JP5404028B2 - Method for manufacturing substrate to be etched - Google Patents

Description

The present invention relates to the production how the etched substrate.

  Plasma display panels (hereinafter also simply referred to as “PDP”) are widely used as large-screen full-color display devices. Since each pixel emits light by itself to form an image, the PDP has the advantages of a wider viewing angle, faster response speed, and better color purity than a liquid crystal display using a backlight and a color filter.

A Cr / Cu / Cr wiring structure in which a Cr (chromium) layer, a Cu (copper) layer, and a Cr layer are sequentially laminated on a glass substrate as one wiring structure that supplies power for light emission to each pixel of a PDP The body is known. In such a wiring structure, a first Cr layer, a Cu layer, and a second Cr layer are sequentially formed by a vapor deposition method or a sputtering method to form a Cr / Cu / Cr laminated film, followed by photolithography. A resin pattern for forming a wiring pattern is formed using a method, and a multi-stage etching process is performed using the resin pattern as a mask (see, for example, Patent Document 1).
JP 2000-11863 A

  By the way, in the said patent document 1, in order to selectively etch a Cr / Cu / Cr layer sequentially, the process using an acidic etching liquid and the process using an alkaline etching liquid are implemented combining. For example, according to the first embodiment described in Patent Document 1, after etching the second Cr layer located in the upper layer using an acidic etchant mainly composed of aluminum chloride and phosphoric acid, Etching the Cu layer with an acidic etchant composed mainly of iron and sulfuric acid, and finally using a strong alkaline etchant containing sodium hydroxide or calcium hydroxide to form a first Cr layer located in the lower layer Etching.

  A resin pattern serving as an etching mask for forming a wiring pattern is developed with an alkali developer and stripped with an alkali stripper. For this reason, it is common that the tolerance with respect to an alkaline chemical | medical solution is scarce. For this reason, in the above method proposed as the first embodiment of Patent Document 1, the resin pattern serving as an etching mask is removed prior to the first Cr layer etching step performed under strongly alkaline conditions. . Therefore, in the step of etching the first Cr layer, the first Cr layer is etched, and the second Cr layer that has already been patterned is also etched. It is necessary to devise the process of forming the Cr layer thick.

  Thus, there is no material for forming a resin pattern that is resistant to both acidic and alkaline etchants and that can be removed by an alkaline stripper after completion of wiring pattern formation. In the pattern forming method including the alkaline etching process, the present situation is that various devices on the process are required.

The present invention has been made in view of the above situation, and has a resin pattern as a mask that has etching resistance under acidic and alkaline conditions and can be peeled off by an alkaline stripping solution after completion of the etching step. and to provide a prepared how the etched substrate was.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors use a photosensitive resin composition containing a specific alkali-soluble resin and a trifunctional or higher polyfunctional monomer, and are etched acidic or alkaline. It has been found that the above problem can be solved if different temperature conditions are used in the step of performing the step and the step of stripping the resin pattern using the alkaline stripping solution, and the present invention has been completed. Specifically, the present invention provides the following.

In the first aspect of the present invention, a photosensitive resin composition is applied on a substrate to form a photosensitive resin layer having a thickness of 1 to 3 μm, and after selectively exposing the photosensitive resin layer, A step of developing to form a resin pattern, an etching step of selectively etching the substrate using an acidic or alkaline etching solution of 45 ° C. or lower using the resin pattern as a mask, and an alkaline of 50 to 80 ° C. A step of stripping the resin pattern using a stripping solution, wherein the photosensitive resin composition is produced by a reaction between an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound. And a trifunctional or higher polyfunctional monomer and a photopolymerization initiator , wherein the polyfunctional monomer is hexafunctional or higher .

In the second aspect of the present invention , a photosensitive resin composition is applied on a substrate to form a photosensitive resin layer having a thickness of 3.5 to 5 μm, and the photosensitive resin layer is selectively exposed. Thereafter, a step of developing to form a resin pattern, an etching step of selectively etching the substrate using an acidic or alkaline etching solution of 45 ° C. or lower using the resin pattern as a mask, and a temperature of 50 to 80 ° C. A step of stripping the resin pattern using an alkaline stripping solution, wherein the photosensitive resin composition is generated by a reaction between an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound. Production of a substrate to be etched comprising a soluble resin, a trifunctional or higher polyfunctional monomer, a bifunctional or lower monomer, and a photopolymerization initiator, wherein the polyfunctional monomer is trifunctional. It is a method.

According to the present invention, has an etching resistance in acidic and alkaline conditions, and producing how the etched substrate with a mask of resin pattern that can be peeled off is provided by the alkaline stripping solution after the etching step is completed .

  Hereinafter, although embodiment of this invention is described, this invention is not limited to the following embodiment at all.

<Method for manufacturing substrate to be etched>
The manufacturing method of the substrate to be etched according to the present invention will be described. The method for producing a substrate to be etched of the present invention includes (1) a step of applying a photosensitive resin composition on a substrate to form a photosensitive resin layer, and (2) selectively exposing the photosensitive resin layer. And (3) an etching step of selectively etching the substrate using an acidic or alkaline etching solution of 45 ° C. or lower, using the resin pattern as a mask, and (4) And a step of stripping the resin pattern using an alkaline stripping solution of 50 to 80 ° C. Hereinafter, each step will be described.

