JP6759666B2 - Method for manufacturing photosensitive composition for etching protection and metal processed plate - Google Patents

Description

The present invention relates to a photosensitive composition that is cured by active energy rays such as ultraviolet rays, and more particularly to a photosensitive composition for etching protection used during processing of a metal plate.

In the electronics industry, pattern formation on metal plates by partial etching of metal plates such as lead frames, vapor deposition masks and package substrates, short-circuit protection during soldering on printed wiring boards, insulating layers between electrodes in touch panels, and liquid crystal panels. Photosensitive compositions are used in a wide range of applications such as colored pixels and protective layers.

In particular, when the metal plate processing is carried out by the double-sided etching method, the etching protective photosensitive composition used for protecting the first etched surface at the time of the second etching is imparted by curing such as etching resistance. In addition to the properties to be achieved, alkali solubility is required. This is because it is necessary to remove it after metal processing by etching as a member that is used only in the process and does not remain in the final product, and for metal plate processing applications, a photosensitive composition that satisfies these contradictory characteristics is required. Has been done.

As a method for imparting alkali solubility without lowering the etching resistance, Patent Document 1 and Patent Document 2 disclose a method for blending a monothiol compound such as dodecyl mercaptan as a chain transfer agent. In the compositions disclosed in these publications, the en-thiol reaction between the (meth) acryloyl group, which is an unsaturated bond, and thiol proceeds. Therefore, if the amount added is too large, viscosity increase or gelation may occur. There is a problem that the etching resistance and the tackiness are lowered because the degree of polymerization due to photocuring becomes too low. Further, Patent Document 3 discloses a method of using α-styrene dimer or turpinolene as a chain transfer agent having no thiol group in order to solve these problems. However, it has been difficult to obtain sufficient alkali solubility due to the low ability of these chain transfer agents to reduce the degree of polymerization.

Japanese Patent No. 2592733 Japanese Patent No. 3491531 Japanese Unexamined Patent Publication No. 2001-354876

The present invention has been made in view of the above circumstances, and provides a photosensitive composition for processing a metal plate, which has alkali solubility while maintaining etching resistance and tackiness during processing of a metal plate and has excellent stability over time. The purpose is to do.

An object of the present invention has adopted the following configuration in order to solve the above problems.

One aspect of the first invention according to claim 1 is a photosensitive composition for etching protection used for processing a metal plate, wherein at least (A) a monofunctional photopolymerization having at least two aromatic rings in one molecule. It contains a sex monomer, (B) a monofunctional photopolymerizable monomer containing a carboxyl group, (C) a photopolymerization initiator, and (D) a secondary or higher polyfunctional thiol compound, and carboxyl is contained in the (B) one molecule. The content of the monofunctional photopolymerizable monomer containing a group in the total solid content of the photosensitive composition is 40% by weight or more based on the total amount of the photopolymerizable monomer in the total solid content of the photosensitive composition. It is a photosensitive composition for etching protection.

One aspect of the second invention according to claim 2 is (A) a monofunctional photopolymerizable monomer having at least two aromatic rings in one molecule and (B) a single molecule containing a carboxyl group in one molecule. A claim characterized in that the sum of the contents of the functional photopolymerizable monomer in the total solid content of the photosensitive composition is 70% by weight or more with respect to the total amount of the photopolymerizable monomer in the total solid content in the photosensitive composition. Item 2. The photosensitive composition for etching protection according to Item 1.

One aspect of the third invention according to claim 3 is
In a method for manufacturing a metal processed plate in which openings of different sizes are formed on the first surface and the second surface of the metal plate and penetrated by a double-sided etching method.
Using the etching protective photosensitive composition according to claim 1 or 2 ,
Metal processing including a step of forming a protective layer so that the other surface is not etched when etching one of the first surface and the second surface and changing the etching amount of each. It is a method of manufacturing a board .

One aspect of the fourth invention according to claim 4 is
The third aspect of claim 3, wherein the metal plate is a rolled metal obtained by rolling a base metal of a metal material with a roll and annealing the rolled base metal, and the metal thickness of the metal processed plate is 30 μm or less. This is a method for manufacturing a metal processed plate .

According to the present invention, it is possible to provide a photosensitive composition for metal processing and a metal processed plate, which have alkali solubility and are excellent in stability over time while maintaining etching resistance and tackiness during metal plate processing. As the metal processed plate, a lead frame, a vapor deposition mask, a shadow mask, or the like can be used for the electronic member.

FIG. 5 is a cross-sectional view of an example of a metal processed plate in the present invention. FIG. 3 is an enlarged cross-sectional view of an example of a metal processed plate in the present invention. The manufacturing process diagram in the example of the metal processed plate by the double-sided etching method.

