aperture grill according to such a method includes one carboxyl group and one (meth) acryloyl as proposed in Japanese Patent No. 2592733. It is effective to use a compound having a group.

[0005]

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, such as fluctuations in resist film thickness and insufficient washing. As a result, the possibility that a resist film that should have been originally stripped in the stripping step and not remained on the product has increased. However, the shadow mask and the aperture grill that have completed the peeling process are washed with water, dried, and then subjected to an annealing process and a press process when incorporated into a CRT, followed by a blackening process for forming a dense oxide film on the surface. Blackening treatment is 400-800
This is carried out by baking at a high temperature of ° C. At this time, even if the resist film remains, no problem occurs if it is completely thermally decomposed.
However, if the resist film containing a large amount of halogen remains, firing the shadow mask or aperture grill after the peeling process will cause the metal base on which the fine pattern is formed to be corroded by the strong acid gas generated from the halogen. ,
Discoloration is caused, or the shape is distorted, resulting in failure.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and exhibits excellent etching resistance and alkali solubility, does not cause corrosion even when fired, and has a residue generated by the fire. It is intended to provide a thermally decomposable active energy ray-curable composition.

[0007]

Means for Solving the Problems The present inventors have studied to solve the above problems, and as a result, by suppressing the halogen content of the material constituting the resist material to less than a specific amount,
We found that we could solve the problem. By using this composition, we found that as a result of increasing the line speed for the purpose of improving productivity, even if a resist film remained on the product after the completion of the resist stripping process, the yield did not decrease due to corrosion during firing. Thus, the present invention has been completed.

That is, the present invention is suitable for a resist for producing a shadow mask and an aperture grill, and has at least one carboxyl group and at least one carboxyl group in a molecule.
A composition comprising a compound (A) having two (meth) acryloyl groups, wherein the halogen element content of the composition is 10%.
An active energy ray-curable composition characterized by being less than 0 ppm. In the present invention, a major feature is that the halogen content of the curable composition is less than 100 ppm. Therefore, it is necessary to use a material having a low halogen content for the components constituting the curable composition. is there. Among halogens, the case where chlorine or fluorine is contained is the most unfavorable, and when the resist film remains on the shadow mask or the aperture grill, when sintering, hydrochloric acid, perchloric acid, hydrogen fluoride, etc. at a high temperature. May cause the discoloration of the base material, or the pore shape may be significantly destroyed by corrosion. In addition, the halogen content defined in the present invention means, in particular, the total amount of the total fluorine content and the total chlorine content that can be a strongly acidic gas, and fluorine and its non-existent form in the curable composition. The total chlorine content is defined as the halogen content. Among them, the total chlorine content is 99% in the composition of the present invention.
It is preferably less than 1 ppm, and the total fluorine content is preferably less than 1 ppm. The term “total chlorine content” as used herein means that the chlorine content obtained by burning a sample in an oxygen stream and titrating the generated hydrogen halide with silver ions generated electrolytically is expressed in ppm. The total fluorine content here means the sample was burned in a stainless steel sealed container filled with oxygen, and the solution in which the generated gas was absorbed in an aqueous sodium hydroxide solution was subjected to ion selective electrode method. F ^- means a representation measured in ppm fluorine content obtained by performing the.

The compound (A) desirably contains a compound (a) having at least one carboxyl group and at least two (meth) acryloyl groups in the molecule. Compound (A) 20 to 70 parts by mass, ethylenically unsaturated compound (B) 20 to 70 other than component (A)
Those having 70 parts by mass and 0.01 to 10 parts by mass of the photopolymerization initiator (C) are more preferable. Here, it is desirable that the ethylenically unsaturated compound (B) contains an acrylic acid polymer ester compound (b) represented by the following general formula [1]. _{[CH 2 = CHCOO- (CH 2 CH} 2 COO) p ] _{q -R- (OH) r ··· [} 1] ( wherein, p is an integer of from 1 to 10, q is an integer of from 2 to 6, r Is an integer of 0 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.

[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 curable composition of the present invention is a compound having at least one carboxyl group and at least one (meth) acryloyl group in the molecule. In the present invention, by having the component (A), it is possible to have high-performance alkali solubility and, at the same time, exhibit good etching resistance. (A)
Specific examples of the component include, for example, at least one
And a product obtained by adding a compound having one hydroxyl group and at least one (meth) acryloyl group in the molecule.