  First, (1) the process of applying a photosensitive resin composition on a substrate to form a photosensitive resin layer will be described.

In this step, a photosensitive resin composition, which will be described later, is applied on a substrate to form a photosensitive resin layer.
In many cases, a glass substrate is used as the substrate. On a glass substrate used as a substrate, a metal film to be etched is formed by vapor deposition or sputtering. Although the metal film may be a single layer, the present invention is characterized in that a composite metal film composed of a plurality of metal films having different etching conditions can be selectively etched. As such a composite metal film, a Cr / Cu / Cr laminated film in which a first Cr (chromium) layer, a Cu (copper) layer, and a second Cr layer are formed is exemplified.

  A photosensitive resin composition is applied to the substrate using a contact transfer type coating device such as a roll coater, reverse coater, bar coater, slit coater, etc., or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater. The photosensitive resin layer is formed on the substrate by applying and drying to remove the solvent. In the present invention, when the photosensitive resin layer is formed, the photosensitive resin layers formed on the substrate have different compositions depending on whether the thickness is 1 to 3 μm or 3.5 to 5 μm. A functional resin composition is used. Details of the composition of the photosensitive resin composition will be described later.

  Next, (2) the process of selectively exposing the photosensitive resin layer and developing it to form a resin pattern will be described.

In order to selectively expose the photosensitive resin layer, the exposure may be performed by irradiating an active energy ray such as an ultraviolet ray or an excimer laser through a light shielding pattern. For the exposure, a light source that emits ultraviolet rays such as a high-pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used. Although the energy dose to be irradiated varies depending on the composition of the photosensitive resin composition, it is preferably, for example, about 5 to 2000 mJ / cm ² .

  Next, a resin pattern is created by developing the exposed resin layer with a developer. The development method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. Specific examples of the developer include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. Then, the developed resin pattern may be post-baked and cured by heating. The post-bake temperature is preferably 150 to 250 ° C.

  Next, (3) an etching process for selectively etching the substrate using an acidic or alkaline etching solution of 45 ° C. or lower using the resin pattern as a mask will be described.

  As an etching method, for example, a commonly performed wet etching method in which the substrate is immersed in an etching solution may be used. As the etching solution used for wet etching, an acidic type or alkaline type may be selected as appropriate in accordance with an object to be etched. Examples of acidic etching solutions include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and mixed aqueous solutions of acidic components and salts of ferric chloride, ammonium fluoride, potassium permanganate, and the like. Is done. As the acidic component, a combination of a plurality of acidic components may be used. In addition, alkaline type etching solutions include sodium hydroxide, potassium hydroxide, ammonia, organic amines, aqueous solutions of alkali components such as organic amine salts such as tetramethylammonium hydroxide, alkaline components and potassium permanganate. A mixed aqueous solution of a salt such as A combination of a plurality of alkali components may be used as the alkali component.

  In the method for manufacturing a substrate to be etched according to the present invention, the temperature of the etching solution is 45 ° C. or lower. The resin pattern used as an etching mask in the present invention exhibits resistance to acidic and alkaline etching solutions in such a temperature range by being formed using a photosensitive resin composition described later. Therefore, the resin pattern is prevented from peeling off during the etching process, and the portion where the resin pattern does not exist is selectively etched.

  The method for manufacturing a substrate to be etched according to the present invention is suitably applied to a substrate on which a first Cr layer, a Cu layer, and a second Cr layer are sequentially formed. In this type of substrate, for example, the second Cr layer and Cu layer located on the outermost surface are etched using an acidic etchant, and then the first Cr layer is etched using an alkaline etchant. . According to the method of manufacturing a substrate to be etched according to the present invention, etching is performed without peeling the resin pattern on a substrate that requires an etching step under acidic conditions and an etching step under alkaline conditions. be able to.

  Next, (4) the process of peeling the said resin pattern using 50-80 degreeC alkaline peeling liquid is demonstrated.

  The method for producing a substrate to be etched according to the present invention uses an alkaline stripping solution of 50 to 80 ° C. when stripping a resin pattern used as an etching mask. As already described, in the present invention, an etching solution having a temperature of 45 ° C. or lower is used in the etching step, so that there is a difference in the temperature of the chemical solution between the etching step and the resin pattern peeling step. The resin pattern created by the photosensitive resin composition used in the present invention has a property of swelling with an alkaline stripping solution at 50 ° C. or higher. Therefore, the presence of the temperature difference as described above prevents the resin pattern from being peeled in the etching process, and the resin pattern is peeled in the resin pattern peeling process.

  Although it does not specifically limit as a peeling method of a resin pattern, For example, the method of immersing a board | substrate in the alkaline peeling liquid under stirring at 50-80 degreeC for 5 to 30 minutes is mentioned. Examples of the alkaline stripping solution include a solution obtained by dissolving an inorganic alkali component such as sodium hydroxide or potassium hydroxide in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Although it is possible to use a stripping solution containing an organic alkali component such as an organic amine or an organic ammonium salt, it is preferable to use a stripping solution containing an inorganic alkali component from the viewpoint of cost. The resin pattern may be peeled off by a spray method, a shower method, a paddle method or the like using the above-described stripping solution.