In the present invention, the following configuration is adopted in order to solve the above inconvenience.

[Structure of photosensitive composition]
The photosensitive composition for etching protection used in the present invention is (A) a monofunctional photopolymerizable monomer having at least two aromatic rings in one molecule, and (B) a monofunctional monomer containing a carboxyl group in one molecule. It contains a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a secondary or higher polyfunctional thiol compound.

Examples of the monofunctional photopolymerizable monomer having at least two aromatic rings in one molecule (A) used in the photosensitive composition of the present invention include ethoxylated-o-phenylphenol acrylate and 2-hydroxy-o-phenylphenol. Examples thereof include propyl acrylate, ethoxylated paracumylphenol acrylate, and m-phenoxybenzyl acrylate. These photopolymerizable monomers can be used alone or in admixture of two or more.

(A) The monofunctional photopolymerizable monomer having at least two aromatic rings in one molecule is preferably 1 to 60% by weight, more preferably 30 to 60% by weight, based on the total solid content of the photosensitive composition. It is 60% by weight. It is considered that the photosensitive composition of the present invention has improved etching resistance and tackiness by having two or more aromatic rings in the molecule.

Examples of the monofunctional photopolymerizable monomer (B) containing a carboxyl group in one molecule used in the photosensitive composition of the present invention include ω-carboxy-polycaprolactone monoacrylate, monohydroxyethyl phthalate acrylate, and 2-acryloyloxy. Ethylsuccinic acid, 2-acryloyloxyethyl tetrahydrophthalic acid, 2-acryloyloxypropylphthalic acid, 2-acryloyloxypropyltetrahydrophthalic acid, 2-acryloyloxypropylsuccinic acid, methacryloyloxyethyl succinic acid, methacryloyloxyethylphthalic acid, Examples thereof include methacryloyloxyethyl tetrahydrophthalic acid, methacryloyloxypropyl succinic acid, methacryloyloxypropylphthalic acid, and methacryloyloxypropyl tetrahydrophthalic acid. These photopolymerizable monomers can be used alone or in admixture of two or more.

(B) The monofunctional photopolymerizable monomer containing a carboxyl group in one molecule is preferably 30 to 95% by weight, more preferably 40 to 80% by weight, based on the total solid content of the photosensitive composition. Is. At this time, if the ratio of the monofunctional photopolymerizable monomer containing a carboxyl group to the total photopolymerizable monomer is 40% by weight or more, the monofunctional photopolymerizable monomer containing a carboxyl group improves the solubility in alkali. It is thought that.

Further, the sum of the amounts of (A) a monofunctional photopolymerizable monomer having at least two aromatic rings in one molecule and (B) a monofunctional photopolymerizable monomer containing a carboxyl group in one molecule is photosensitive. It is preferably 70% by weight or more based on the solid content of the total photopolymerizable monomer of the sex composition.

As the (C) photopolymerization initiator used in the photosensitive composition of the present invention, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy Acetphenone compounds such as -2-methylpropane-1-one, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, benzoin, benzoin Benzoin compounds such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4'- Methyldiphenyl sulfide, benzophenone compounds such as 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropyl Thioxanthone compounds such as thioxanthone and 2,4-diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4) Triazine compounds such as'-methoxystyryl) -6-triazine, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-Phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) Oxime ester compound such as hydroxylamine, bis (2,4,6-trimethylbenzoyl) fe Phosphine compounds such as nylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, quinone compounds such as 9,10-phenanthrene quinone, camphorquinone and ethylanthraquinone, borate compounds, carbazole compounds, imidazole A system compound, a titanosen system compound, or the like is used. These photopolymerization initiators can be used alone or in admixture of two or more.

The amount of the photopolymerization initiator used (C) is preferably 0.5 to 20% by weight, more preferably 3 to 10% by weight, based on the total solid content of the photosensitive composition.

As the (D) secondary or higher polyfunctional thiol compound used in the photosensitive composition of the present invention, ethylene glycol bis (2-mercaptobutyrate) and trimethylolpropanthris (2-mercaptobuty) are used as the secondary polyfunctional thiol. Rate), trimethylol ethanetris (2-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutylyloxy) butane, 1,3,5-tris (3) -Mercaptobutylyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like. Examples of the tertiary polyfunctional thiol include ethylene glycol bis (2-mercaptoisobutyrate) and trimethylolpropanetris (2-mercaptoisobutyrate). It is considered that the use of a secondary or higher polyfunctional thiol compound improves the stability over time while maintaining the reactivity due to steric hindrance around the mercapto group.