Specific examples of such components include dibasic acid 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 to which ethylene oxide adducts, propylene oxide adducts, caprolactone adducts, and the like have been added; trimethylolpropane diacrylate, glycerin diacrylate, and ditriol Methylolpropane triacrylate, pentaerythritol triacrylate,
Compounds to which dipentaerythritol pentaacrylate or the like has been added may be mentioned. Among these compounds, while maintaining the alkali solubility of the resulting cured film,
It is preferable to use the compound (a) having at least one carboxyl group and at least two (meth) acryloyl groups in the molecule, since the film strength can be increased.

In the curable composition of the present invention, the component (A) is preferably blended in the range of 20 to 70 parts by mass based on 100 parts by mass of the total composition. If the amount of the component (A) is less than 20 parts by mass, the alkali solubility of the protective coating obtained by curing the component tends to decrease, which is not preferable. On the other hand, if the amount exceeds 70 parts by mass, the etching resistance of the obtained protective film tends to decrease, which is not preferable. A particularly preferred range is 30 to 65 parts by mass.

In the curable composition of the present invention, in addition to the component (A), an ethylenically unsaturated compound (B) other than the component (A) is added in order to impart good curability to the composition. It is preferred to use. Specific examples of the component (B) include vinyl ester monomers such as N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam and divinyl adipate; and ethyl vinyl ether and phenyl vinyl ether. Vinyl ethers; acrylamide, N-
Methylol acrylamide, N-methoxymethyl acrylamide, N-butoxymethyl acrylamide, Nt
Acrylamides such as butylacrylamide, acryloylmorpholine, methylenebisacrylamide; (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 esters, 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 a hydroxyl group such as acrylates and their caprolactone adducts are added. It is preferable to use the acrylic acid polymer ester compound (b) represented by the following general formula [1] as a part of the component (B) in order to balance the etching resistance and the stripping time. _{[CH 2 = CHCOO- (CH 2 CH} 2 COO) p ] _{q -R- (OH) r ··· [} 1] ( wherein, p is an integer of from 1 to 10, q is an integer of from 2 to 6, r Is an integer of 0 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.

These components (B) can be used singly or in combination of two or more. However, from the viewpoint that excellent etching resistance and alkali solubility can be imparted, the compounds (B) can be used. b) is preferred. Specific examples of preferred compounds include 1,4-butanediol diacryl dimer acid ester, 1,6-hexanediol diacryl dimer acid ester, neopentyl glycol diacryl dimer acid ester, diethylene glycol diacryl dimer acid ester, tetraethylene Glycol diacrylic dimer acid ester, tripropylene glycol diacrylic dimer acid ester, polyoxyethylene bisphenol A diacrylic dimer acid ester,
Trimethylolpropane triacrylic dimer acid ester, glycerol triacrylic dimer acid ester, pentaerythritol triacrylic dimer acid ester,
Examples include pentaerythritol tetraacryl dimer acid ester, ditrimethylolpropane tetraacryl dimer acid ester, dipentaerythritol pentaacryl dimer acid ester, and dipentaerythritol hexaacryl 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 (B) is used in a total of 100 parts by mass of the composition.
It is preferable to mix in the range of 0 to 70 parts by mass.
If the amount of the component (B) is less than 20 parts by mass, the curability of the composition tends to decrease, and the etching resistance of the resulting protective coating tends to decrease. Alkali solubility of the resulting protective coating tends to decrease.

In the curable composition of the present invention, a photopolymerization initiator (C) is used to impart practical ultraviolet curability.
May be added. Specific examples thereof include, for example, benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methylorthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2-ethylanthraquinone, Thioxanthones such as 2,4-diethylthioxanthone and isopropylthioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-
Phenylpropan-1-one, benzyldimethylketal, 1-hydroxycyclohexyl-phenylketone,
Acetophenones such as 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoin methyl ether, benzoin Benzoin ethers such as ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl)-
Examples include acylphosphine oxides such as phenylphosphine oxide, methylbenzoyl formate, 1,7-bisacridinylheptane, 9-phenylacridine and the like. These photopolymerization initiators can be used alone or in combination of two or more.