<Photosensitive resin composition>
Next, the photosensitive resin composition used in the manufacturing method of the substrate to be etched will be described. The photosensitive resin composition used in the method for producing the substrate to be etched is also one aspect of the present invention. The photosensitive resin composition of the present invention comprises an alkali-soluble resin (A) produced by a reaction between an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound, and a trifunctional or higher polyfunctional monomer (B). And a photopolymerization initiator (C).

[Alkali-soluble resin (A) produced by reaction of acid group-containing acrylic resin and alicyclic epoxy group-containing unsaturated compound]
The alkali-soluble resin (hereinafter, also referred to as “component (A)”) contained in the photosensitive resin composition of the present invention comprises a part of acid groups derived from the acid group-containing acrylic resin (a1) and an alicyclic epoxy. An epoxy group derived from the group-containing unsaturated compound (a2) is reacted to introduce an unsaturated group derived from the alicyclic epoxy group-containing unsaturated compound (a2) necessary for curing with active energy rays. is there.
Each component is as follows.

[Acid group-containing acrylic resin (a1)]
Acid group-containing acrylic resins (hereinafter also referred to as “component (a1)”) include acids having an ethylenically unsaturated bond, esters of (meth) acrylic acid, vinyl aromatic compounds, amide-based unsaturated compounds. A copolymer obtained by copolymerizing one or more selected from monomers such as compounds and polyolefin-based compounds can be used. Specifically, an acid having an ethylenically unsaturated bond such as (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, and (anhydrous) maleic acid is an essential component. Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl ( Esters of (meth) acrylic acid such as (meth) acrylate; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene; (meth) acrylamide, diacetone acrylamide, N-methylolacrylamide, N − Amide-type unsaturated compounds such as toximethylacrylamide; Polyolefin-type monomers such as butadiene, isoprene and chloroprene, and (meth) acrylonitrile, methylisopropenyl ketone, vinyl acetate, Veova monomer (shell chemical products), vinyl propionate, Examples thereof include a copolymer obtained by copolymerizing one or more monomers selected from other monomers such as vinyl pivalate.

  The acid value of the component (a1) is preferably 15 mgKOH / g or more and in the range of 40 to 500 mgKOH / g. When the component (a1) has such an acid value, the component (a1) is reacted with an alicyclic epoxy group-containing unsaturated compound (a2) described later to cause the component (A) to have a desired amount of unsaturation. Even after the introduction of groups, a sufficient amount of acid groups remains in the component (A). Thereby, (A) component can have the outstanding developability.

[Aliphatic epoxy group-containing unsaturated compound (a2)]
As the alicyclic epoxy group-containing unsaturated compound (hereinafter also referred to as “component (a2)”), a compound having one ethylenically unsaturated group and an alicyclic epoxy group in one molecule is preferable. Specific examples include compounds represented by the following formulas (I) to (XV).

Here, R ¹ is a hydrogen atom or a methyl group. R ² is a C 1-6 divalent aliphatic saturated hydrocarbon group. R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms. l is an integer of 0-10. R ² is preferably a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. Examples of R ³ include methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, hexamethylene group, phenylene group, cyclohexylene group, —CH ₂ —Ph—CH ₂ — (Ph Is a phenylene group).

[Preparation of alkali-soluble resin (A)]
The component (A) is prepared by reacting the components (a1) and (a2) and introducing an unsaturated group into the component (a1). Specifically, for example, it is prepared by reacting an inert organic solvent solution of the component (a1) with the component (a2) at about 20 to 120 ° C. for about 1 to 5 hours. Examples of the inert organic solvent include, but are not limited to, alcohols, esters, aliphatic or aromatic hydrocarbons. The ratio of the component (a1) to the component (a2) can be changed according to the type of monomer used for the synthesis of the component (a1), but the ratio of the component (a2) to the component (a1) is 15 mol%. The above is preferable. If the ratio of the component (a2) to the component (a1) is 15 mol% or more, the resin pattern obtained by curing the photosensitive resin composition containing the component (A) has good etching resistance. Can be granted.

  The mass average molecular weight of the component (A) thus prepared can be determined by a gel permeation chromatography method, and the value is preferably 1000 to 100,000, more preferably 3000 to 70000, and still more preferably 9000 to 30000. is there. Since the component (A) has a double bond in the side chain, it can be cured by light in the presence of a photopolymerization initiator. That is, since the component (A) which is a resin has high photosensitivity, it is possible to improve the curing density when crosslinked, and to increase the degree of curing of the photosensitive resin composition by exposure. it can. Moreover, since it has an acid group in the side chain, it is possible to perform development with an alkaline developer or to remove the formed resin pattern with an alkaline stripping solution. The acid value of such component (A) is preferably 20 to 200 mgKOH / g, more preferably 30 to 150 mgKOH / g, and further preferably 50 to 140 mgKOH / g. By setting it to the lower limit value or more, excellent developability can be obtained, and by setting the upper limit value or less, etching resistance is improved and an excellent pattern shape is obtained. Moreover, etching resistance can be improved by having an alicyclic group derived from the component (a2).