The amount of the (D) secondary or higher polyfunctional thiol compound used is preferably 1 to 20% by weight, more preferably 3 to 10% by weight, based on the total solid content of the photosensitive composition. If the amount of the thiol compound used is 1% by weight or less, the degree of polymerization does not sufficiently decrease during photocuring and the alkali solubility decreases, and if it is 20% by weight, the degree of polymerization decreases too much and the etching resistance deteriorates.

The photosensitive composition used in the present invention further includes (A) a monofunctional photopolymerizable monomer having at least two aromatic rings in one molecule and (B) a monofunctional photopolymerization containing a carboxyl group in one molecule. It can contain a photopolymerizable monomer other than the sex monomer, a surfactant, an adhesion imparting agent, a polymerization inhibitor and the like.

[Structure of metal processed plate]
The configuration of the metal processed plate 10 using the etching protection photosensitive composition of the present invention will be described with reference to FIGS. 1 and 2.
FIG. 1 is an example of a metal processed plate 10 to which the present invention is applied, which includes a metal plate 11, and the metal plate 11 is a surface on the back side of a first surface 12a and a first surface 12a. The surface 12b is provided. The metal plate 11 has an opening 13 that penetrates the first surface 12a and the second surface 12b.

[Manufacturing method of metal processed plate]
The method for manufacturing the metal processed plate 10 used in the present invention will be described below.
As a method for manufacturing the metal processed plate 10, an etching method is used in which the metal plate 10 is selectively dissolved by an etching solution. As the etching method, a single-sided etching method in which processing is performed from only one side and a double-sided etching method as shown in FIG. 3 are used. Since the opening 13a on the first surface and the opening 13b on the second surface can be controlled, it is desirable to use the double-sided etching method.

The manufacturing method of the metal processed plate by the double-sided etching method is shown below.
(A) Manufacture of Metal Plate As shown in FIG. 3, the method for manufacturing the metal processing plate 10 for forming a vapor deposition pattern by the double-sided etching method includes the method for manufacturing the metal plate 11, and the method for manufacturing the metal plate 11 is a metal material. A rolled metal obtained by rolling the base metal of the above with a roll and annealing the rolled base metal is generally used.

(B) Formation of Photosensitive Material After the metal plate 11 is acid-treated with hydrochloric acid, sulfuric acid or the like, the photosensitive material 14 for pattern formation is formed on both sides of the first surface 12a and the second surface 12b. The photosensitive material may be a negative-type photosensitive material in which the UV-exposed portion is cured, or a positive-type photosensitive material in which the UV-exposed portion is dissolved in a developing solution. Further, as a method of forming the photosensitive material 14, even in a method of laminating a dry film resist on a metal plate 11 while applying heat, a liquid resist material is applied to a metal plate by gravure coating, screen coating, or the like with a hot air dryer or the like. Any method of removing the solvent may be used.

(C) Patterning of photosensitive material On the metal plate 11 coated with the photosensitive material 14, the photosensitive material is patterned by using a photolithography method. Through a desired pattern mask, the portion where the opening 13 is not formed is exposed when the negative type photosensitive material is used, and the portion where the opening 13 is formed when the positive type photosensitive material is used. A normal high-pressure mercury lamp or the like may be used as the light source. Subsequently, the carrier film of the dry film resist is peeled off and then developed. An alkaline aqueous solution is used as the developer. Examples of the alkaline aqueous solution include a sodium hydroxide aqueous solution, a sodium carbonate aqueous solution, a sodium hydrogen carbonate aqueous solution, an amine-based aqueous solution, a mixed aqueous solution thereof, or a mixture thereof to which an appropriate surfactant or the like is added. After development, it is dried using a hot air dryer or an IR dryer.

(D) Formation of protective layer on the first surface In the double-sided etching method, the etching amounts of the openings 13a on the first surface and the openings 13b on the second surface are changed in order to adjust the sizes, that is, they are separated. Need to be etched. Therefore, when etching one of the first surface 12a and the second surface 12b, a protective layer is formed so that the other surface is not etched. An adhesive film or a liquid photosensitive material is used to form the protective layer. As the protective layer 15a of the first surface 12a, an adhesive film is preferably used because it can be formed and peeled on the photosensitive material 14 and can also serve as a support during substrate transportation. As the thickness of the protective layer of the first surface 12a, 10 μm or more and 50 μm or less is preferably used.

(E) Etching of the second surface Etching with an acidic etching solution is performed in order to form the opening 13b of the second surface in the metal plate 11 having the protective layer formed on the first surface 12a. The etching can be carried out under known conditions, and the acidic etching solution includes, for example, a ferric perchlorate solution and a mixed solution of a ferric perchlorate solution and a ferric chloride solution. , Perchloric acid, hydrochloric acid, sulfuric acid, formic acid, and acetic acid mixed solutions are used.
The etching method used in the present invention may be a dip type in which the metal plate 11 is immersed in an acidic etching solution, a spray type in which the acidic etching solution is sprayed onto the metal plate 11, or a metal plate 11 rotated by a spinner. It may be a spin type in which an acidic etching solution is dropped.