Further, the curable composition of the present invention may contain, if necessary, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine,
Known photosensitizers such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, and 4-dimethylaminoacetophenone can also be added.

The component (C) in the curable composition of the present invention is preferably blended in an amount of 0.01 to 10 parts by mass, particularly preferably 0.1 to 10 parts by mass, per 100 parts by mass of the total amount of the composition. 8 parts by mass. (C) The compounding amount of the component is 0.01.
If the amount is less than 10 parts by mass, the necessary curing rate for industrial production cannot be obtained, and if the amount exceeds 10 parts by mass, the protective coating obtained by curing the composition is used as an etching resist. In this case, the photopolymerization initiator residue in the protective film is eluted into the etching solution, which may adversely affect the product yield.

Further, the curable composition of the present invention contains (D)
As a component, a radical polymerization chain transfer agent containing no thiol group may be added. By blending the components,
It is possible to suppress the molecular weight of the polymer obtained by curing and shorten the alkali dissolution time of the obtained protective coating. However, in the thiol-based chain transfer agent disclosed in Japanese Patent Publication No. 2592733 or the like, an ene-thiol reaction occurs between the thiol and the double bond contained in the component (A) or the component (B). The storage stability of the composition deteriorates, which is not preferable. Specific examples of the component (D) include α-methylstyrene dimer, terpinolene, triethylamine, tributylamine, tributylphosphine, and the like. Preferred specific examples are α-methylstyrene dimer and terpinolene, and particularly preferably low odor. From the viewpoint of α-methylstyrene dimer. The component (D) in the curable composition of the present invention has a total amount of 10
It is preferably added in the range of 0.01 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass, per 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 tensile strength at break of the cured film is insufficient. There is a tendency that cannot be given.

The curable composition of the present invention may contain a leveling agent, a slip agent, a plasticizer, an antifoaming agent, an anti-repellent agent, a wetting agent, an anti-settling agent, a dripping inhibitor, a light stabilizer, if necessary. , UV absorbers, antioxidants, polymerization inhibitors, fillers,
Various additives such as a chelating agent and a coupling agent can be contained.

Among the above, it is preferable to add a leveling agent to the curable composition of the present invention for the purpose of improving the surface smoothness during coating. Known silicone-based leveling agents, fluorine-based leveling agents and the like can be used, but for shadow masks and aperture grills, silicone-based leveling agents that do not leave fluorine residue on the product are preferred. Preferred specific examples are "L7604" and "L720" manufactured by Nippon Unicar, "SH28PA" manufactured by Dow Corning Toray Silicone Co., Ltd., "KF351", "KF354A", "KF354" manufactured by Shin-Etsu Chemical Co., Ltd.
355A "," KP341 "and the like. When a leveling agent is used, it is in the range of 0.01 to 5 parts by mass, preferably 0.1, based on 100 parts by mass of the total amount of the composition.
It can be added in the range of 1 to 1 part by mass. If the amount is less than 0.01 part by mass, it tends to be difficult to obtain a smooth coating film. If the amount exceeds 5 parts by mass, bubbles are generated when the composition for forming a protective film is applied. It tends to be difficult.

The substrate to which the curable composition of the present invention can be applied includes, for example, inorganic substances such as a glass plate, an iron plate, a tin plate, a galvanized plate, an aluminum plate, a zinc steel plate, wood, paper, plastic, and organic paint films. And the like, but not limited thereto. 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 curable composition of the present invention to a substrate includes, for example, a spray coating method, a curtain flow coating method, a roll coating method, a bar coating method, a dipping coating method, a spin coating method, and a gravure method. Examples include a coating method and a screen coating method, but are not particularly limited. The coating amount is such that the thickness of the cured coating film is in the range of 1 to 500 μm, preferably 5 to 300 μm.
m may be applied.

As a means for curing the coating applied to the substrate, a known method of irradiating active energy rays such as X-rays, ultraviolet rays and visible rays can be used. It is preferable to use ultraviolet rays as a means for curing. Practical as a source of ultraviolet light,
Ultraviolet lamps are generally used in terms of economy. Specifically, low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, gallium lamp,
Metal halide lamps and the like.