[Monomer (B)]
The monomer component (hereinafter, also referred to as “component (B)”) contained in the photosensitive resin composition of the present invention requires a tri- or higher functional monomer component (hereinafter also referred to as “component (b1)”) as an essential component. Including. Here, “a tri- or higher functional monomer component” means a monomer component having three or more ethylenic double bonds per molecule that can be addition-polymerized by light irradiation in the presence of a photopolymerization initiator. is there. In the manufacturing method of the to-be-etched substrate of the present invention, the resin pattern formed as an etching mask is included in the photosensitive resin composition when the film thickness is 1 to 3 μm and when the film thickness is 3.5 to 5 μm (B ) Component composition is different. Hereinafter, each of the resin patterns formed as an etching mask will be described in terms of film thickness.

When the film thickness of the resin pattern formed as an etching mask is 1 to 3 μm In the case of thin film conditions where the film thickness of the resin pattern is 1 to 3 μm, it is advantageous with respect to peeling the resin pattern with an alkaline stripping solution after etching. It can be said that it is a condition. However, since the resin pattern is a thin film, it is a severe condition from the viewpoint of etching resistance, that is, resistance to an acidic or alkaline etching solution, and it can be said that it is a disadvantageous condition.
Therefore, in the present invention, when the etching process is performed under a thin film condition where the film thickness of the resin pattern is 1 to 3 μm, a monomer having 6 or more functional groups is preferably used as the component (b1). By including such a monomer component in the photosensitive resin composition, the crosslink density is increased inside the resin pattern obtained by photocuring the photosensitive resin composition, so that it can be applied to an acidic or alkaline etching solution. Resistance can be improved.

  In this case, as component (b1), dipentaerythritol hexa (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate monomer, polyhydric alcohol and N -Condensates with methylol (meth) acrylamide and the like. These hexafunctional or higher functional monomers can be used alone or in combination of two or more. Among them, dipentaerythritol hexaacrylate (DPHA) is preferably used to form a strong resin pattern with high etching resistance, and polyfunctional urethane (meth) acrylate improves the flexibility of the resin pattern and is etched. It is suitably used for improving the adhesion of the resin pattern to the substrate.

  Moreover, when the film thickness of a resin pattern is 1-3 micrometers, it is preferable to contain the monofunctional monomer (henceforth "(b2) component") containing a nitrogen atom as (B) component. A monofunctional monomer means a monomer having one ethylenically unsaturated group. By including the component (b2) in the photosensitive resin composition of the present invention, flexibility can be imparted to the film of the resin pattern obtained by curing the photosensitive resin composition. Improved adhesion.

  The component (b2) is preferably a monomer such that the homopolymer obtained by polymerizing the component (b2) has a glass transition temperature (Tg) of 80 ° C. or higher. When the component (b2) satisfies such a condition, fastness to chemicals can be imparted to the resin pattern, and as a result, chemical resistance of the resin pattern is improved and etching resistance is improved. Examples of such component (b2) include acrylamide (Tg of homopolymer: 179 ° C., the same shall apply hereinafter), methacrylamide (171 ° C.), N-methylacrylamide (171 ° C.), dimethylacrylamide (119 ° C.), N-isopropyl. Acrylamide (134 ° C), acryloylmorpholine (145 ° C), N-tert-butylacrylamide (135 ° C), N-phenylacrylamide (160 ° C), diacetone acrylamide (86 ° C), acryloylpiperidine (116 ° C), diethylacrylamide (81 ° C.), 2-hydroxyethyl acrylamide (98 ° C.), dimethylaminopropyl acrylamide (134 ° C.) and the like. Among these, acrylamide, methacrylamide, N-methyl acrylamide, acryloyl morpholine, and N-phenyl acrylamide with a homopolymer Tg of 140 ° C. or higher are more preferable, and acryloyl morpholine is most preferable.

  The component (b1) is preferably contained in an amount of 110 to 300 parts by mass, more preferably 115 to 200 parts by mass, and more preferably 115 to 170 parts by mass with respect to 100 parts by mass of the component (A). Further preferred. By setting it to the lower limit value or more, excellent etching resistance can be obtained, and by setting it to the upper limit value or less, the resin pattern can be satisfactorily removed with an alkaline stripping solution after the etching process is completed.

  The component (b2) is preferably contained in an amount of 10 to 80 parts by mass, more preferably 20 to 75 parts by mass, and more preferably 30 to 70 parts by mass with respect to 100 parts by mass of the component (A). More preferably. By setting it to the lower limit value or more, good flexibility and adhesion to the substrate can be imparted to the resin pattern, and by setting the upper limit value or less, good etching resistance can be obtained.

  As the component (B), various monomer components can be contained in addition to the component (b1) or the components (b1) and (b2). Examples of such a monomer component include a compound having an ethylenically unsaturated group, a monofunctional monomer having one ethylenically unsaturated group, and a polyfunctional monomer having 2 to 5 ethylenically unsaturated groups. And so on. One or more of these components are appropriately selected and used according to the properties required for the photosensitive resin composition, such as polymerization reactivity and monomer viscosity. In addition, it is preferable that the addition amount of monomer components other than (b1) component and (b2) component is 80 mass parts or less with respect to 100 mass parts of (A) component, and it is more preferable that it is 1-60 mass parts. preferable. By setting it to the upper limit or less, a sufficient crosslinking density is maintained inside the resin pattern, and resistance to acidic or alkaline etching solutions can be improved.