(F) Peeling of the photosensitive material on the second surface The photosensitive material 14 on the second surface from the metal plate 11 on which the opening 13b on the second surface is formed for forming the protective layer on the second surface, which is a subsequent step. Peel off. The peeling may be carried out under known conditions, and for example, an alkaline stripping solution is used. Examples of the alkaline stripping solution include a sodium hydroxide aqueous solution, a sodium carbonate aqueous solution, a sodium hydrogen carbonate aqueous solution, an amine-based aqueous solution, a mixed aqueous solution thereof, or a mixture thereof to which an appropriate surfactant is added.

(G) Formation of Protective Layer on Second Surface When etching the first surface 12a, which is a subsequent step, the protective layer 15b on the second surface is formed so that the second surface 12b is not etched. For the formation of the protective layer 15b on the second surface, (A) a monofunctional photopolymerizable monomer having at least two aromatic rings in one molecule, and (B) a monofunctional photopolymerizable monomer containing a carboxyl group. , (C) Photopolymerization initiator, (D) Photosensitive composition containing a secondary or higher polyfunctional thiol compound is used.

As the thickness of the protective layer of the second surface 12b, 5 μm or more and 20 μm or less is preferably used.

(H) Peeling of the protective layer on the first surface The protective layer 15a on the first surface is peeled off for etching of the first surface 12a, which is a subsequent step. As a method of peeling the protective layer 15a on the first surface, physical peeling is performed by winding.

(I) Etching of the first surface The first surface 12a is etched in order to form the opening 13a of the first surface and connect it to the opening 13b of the second surface. Etching of the first surface 12a can be performed under the same conditions as the second surface 12b.

(J) Exfoliation of the photosensitive material on the first surface and the protective layer on the second surface The photosensitive material 14 on the first surface 12a from the metal plate 11 forming the opening 13a on the first surface and the opening 13b on the second surface. By peeling off the protective layer 15a on the second surface, a metal processed plate 10 for forming a vapor deposition pattern is obtained. The peeling of the photosensitive material on the first surface and the protective layer 15b on the second surface can be performed under the same conditions as the peeling of the photosensitive material on the second surface. At this time, if the metal plate is a thin plate of 30 μm or less, if the photosensitive material 14 on the first surface 12a and the protective layer 15a on the second surface have poor peelability, deformation will occur due to the in-plane stress difference during the peeling process. It may occur. The metal processing plate 10 for forming a vapor deposition pattern may be slit processed, if necessary.

[Example]
Hereinafter, the present invention will be specifically described with reference to Examples and the like, but the present invention is not limited to these examples.

First, a method for preparing the photosensitive composition used in Examples and Comparative Examples will be described.

[Preparation of Photosensitive Composition A]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare the photosensitive composition A.
-Photopolymerizable monomer 1: 2-hydroxy-o-phenylphenol propyl acrylate 45.0% by weight
("NK Ester 401P" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxypropyl hexahydrophthalic acid
45.0% by weight
("NK Ester ACB-23" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: 1,4-bis (3-mercaptobutyryloxy) butane 5.0% by weight
(Showa Denko "Karensu MT BD1")

[Preparation of Photosensitive Composition B]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a photosensitive composition B.
・ ・ Photopolymerizable monomer 1: 2-hydroxy-o-phenylphenol propyl acrylate 45.0% by weight
("NK Ester 401P" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxypropyl hexahydrophthalic acid
45.0% by weight
("NK Ester ACB-23" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione 5.0% by weight
(Showa Denko "Karensu MT NR1")

[Preparation of Photosensitive Composition C]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare the photosensitive composition C.
-Photopolymerizable monomer 1: 2-hydroxy-o-phenylphenol propyl acrylate 45.0% by weight
("NK Ester 401P" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxypropyl hexahydrophthalic acid
45.0% by weight
("NK Ester ACB-23" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
・ Thiol: Trimethylolpropane tris (3-mercaptobutyrate)
5.0% by weight
(Showa Denko "Karensu MT TPMB")

[Preparation of Photosensitive Composition D]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a photosensitive composition D.
-Photopolymerizable monomer 1: 2-hydroxy-o-phenylphenol propyl acrylate 45.0% by weight ("NK ester 401P" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxypropyl hexahydrophthalic acid
45.0% by weight
("NK Ester ACB-23" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
・ Thiol: Pentaerythritol Tetrakis (3-mercaptobutyrate)
5.0% by weight
(Showa Denko "Karensu MT PE1")