The atmosphere for the exposure of the composition used in the present invention may be air, nitrogen, or an inert gas such as argon. Irradiation sources such as 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 can be used for ultraviolet irradiation after application to the substrate. The curable composition of the present invention is applicable to various substrates,
In particular, it can be suitably used in a secondary resist such as a shadow mask and / or an aperture grill. Others
It can be used as an etching resist for printed wiring boards, lead frames and TAB tapes.
It can also be applied as a paint, molding material or casting material.

[0027]

The present invention will be described below in more detail with reference to examples. In addition, the part in an Example means a mass part.

Synthesis Example 1 (Synthesis of (A) -1) In a 2 L flask equipped with a stirrer, a thermometer and a condenser, 590.4 g of ethylene glycol bis (anhydrotrimellitate), 2-hydroxyethyl 381.2 g of acrylate, 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., 2
After holding for a time, cooling was performed to obtain compound (A) -1.

Example 1 Compound (A) -1 (40 parts by mass), pentaerythritol tetraacrylic dimer acid ester (Viscoat # 400 manufactured by Osaka Organic Chemical Industry Co., Ltd.)
D) 10 parts by mass, 30 parts by mass of trimethylolpropane triacrylate (Aronix M-308 manufactured by Toagosei Co., Ltd.), acryloylmorpholine (ACM manufactured by Kojin Co., Ltd.)
O) 15 parts by mass, 5 parts by mass of a photopolymerization initiator Irgacure 184 manufactured by Ciba Specialty Chemicals, and 1 part by mass of α-methylstyrene dimer were blended, and the mixture was stirred at room temperature until the whole became uniform. The active energy ray-curable composition of Example 1 was obtained. 20 mg of the composition was weighed into a quartz sample port, and the sample was oxidized and burned oxidatively by a total chlorine analysis system TOX-10 # manufactured by Mitsubishi Chemical Corporation, and the generated HCl was generated electrolytically in the cell. When the amount of chlorine was measured from the amount of electricity required by automatic titration with silver ions, the total chlorine content in the composition was 12 pp.
m. Also, 1 g of the composition was weighed and the amount of oxygen was 20 g.
It burns in a stainless steel closed vessel under the condition of kg / cm ² , absorbs the produced gas in a 0.2N aqueous sodium hydroxide solution, and uses an ion selective electrode method to produce an ionizer 901 type ionizer manufactured by Orion Research. As a result, the total fluorine content in the composition was less than 1 ppm.

Preparation of cured sample The composition was coated on a steel plate having a thickness of 0.15 mm with a bar coater at room temperature to a film thickness of 25 μm, and a peak illuminance of 350 mw was observed with a high-pressure mercury lamp on a 320 to 390 nm monitor. / Cm ² , and cured under an ultraviolet irradiation condition of an integrated light quantity of 600 mj / cm ² . Further, the backside was subjected to coating and curing under the same conditions to obtain a cured sample.

Etching Resistance The cured sample was subjected to an etching resistance test in a 43% aqueous solution of FeCl ₃ in an etching solution at a temperature of 90 ° C. for 20 minutes. After completion of the etching resistance test, the film was washed with water, dried, and visually observed for the cured film. As a result, it was confirmed that the appearance was unchanged and the etching resistance was very good (determination: A). . The criteria for visual determination of etching resistance were as follows. A: very good without abnormal appearance B: good swelling but good C: film loss observed and insufficient D: film peeling occurred and poor

Alkali solubility The cured sample was immersed in a 20% aqueous sodium hydroxide solution at 75 ° C., and the time required for the cured film to completely dissolve was measured. The result was 70 seconds, which was good (determination: A). Was. The determination criteria for alkali solubility were determined as follows. A: good for 90 seconds or less B: good for 90 to 110 seconds C: bad for 110 seconds or more

Baking property The cured sample is cut into a 3 mm square, placed in a platinum measuring cell, and heated at a heating rate of 20 in an air atmosphere using a heating loss measuring unit of a multi-thermal analysis system of Vacuum Riko Co., Ltd.
The change in weight when the temperature was raised from room temperature to 570 ° C. at a rate of ° C./min was measured, and it was confirmed that 100% of the cured film was burned out 3 minutes after the temperature reached 570 ° C. When the sample was taken out of the cell, no hardened film residue was observed, and no discoloration or corrosion was observed on the base steel sheet.
A). The criterion for determining the sinterability was as follows. A: No residue after firing and good without discoloration and corrosion of the substrate B: No residue after firing but discoloration of the substrate and insufficient C: Corrosion and failure of the substrate