When the film thickness of the pattern to be formed as an etching mask is 3.5 to 5 μm When the film thickness of the resin pattern is 3.5 to 5 μm, it is an advantageous condition for obtaining sufficient etching resistance. It can be said. However, since the resin pattern is a thick film, if the internal cross-linking of the resin pattern is excessively advanced, the resin pattern may not be sufficiently removed after the etching process, and a residue may be a problem. Therefore, it is preferable that the internal cross-linking density is lower than that in the above case where the film thickness of the resin pattern is 1 to 3 μm.

  Therefore, in the present invention, when the etching step is performed under the condition that the resin pattern has a film thickness of 3.5 to 5 μm, the component (b1) is a trifunctional monomer, and further a bifunctional or lower monomer (hereinafter, “ (B3) component ”) is preferably included in the component (B). When such a component (b1) and a component (b3) are contained in the photosensitive resin composition as the component (B), the crosslinking density inside the resin pattern obtained by photocuring the photosensitive resin composition. Is prevented from becoming excessively high, and even if the resin pattern is formed as a thick film, it is satisfactorily removed by the stripper after the etching process.

  In this case, examples of the component (b1) include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerin tri (meth) acrylate, and triacryl formal. These trifunctional monomers can be used alone or in combination of two or more.

  As the component (b3), (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N -Methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2 -Acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Rate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl ( Monofunctional monomers such as (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, half (meth) acrylate of phthalic acid derivatives; ethylene glycol di (meth) acrylate, di Tylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, hexaethylene glycol (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate butylene glycol di (meth) acrylate, neopentyl Glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl ) Propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol glycidyl ether di (meth) acrylate, diethyleneglycol Ludiglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, urethane (meth) acrylate (ie tolylene diisocyanate), trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate And a bifunctional monomer such as methylene bis (meth) acrylamide and (meth) acrylamide methylene ether. These monomers may be used alone or in combination of two or more.

  Among the components (b3) exemplified above, EO-modified linear bifunctional monomers are preferably used, and in particular, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, hexaethylene glycol diacrylate. Etc. are preferably used.

  The component (b1) is preferably contained in an amount of 30 to 200 parts by mass and more preferably 35 to 160 parts by mass with respect to 100 parts by mass of the component (A). By setting the lower limit value or more, excellent etching resistance can be obtained, and by setting the upper limit value or less, the resin pattern can be satisfactorily removed by the stripping solution after the etching process is completed.

  Moreover, it is preferable to contain 1-60 mass parts with respect to 100 mass parts of (A) component, and, as for the said (b3) component, it is more preferable to contain 2-55 mass parts. In the method for manufacturing a substrate to be etched according to the present invention in which a difference in the temperature of the treatment liquid is provided between the etching step and the resin pattern peeling step by setting the lower limit value or more, both etching resistance and ease of removal of the resin pattern are compatible. Is done. That is, in the etching process performed at a low temperature (for example, 20 ° C. to 45 ° C.), the resin pattern is prevented from peeling because the swelling of the resin pattern is small. In this peeling process, the resin pattern is greatly swelled, so that the peeling of the resin pattern is promoted. Moreover, the outstanding etching tolerance is acquired by setting it as an upper limit or less.

[Photoinitiator (C)]
Although it does not specifically limit as a photoinitiator (henceforth "(C) component") contained in the photosensitive resin composition of this invention, For example, 1-hydroxy cyclohexyl phenyl ketone, 2-hydroxy-2 -Methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1 -One, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, Dil-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- 1- (o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4-dimethyl Ethyl aminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexyl benzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl -1,2-propanedione-2- (o-ethoxycarbonyl) oxy , Methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4- Diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene Peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer Benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloro Acetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloro Acetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6- Tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6- Bis (trichloromethyl) -s-triazine, 2- [2- (furan-2- L) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s- Triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo 4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2 -Bromo-4-methoxy) styrylphenyl-s-triazine and the like. These photopolymerization initiators can be used alone or in combination of two or more.

  Although content of (C) component should just adjust suitably according to content of (B) component, it is preferable that it is 1-30 mass parts with respect to 100 mass parts of alkali-soluble resin (A), 5 -25 mass parts is more preferable, and 10-20 mass parts is further more preferable. By setting it as said range, sufficient heat resistance and chemical-resistance can be acquired, a coating-film formation ability can be improved, and photocuring failure can be suppressed.

[Sensitizer]
The photosensitive resin composition of the present invention may contain a compound having a thiol group as a sensitizer. Such a sensitizer generates S radicals by ene-thiol reaction when irradiated with ultraviolet rays. Since the polymerization reaction by S radicals accelerates the curing of the photosensitive resin composition without being affected by oxygen inhibition, it is possible to improve the pattern remaining film ratio in development and to improve etching resistance. Examples of such compounds include esters such as trimethylolpropane tris (3-mercaptopropionate); alcohols such as 2-mercaptoethanol, 1-thioglycerol, glycerol monothioglycolate, and 4-mercaptophenol; thioglycol Carboxylic acids such as acid, 3-mercaptopropionic acid, 2-mercaptopropionic acid, thiomalic acid, mercaptoisobutyric acid, meso-2,3-dimercaptoisobutyric acid, thiosalicylic acid; 2-aminoethanethiol, 2-aminobenzenethiol , Amines such as 4-aminobenzenethiol; and cysteine.