[Preparation of Photosensitive Composition E]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a photosensitive composition E.
-Photopolymerizable monomer 1: 2-hydroxy-o-phenylphenol propyl acrylate 36.0% by weight
("NK Ester 401P" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxypropyl hexahydrophthalic acid
36.0% by weight
("NK Ester ACB-23" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 3: n-butyl methacrylate 18.0% by weight
(Kyoeisha Chemical Co., Ltd. "Light Ester NB")
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: 1,4-bis (3-mercaptobutyryloxy) butane 5.0% by weight
(Showa Denko "Karensu MT BD1")

[Preparation of Photosensitive Composition F]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare the photosensitive composition F.
-Photopolymerizable monomer 1: 2-hydroxy-o-phenylphenol propyl acrylate
27.0% by weight ("NK Ester 401P" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxypropyl hexahydrophthalic acid
36.0% by weight
("NK Ester ACB-23" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 3: n-butyl methacrylate 27.0% by weight
(Kyoeisha Chemical Co., Ltd. "Light Ester NB")
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: 1,4-bis (3-mercaptobutyryloxy) butane 5.0% by weight
(Showa Denko "Karensu MT BD1")

[Preparation of Photosensitive Composition G]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare the photosensitive composition G.
-Photopolymerizable monomer 1: 2-hydroxy-o-phenylphenol propyl acrylate
18.0% by weight
("NK Ester 401P" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxypropyl hexahydrophthalic acid
36.0% by weight
("NK Ester ACB-23" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 3: n-butyl methacrylate 36.0% by weight
(Kyoeisha Chemical Co., Ltd. "Light Ester NB")
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: 1,4-bis (3-mercaptobutyryloxy) butane 5.0% by weight
(Showa Denko "Karensu MT BD1")

[Preparation of Photosensitive Composition H]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare the photosensitive composition H.
-Photopolymerizable monomer 1: 2-hydroxy-o-phenylphenol propyl acrylate 18.0% by weight
("NK Ester 401P" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxypropyl hexahydrophthalic acid
45.0% by weight
("NK Ester ACB-23" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 3: n-butyl methacrylate 27.0% by weight
(Kyoeisha Chemical Co., Ltd. "Light Ester NB")
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: 1,4-bis (3-mercaptobutyryloxy) butane 5.0% by weight
(Showa Denko "Karensu MT BD1")

[Preparation of Photosensitive Composition I]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare the photosensitive composition I.
-Photopolymerizable monomer 1: Ethoxylation-o-phenylphenol acrylate
27.0% by weight ("NK Ester A-LEN-10" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxypropyl hexahydrophthalic acid
36.0% by weight ("NK Ester ACB-23" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 3: n-butyl methacrylate 27.0% by weight
(Kyoeisha Chemical Co., Ltd. "Light Ester NB")
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: 1,4-bis (3-mercaptobutyryloxy) butane 5.0% by weight
(Showa Denko "Karensu MT BD1")

[Preparation of Photosensitive Composition J]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare the photosensitive composition J.
-Photopolymerizable monomer 1: Ethoxylation-o-phenylphenol acrylate
27.0% by weight ("NK Ester A-LEN-10" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxypropyl hexahydrophthalic acid
45.0% by weight
("NK Ester ACB-23" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 3: n-butyl methacrylate 18.0% by weight
(Kyoeisha Chemical Co., Ltd. "Light Ester NB")
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: 1,4-bis (3-mercaptobutyryloxy) butane 5.0% by weight
(Showa Denko "Karensu MT BD1")

[Preparation of Photosensitive Composition K]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare the photosensitive composition K.
-Photopolymerizable monomer 1: Ethoxylation-o-phenylphenol acrylate
27.0% by weight
("NK Ester A-LEN-10" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxypropyl hexahydrophthalic acid
54.0% by weight
("NK Ester ACB-23" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 3: n-butyl methacrylate 9.0% by weight
(Kyoeisha Chemical Co., Ltd. "Light Ester NB")
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: 1,4-bis (3-mercaptobutyryloxy) butane 5.0% by weight
(Showa Denko "Karensu MT BD1")

[Preparation of Photosensitive Composition L]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare the photosensitive composition L.
-Photopolymerizable monomer 1: Ethoxylation-o-phenylphenol acrylate
18.0% by weight ("NK Ester A-LEN-10" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxypropyl hexahydrophthalic acid
36.0% by weight
("NK Ester ACB-23" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 3: n-butyl methacrylate 36.0% by weight
(Kyoeisha Chemical Co., Ltd. "Light Ester NB")
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: 1,4-bis (3-mercaptobutyryloxy) butane 5.0% by weight
(Showa Denko "Karensu MT BD1")