[Examples 2 to 4, Comparative Examples 1 to 5] The components shown in Table 1 were blended in the same manner as in Example 1.
The active energy ray-curable compositions of Comparative Examples 1 to 5 were prepared. For each composition, the total chlorine amount and total fluorine amount were quantified in the same manner as in Example 1, and the results are shown in the evaluation result column of Table 1. Further, after coating and curing on a steel sheet in the same manner as in Example 1 to obtain a cured sample, evaluation of etching resistance, alkali solubility and firing properties was performed in the same manner as in Example 1, and the results were shown in Table 1. This is shown in the evaluation result column. Table 1
The components shown therein are shown in Table 2.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

The active energy ray-curable composition of the present invention is excellent in etching resistance and alkali solubility, and has a small halogen content. Does not cause corrosion. Therefore, it is very useful as an etching-resistant protective film required when manufacturing shadow masks, aperture grilles, printed wiring boards, lead frames, TAB tapes, metal masks, and the like. In particular, when compound (A) has at least one carboxyl group and at least 2
When the compound (a) having two (meth) acryloyl groups is contained, the film strength can be further increased while maintaining alkali solubility. Further, by containing the ethylenically unsaturated compound (B), the curability can be further improved. Further, by containing the photopolymerization initiator (C), the ultraviolet curability can be further improved. The balance between the etching resistance and the stripping time can be further improved by including the acrylic acid polymer ester compound (b) represented by the general formula [1] as the ethylenically unsaturated compound (B).

[Brief description of the drawings]

FIG. 1 is a process chart showing an example of manufacturing a shadow mask.

[Explanation of symbols]

 10 Base material 12 Primary resist 14 Secondary resist

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiroshi Fukushima 4-160 Sunadabashi, Higashi-ku, Nagoya-shi, Aichi F-term in Mitsubishi Rayon Co., Ltd. Product Development Laboratory (Reference) 2H025 AB17 AC01 AD01 BC14 BC43 BC82 BC83 BC85 4J011 AC04 QA03 QA06 QA07 QA08 QA17 QA23 QA24 QB16 SA05 SA06 SA22 SA24 SA25 SA26 SA34 SA54 SA63 SA64 SA78 SA84 UA01 UA02 UA04 VA01 WA01 4J027 AA02 BA07 BA19 BA25 CC03 CC04 CC05 CD10 4J100 AL08Q AL66P AL71P BA03 BA03 BA08

Claims (7)

[Claims] 1. A composition comprising a compound (A) having at least one carboxyl group and at least one (meth) acryloyl group in a molecule, wherein the composition has a halogen element content of less than 100 ppm. An active energy ray-curable composition, comprising: 2. A total chlorine content of less than 99 ppm,
2. The active energy ray-curable composition according to claim 1, wherein the total fluorine content is less than 1 ppm. 3. The compound according to claim 1, wherein the compound (A) includes a compound (a) having at least one carboxyl group and at least two (meth) acryloyl groups in a molecule. Active energy ray-curable composition. 4. 20 to 70 parts by mass of the compound (A) and 20 to 70 parts by mass of an ethylenically unsaturated compound (B) other than the component (A).
The active energy ray-curable composition according to any one of claims 1 to 3, comprising 70 parts by mass and 0.01 to 10 parts by mass of a photopolymerization initiator (C). 5. The method according to claim 1, wherein the ethylenically unsaturated compound (B) is
The active energy ray-curable composition according to claim 4, comprising an acrylic acid polymer ester compound (b) represented by the following general formula [1]. _{[CH 2 = CHCOO- (CH 2 CH} 2 COO) p ] _{q -R- (OH) r ··· [} 1] ( wherein, p is an integer of from 1 to 10, q is an integer of from 2 to 6, r Is an integer of 0 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. 6. The active energy ray-curable composition according to claim 1, which is a resist for producing a shadow mask. 7. The active energy ray-curable composition according to claim 1, which is a resist for producing an aperture grill.