  The content of the sensitizer in the photosensitive resin composition may be appropriately adjusted according to the contents of the component (A) and the component (B), but is 0 with respect to 100 parts by mass of the alkali-soluble resin (A). 0.1-30 parts by mass is preferable, 0.5-25 parts by mass is more preferable, 0.8-20 parts by mass is further preferable, and 1-15 parts by mass is particularly preferable. By setting it as said range, developability and etching tolerance can be improved.

[Organic solvent]
The photosensitive resin composition of the present invention preferably contains an organic solvent for improving coating properties and adjusting the viscosity. Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether , Dipropylene glycol monomethyl ether , (Poly) alkylene glycol monoalkyl ethers such as dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether (Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; Diethylene glycol Other ethers such as methyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. Alkyl 2-lactic acid esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxy Ethyl acetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyrate Tylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-butyrate Other esters such as propyl, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate; toluene, xylene, etc. Aromatic hydrocarbons; amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and the like. These solvents can be used alone or in combination of two or more.

  The content of the organic solvent is not particularly limited, and is appropriately set according to the coating film thickness at a concentration that can be applied to a substrate or the like. In this case, the solid content concentration is preferably 5 to 70% by mass, and more preferably 10 to 60% by mass.

[Other ingredients]
The photosensitive resin composition of this invention can contain additives, such as an antifoamer and surfactant, as another component as needed. The antifoaming agent is not particularly limited, and examples thereof include silicone-based and fluorine-based compounds. The surfactant is not particularly limited, and examples thereof include anionic, cationic, and nonionic compounds.

  The present invention will be described more specifically with reference to the following examples. However, these examples are illustrative of the present invention and are not intended to limit the scope of the invention.

<Preparation of photosensitive resin composition>
According to Table 1 to Table 4, to prepare a photosensitive resin composition of Preparation Example 17 and Comparative Preparation Examples 1 to 3. Each component described in Table 1 is as follows. In addition, 45 mass% DPGME (dipropylene glycol monomethyl ether) solution was produced for alkali-soluble resin (A), and it used for preparation of the photosensitive resin composition. Here, in Tables 1 to 4, 100 parts by mass of the alkali-soluble resin (A-1 or A-2) means that the solid content of the alkali-soluble resin is 100 parts by mass.

［式（１）中、Ｒ^４はアルキル基またはヒドロキシアルキル基を表し、式（１）、式（２）及び式（３）中、Ｘは水素原子又はメチル基を表す。］
Ａ−２：ベンジルメタクリレート及びメタクリル酸の共重合体（ベンジルメタクリレート／メタクリル酸＝８０：２０（質量比）、質量平均分子量６００００） Alkali-soluble resin (A)
A-1: Cyclomer ACA Z250 (manufactured by Daicel Chemical Industries, Ltd., mass average molecular weight 20000, acid value 101.7 mg KOH / g, produced by reaction of acid group-containing acrylic resin and alicyclic epoxy group-containing unsaturated compound) It is a resin composed of structural units represented by the following formula (1), formula (2) and formula (3).

[In Formula (1), R ⁴ represents an alkyl group or a hydroxyalkyl group, and in Formula (1), Formula (2), and Formula (3), X represents a hydrogen atom or a methyl group. ]
A-2: Copolymer of benzyl methacrylate and methacrylic acid (benzyl methacrylate / methacrylic acid = 80: 20 (mass ratio), mass average molecular weight 60000)

Monomer (B)
B-1: Tetraethylene glycol diacrylate (bifunctional monomer)
B-2: Tricyclodecane methanol diacrylate (bifunctional monomer)
B-3: TMPTA (trimethylolpropane triacrylate, trifunctional monomer)
B-4: DPHA (dipentaerythritol hexaacrylate, hexafunctional monomer)
B-5: CN9006 (Sartomer, urethane acrylate, hexafunctional monomer)
B-6: Acrylylmorpholine (nitrogen-containing monofunctional monomer)
B-7: CN2300 (manufactured by Sartomer, 8-functional monomer)
B-8: CN2302 (Sartomer Co., 16 functional monomer)
B-9: 2-phenoxyethyl acrylate

Photopolymerization initiator (C)
IR369: Irgacure 369 (Ciba Specialty Chemicals)
EAB-F: 4,4′-bis (diethylamino) benzophenone (Hodogaya Chemical Co., Ltd.)

<Creation of substrate to be etched>
A glass substrate (thickness 1.8 mm) on which the second Cr layer / Cu layer / first Cr layer was laminated was produced by sputtering, and used as an evaluation substrate. In the evaluation substrate, the second Cr layer and the first Cr layer are located at the outermost surface and the lowermost layer, respectively, and the Cu layer is located between them. The thickness of each layer is 100 nm for the second Cr layer, 2.0 μm for the Cu layer, and 50 nm for the first Cr layer. Evaluation having a photosensitive resin layer having a film thickness of 2.0 μm, 2.5 μm, or 5 μm by applying a photosensitive resin composition to the evaluation substrate using a spin coater and drying at 65 ° C. for 6 minutes. A substrate was obtained. Next, these photosensitive resin layers are selectively irradiated with ultraviolet rays (light source: ultra-high pressure mercury lamp) through a negative mask at an exposure amount of 75 mJ / cm ² , and a 0.25 mass% sodium carbonate solution is used as a developer. A resin pattern was formed by spray development at 30 ° C. for 120 seconds, washed with pure water, and air blow dried. Thereafter, the formed resin pattern was subjected to post-exposure by irradiating with ultraviolet rays (light source: ultra-high pressure mercury lamp) at an exposure amount of 300 mJ / cm ² .