[Preparation of Photosensitive Composition M]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a photosensitive composition M.
-Photopolymerizable monomer 1: 2-hydroxy-o-phenylphenol propyl acrylate 27.0% by weight
("NK Ester 401P" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxyethyl succinic acid
36.0% by weight
("NK Ester A-SA" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 3: n-butyl methacrylate 27.0% by weight
(Kyoeisha Chemical Co., Ltd. "Light Ester NB")
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: 1,4-bis (3-mercaptobutyryloxy) butane 5.0% by weight
(Showa Denko "Karensu MT BD1")

[Preparation of Photosensitive Composition N]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare the photosensitive composition N.
-Photopolymerizable monomer 1: 2-hydroxy-o-phenylphenol propyl acrylate 18.0% by weight
("NK Ester 401P" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxyethyl succinic acid
45.0% by weight ("NK Ester A-SA" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 3: n-butyl methacrylate 27.0% by weight
(Kyoeisha Chemical Co., Ltd. "Light Ester NB")
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: 1,4-bis (3-mercaptobutyryloxy) butane 5.0% by weight
(Showa Denko "Karensu MT BD1")

[Preparation of Photosensitive Composition O]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare the photosensitive composition O.
-Photopolymerizable monomer 1: 2-hydroxy-o-phenylphenol propyl acrylate
9.0% by weight
("NK Ester 401P" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxyethyl succinic acid 54.0% by weight ("NK ester A-SA" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 3: n-butyl methacrylate 27.0% by weight
(Kyoeisha Chemical Co., Ltd. "Light Ester NB")
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: 1,4-bis (3-mercaptobutyryloxy) butane 5.0% by weight
(Showa Denko "Karensu MT BD1")

[Preparation of Photosensitive Composition P]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a photosensitive composition P.
-Photopolymerizable monomer 1: 2-hydroxy-o-phenylphenol propyl acrylate 18.0% by weight
("NK Ester 401P" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxyethyl succinic acid 36.0% by weight ("NK ester A-SA" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 3: n-butyl methacrylate 36.0% by weight
(Kyoeisha Chemical Co., Ltd. "Light Ester NB")
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: 1,4-bis (3-mercaptobutyryloxy) butane 5.0% by weight
(Showa Denko "Karensu MT BD1")

[Preparation of Photosensitive Composition Q]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare the photosensitive composition Q.
-Photopolymerizable monomer 1: 2-hydroxy-o-phenylphenol propyl acrylate
45.0% by weight
("NK Ester 401P" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxypropyl hexahydrophthalic acid 45.0% by weight ("NK ester ACB-23" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
-Thiol: 2-mercaptopropionic acid 5.0% by weight
(Manufactured by Tokyo Chemical Industry Co., Ltd.)

[Preparation of Photosensitive Composition R]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare the photosensitive composition R.
-Photopolymerizable monomer 1: 2-hydroxy-o-phenylphenol propyl acrylate 45.0% by weight
("NK Ester 401P" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxypropyl hexahydrophthalic acid
45.0% by weight
("NK Ester ACB-23" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate 5.0% by weight
("TEMPIC" manufactured by SC Organic Chemistry Co., Ltd.)

[Preparation of Photosensitive Composition S]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare the photosensitive composition S.
-Photopolymerizable monomer 1: 2-hydroxy-o-phenylphenol propyl acrylate
45.0% by weight
("NK Ester 401P" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxypropyl hexahydrophthalic acid
45.0% by weight
("NK Ester ACB-23" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
・ Thiol: Pentaerythritol tetrakis (3-mercaptopropionate)
5.0% by weight
("PEMP" manufactured by SC Organic Chemistry Co., Ltd.)

[Preparation of Photosensitive Composition T]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare the photosensitive composition T.
-Photopolymerizable monomer 1: 2-hydroxy-o-phenylphenol propyl acrylate
47.5% by weight
("NK Ester 401P" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxypropyl hexahydrophthalic acid
47.5% by weight ("NK Ester ACB-23" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")

[Preparation of Photosensitive Composition U]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a photosensitive composition U.
-Photopolymerizable monomer 1: 2-hydroxy-o-phenylphenol propyl acrylate 36.0% by weight
("NK Ester 401P" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxypropyl hexahydrophthalic acid
27.0% by weight
("NK Ester ACB-23" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 3: n-butyl methacrylate 27.0% by weight
(Kyoeisha Chemical Co., Ltd. "Light Ester NB")
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: 1,4-bis (3-mercaptobutyryloxy) butane 5.0% by weight
(Showa Denko "Karensu MT BD1")