Next, etching was performed on the evaluation substrate on which the resin pattern was formed. First, the evaluation substrate is immersed for 5 minutes in an acidic etching solution at 35 ° C. composed of an aqueous solution of about 15% by mass of hydrochloric acid (for an evaluation of durability, the immersion time is longer than that of a normal process), and the second substrate located on the outermost surface. The Cr layer was etched and washed with pure water. Thereafter, a 0.3 / 0.3 / 0.3 (mol / L ratio) HCl / FeCl ₃ / Cu ²⁺ aqueous solution is prepared as an acidic etching solution, and the evaluation substrate is immersed in an acidic etching solution at 30 ° C. The Cu layer was etched for 60 seconds while being swung, and washed with pure water. Finally, the evaluation substrate is immersed for 10 minutes in an alkaline etching solution at 40 ° C. in which 5% by mass of potassium permanganate is added to 5% by mass of Na ₂ SiO ₃ aqueous solution, and the first Cr layer located at the bottom layer is formed. Etched and washed with pure water.

  After completion of the etching process, an alkaline stripping solution was used to strip the resin pattern present on the evaluation substrate. As the stripping solution, a 12 mass% sodium hydroxide aqueous solution heated to 60 ° C was used.

<Evaluation>
By the procedure as described above, for the photosensitive resin compositions of Preparation Examples 1 and 3-6 and Comparative Preparation Examples 1 to 3, the evaluation substrate having a resin pattern with a film thickness of 5 μm was used as the photosensitive resin composition of Preparation Examples 7 to 16. For the photosensitive resin composition, an evaluation substrate having a resin pattern with a film thickness of 2.5 μm was used. Further, for the photosensitive resin compositions of Preparation Examples 2, 7, 10 and 17, a resin pattern with a film thickness of 2.0 μm was used. Evaluation substrates having the following characteristics were prepared. Each of the evaluation substrates is etched to evaluate the remaining film ratio after development, the resistance to chemicals (etching resistance), the time required for removing the resin pattern after completion of etching, and the presence or absence of residues after removing the resin pattern. did. The results are shown in Tables 5 to 9. The evaluation method and evaluation criteria for each item are as follows. In addition, when the evaluation board | substrate which has a resin pattern of a 2.5 micrometer film thickness was produced and evaluated using the photosensitive resin composition of the preparation examples 1 and 3-6 evaluated by the film thickness of 5 micrometers, all are acid. Alkali resistance was not obtained (the following Δ evaluation was obtained).

[Remaining film properties during development]
Evaluation was made based on the residual ratio of the resin pattern film after the photosensitive resin layer was exposed and spray developed.
○: Residual film ratio after development of photocured resin pattern is 90% or more Δ: Residual film ratio after development of photocured resin pattern is 50% or more and less than 90% ×: After development of photocured resin pattern The remaining film rate is less than 50%

[Acid and alkali resistance]
It evaluated by observing the peeling state of the resin pattern after completion | finish of the etching process of a 2nd Cr layer, Cu layer, and 1st Cr layer.
(Double-circle): The peeling of the resin pattern after completion | finish of an etching process is not observed.
○: Peeling of the resin pattern after completion of the etching process is hardly observed (peeling part is less than 5% in area ratio).
(Triangle | delta): The peeling of the resin pattern after completion | finish of an etching process generate | occur | produced. (The peeled portion is 5% to less than 30% in area ratio).
X: Peeling occurred in most of the resin pattern during the etching process (the peeled portion was 30% or more in area ratio).

[Peeling time]
After the etching process was completed, the evaluation was made based on the time required for peeling the resin pattern with an alkaline stripping solution.
○: Time required for peeling is less than 100 seconds Δ: Time required for peeling is 100 seconds or more and 150 seconds or less ×: Time required for peeling exceeds 150 seconds

[Peelability]
The resin pattern residue remaining on the substrate was observed and evaluated after the resin pattern was peeled off with an alkaline stripping solution.
○: Resin pattern residue does not exist after peeling.
Δ: Resin pattern remains slightly after peeling.
X: A large amount of the resin pattern remains after peeling.

From the above results, it was confirmed that Examples 1 to 17 and Reference Examples 1 to 2 had good acid / alkali resistance (etching resistance) relative to Comparative Examples 2 to 3. From this, it is understood that the etching resistance of the resin pattern obtained by curing the photosensitive resin composition is improved by using the composition containing the predetermined alkali-soluble resin of the present invention.

In addition, the photosensitive resin compositions of Preparation Examples 2 and 7 to 17 have better acid / alkali resistance in a thin film (2.5 μm or 2.0 μm) than the photosensitive resin compositions of Preparation Examples 1 and 3 to 6. Was confirmed. From this, it is understood that when a thin film resin pattern is prepared and etched, it is preferable to use a photosensitive resin composition containing a monomer having 6 or more functional groups.