[Preparation of Photosensitive Composition V]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare the photosensitive composition V.
-Photopolymerizable monomer 1: 2-hydroxy-o-phenylphenol propyl acrylate 27.0% by weight
("NK Ester 401P" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: 2-acryloyloxypropyl hexahydrophthalic acid
27.0% by weight
("NK Ester ACB-23" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 3: n-butyl methacrylate 36.0% by weight
(Kyoeisha Chemical Co., Ltd. "Light Ester NB")
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: 1,4-bis (3-mercaptobutyryloxy) butane 5.0% by weight
(Showa Denko "Karensu MT BD1")

[Preparation of Photosensitive Composition W]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare the photosensitive composition W.
-Photopolymerizable monomer 1: Ethoxylation-o-phenylphenol acrylate
63.0% by weight
("NK Ester A-LEN-10" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: n-butyl methacrylate 27.0% by weight
(Kyoeisha Chemical Co., Ltd. "Light Ester NB")
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: 1,4-bis (3-mercaptobutyryloxy) butane 5.0% by weight
(Showa Denko "Karensu MT BD1")

[Preparation of Photosensitive Composition X]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare the photosensitive composition X.
-Photopolymerizable monomer 1: 2-acryloyloxypropyl hexahydrophthalic acid
63.0% by weight
("NK Ester ACB-23" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: n-butyl methacrylate 27.0% by weight
(Kyoeisha Chemical Co., Ltd. "Light Ester NB")
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: 1,4-bis (3-mercaptobutyryloxy) butane 5.0% by weight
(Showa Denko "Karensu MT BD1")

[Preparation of Photosensitive Composition Y]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare the photosensitive composition Y.
-Photopolymerizable monomer 1: n-butyl methacrylate 90.0% by weight
(Kyoeisha Chemical Co., Ltd. "Light Ester NB")
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: 1,4-bis (3-mercaptobutyryloxy) butane 5.0% by weight
(Showa Denko "Karensu MT BD1")

[Preparation of Photosensitive Composition Z]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare the photosensitive composition Y.
-Photopolymerizable monomer 1: 2-acryloyloxypropyl hexahydrophthalic acid
63.0% by weight ("NK Ester ACB-23" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Photopolymerizable monomer 2: n-butyl methacrylate 27.0% by weight
(Kyoeisha Chemical Co., Ltd. "Light Ester NB")
-Photopolymerization initiator: 1-hydroxycyclohexyl-phenylketone 5.0% by weight
(BASF's "Irgacure 184")
Thiol: 1,4-bis (3-mercaptobutyryloxy) butane 5.0% by weight
(Showa Denko "Karensu MT BD1")

Table 1 shows the configurations of the photosensitive compositions used in Examples and Comparative Examples.

[Example 1]
As a metal plate, a Fe-36Ni alloy having a metal thickness of 30 μm is surface-treated with 10 wt% hydrochloric acid, washed with water, and dried, and then the photosensitive composition A is coated with a gravure coat and exposed at 1000 mJ / cm ² with a high-pressure mercury lamp. After forming the evaluation substrate, <etching resistance evaluation> and <alkali solubility evaluation> were performed on the obtained cured product. In addition, <evaluation of stability over time> was carried out for the photosensitive composition A.

[Example 2]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition B was used.

[Example 3]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition C was used.

[Example 4]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition D was used.

[Example 5]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition E was used.

[Example 6]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition F was used.

[Example 7]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition G was used.

[Example 8]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition H was used.

[Example 9]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition I was used.

[Example 10]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition J was used.

[Example 11]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition K was used.

[Example 12]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition L was used.

[Example 13]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition M was used.

[Example 14]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition N was used.

[Example 15]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition 0 was used.

[Example 16]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition P was used.

[Comparative Example 1]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition Q was used.

[Comparative Example 2]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition R was used.

[Comparative Example 3]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition S was used.

[Comparative Example 4]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition T was used.

[Comparative Example 5]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition U was used.

[Comparative Example 6]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition V was used.

[Comparative Example 7]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition W was used.

[Comparative Example 8]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition X was used.

[Comparative Example 9]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition Y was used.

[Comparative Example 10]
The photosensitive composition was evaluated in the same manner as in Example 1 except that the photosensitive composition Z was used.
[Evaluation of metal processed plates]
The evaluation substrates and photosensitive compositions produced in Examples and Comparative Examples were evaluated as follows.

<Etching resistance evaluation>
A solution in which 0.2% by weight of hydrochloric acid is mixed with a ferric perchlorate solution in which the evaluation substrate is heated to 50 ° C. and a mixture of ferric perchlorate solution and ferric chloride solution. After immersion for 10 minutes, a change in the appearance of the cured film was confirmed. Those with no change in appearance were evaluated as good etching resistance, those with coloring were evaluated as Δ, and those with swelling or cracking were evaluated as poor etching resistance.

<Evaluation of alkali solubility>
The evaluation substrate was immersed in a 5 wt% sodium hydroxide solution heated to 40 ° C. for 1 minute, and the peeling state of the cured film was visually confirmed. Complete dissolution is considered to be good alkali solubility ○, those that dissolve in sodium hydroxide solution after swelling peeling can be used △, those that cannot be peeled off or those in which a cured film remains in the sodium hydroxide solution after swelling peeling are alkaline dissolved It was marked as x as poor sex.

<Evaluation of stability over time>
The prepared photosensitive composition was measured for initial viscosity with a cone plate type viscometer (PK100D manufactured by HAAKE), and then stored at 40 ° C. for 7 days. The viscosity was measured after storage at 40 ° C. for 7 days, and those having a rate of change from the initial viscosity of less than ± 10% were evaluated as having good aging stability, and those exceeding ± 10% were evaluated as having poor aging stability.

<Tackiness evaluation>
The cured film of the evaluation substrate was touched, and the touched portion was visually confirmed. No change in appearance was marked with good tackiness, and those with fingerprint traces were marked with poor tackiness.

Table 2 shows the evaluation results of the photosensitive compositions in Examples and Comparative Examples.

As shown in Examples 1 to 4 of Table 2, by containing a secondary or higher polyfunctional thiol compound, it is possible to impart alkali solubility while maintaining stability over time. As shown in Comparative Examples 2 and 3, the stability with time deteriorates with the primary polyfunctional thiol compound, and as shown in Comparative Examples 1 and 4, the photosensitive composition without adding the secondary or higher monofunctional thiol compound or thiol compound. Alkaline solubility is poor for compounds. Further, from Examples 5 to 11 and Comparative Examples 5 and 6, (B) the content of the monofunctional photopolymerizable monomer containing a carboxyl group in one molecule in the total solid content of the photosensitive composition is the photosensitive composition. If it is 40% by weight or more based on the total amount of the photopolymerizable monomer in the total solid content, the alkali solubility is good, and (A) the monofunctional photopolymerizable monomer having at least two aromatic rings in one molecule. (B) The sum of the contents of the monofunctional photopolymerizable monomer containing a carboxyl group in one molecule in the total solid content of the photosensitive composition is relative to the total amount of the photopolymerizable monomer in the total solid content in the photosensitive composition. It was confirmed that the etching resistance, tackiness and alkali solubility were particularly good when the content was 70% by weight or more. Further, from Comparative Examples 7 to 10, (A) a monofunctional photopolymerizable monomer having at least two aromatic rings in one molecule, (B) a monofunctional photopolymerizable monomer containing a carboxyl group, (C). A photosensitive composition for etching protection that has alkali solubility while maintaining etching resistance and tackiness and is excellent in stability over time by containing a photopolymerization initiator and a polyfunctional thiol compound of grade 2 or higher. Can be obtained.

10 ... Metal processing plate 11 ... Metal plate 12a ... First surface 12b ... Second surface 13 ... Aperture 13a ... First surface opening 13b ... Second surface opening 14 ... Photosensitive material 15a ... First surface Protective layer 15b ... Protective layer on the second surface

Claims (4)

A photosensitive composition for etching protection used for processing a metal plate, which contains at least (A) a monofunctional photopolymerizable monomer having at least two aromatic rings in one molecule, and (B) a carboxyl group. Photosensitive composition of a monofunctional photopolymerizable monomer containing a polymerizable monomer, (C) a photopolymerization initiator, (D) a secondary or higher polyfunctional thiol compound, and (B) a carboxyl group in one molecule. A photosensitive composition for etching protection, wherein the content in the total solid content of the product is 40% by weight or more with respect to the total amount of the photopolymerized monomer in the total solid content of the photosensitive composition. In the total solid content of the photosensitive composition of (A) a monofunctional photopolymerizable monomer having at least two aromatic rings in one molecule and (B) a monofunctional photopolymerizable monomer containing a carboxyl group in one molecule. The photosensitive composition for etching protection according to claim 1, wherein the sum of the contents of the above is 70% by weight or more based on the total amount of the photopolymerized monomers in the total solid content of the photosensitive composition. In a method for manufacturing a metal processed plate in which openings of different sizes are formed on the first surface and the second surface of the metal plate and penetrated by a double-sided etching method.
Using the etching protective photosensitive composition according to claim 1 or 2 ,
Metal processing including a step of forming a protective layer so that the other surface is not etched when etching one of the first surface and the second surface and changing the etching amount of each. How to make a board. The third aspect of claim 3, wherein the metal plate is a rolled metal obtained by rolling a base metal of a metal material with a roll and annealing the rolled base metal, and the metal thickness of the metal processed plate is 30 μm or less. Manufacturing method of metal processed plate.