As the results of Examples 4 to 17 show, the polyfunctional monomer is contained in the range of 110 to 200 parts by mass with respect to 100 parts by mass of the alkali-soluble resin, thereby forming a thin film (2.5 μm or 2.0 μm). Even in this case, it was confirmed that the acid / alkali resistance was good.
Moreover, as the results of Examples 10 to 13 show, it is understood that acid / alkali resistance is improved by using a photosensitive resin composition containing acryloylmorpholine which is a nitrogen-containing monofunctional monomer. This is due to the effect of improving the adhesion between the substrate and the resin pattern due to the presence of nitrogen atoms introduced into the resin by acryloylmorpholine in addition to the effect of improving the flexibility of the resin pattern by the monofunctional monomer. It is guessed.

In Examples 1 to 3 , it was confirmed that the peeling time in the thick film (5 μm) was short. From this, it is understood that the releasability of the resin pattern is improved if the polyfunctional (trifunctional) monomer is 30 to 100 parts by mass and the bifunctional or lower monomer is 1 to 60 parts by mass with respect to 100 parts by mass of the resin. The

  Considering these results, it is surmised that a polyfunctional monomer such as a hexafunctional monomer increases the crosslink density of the resin, thereby improving the acid / alkali resistance while delaying the peeling of the resin pattern. . For this reason, it becomes a severe condition with respect to the presence of acid / alkaline chemicals like a thin film resin pattern (1 to 3 μm), but if the resin pattern is easy to peel off, a hexafunctional monomer is included. It is understood that it is preferable to use a photosensitive resin composition. On the other hand, when the resin pattern is difficult to peel off while being relatively relaxed with respect to the presence of an acid / alkaline chemical solution, such as a thick film (3.5 to 5 μm), trifunctional It is understood that it is preferable to use a photosensitive resin composition containing a monomer having a relatively small number of functional groups such as a monomer. Furthermore, by using these photosensitive resin compositions and carrying out the etching process at 45 ° C. or less and the process of peeling the resin pattern at 50 to 80 ° C., the chemical resistance of the resin pattern (acid / alkali resistance) ) And the releasability of the resin pattern with an alkaline stripping solution, both conflicting required performances can be satisfied.

Claims (9)

Applying a photosensitive resin composition on a substrate to form a photosensitive resin layer having a thickness of 1 to 3 μm ;
A step of selectively exposing the photosensitive resin layer and then developing to form a resin pattern;
Etching process using the resin pattern as a mask and selectively etching the substrate using an acidic or alkaline etching solution of 45 ° C. or lower;
A step of peeling the resin pattern using an alkaline stripping solution at 50 to 80 ° C.,
The photosensitive resin composition comprises an alkali-soluble resin produced by a reaction between an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound, a trifunctional or higher polyfunctional monomer, and a photopolymerization initiator. Contains ,
A method for producing a substrate to be etched, wherein the polyfunctional monomer has 6 or more functional groups . Applying a photosensitive resin composition on a substrate to form a photosensitive resin layer having a thickness of 3.5 to 5 μm;
A step of selectively exposing the photosensitive resin layer and then developing to form a resin pattern;
Etching process using the resin pattern as a mask and selectively etching the substrate using an acidic or alkaline etching solution of 45 ° C. or lower;
A step of peeling the resin pattern using an alkaline stripping solution at 50 to 80 ° C.,
The photosensitive resin composition comprises an alkali-soluble resin produced by a reaction between an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound, a trifunctional or higher polyfunctional monomer, and a bifunctional or lower monomer. , Containing a photopolymerization initiator,
A method for producing a substrate to be etched, wherein the polyfunctional monomer is trifunctional. 3. The method for manufacturing a substrate to be etched according to claim 1, wherein the alkaline stripping solution contains an inorganic alkali compound. With respect to the 100 parts by weight of the alkali-soluble resin, the manufacturing method of the etched substrate according to claim 1, characterized in that said containing 110 to 300 parts by weight of a polyfunctional monomer. The method for producing a substrate to be etched according to claim 1 or 4, wherein the photosensitive resin composition further contains a nitrogen-containing monofunctional monomer.   6. The method for producing a substrate to be etched according to claim 5, wherein the nitrogen-containing monofunctional monomer is acryloylmorpholine. 3. The etched substrate according to claim 2, comprising 30 to 100 parts by mass of the polyfunctional monomer and 1 to 60 parts by mass of the bifunctional or lower monomer with respect to 100 parts by mass of the alkali-soluble resin. Production method. The method for producing a substrate to be etched according to any one of claims 1 to 7 , wherein a ratio of the alicyclic epoxy group-containing unsaturated compound to the acid group-containing acrylic resin is 15 mol% or more. . The base is formed by sequentially forming a first Cr layer, a Cu layer, and a second Cr layer on a substrate,
The etching step includes a step of selectively etching the second Cr layer using an acidic etchant, a step of selectively etching the Cu layer using an acidic etchant, and an alkaline etchant. A method for manufacturing a substrate to be etched according to any one of claims 1 to 8 , further comprising: selectively etching the first Cr layer by using a material.