WO2014200028A1

WO2014200028A1 - Photosensitive resin composition, photosensitive element, mask material for sand-blasting, and surface treatment method for object to be treated

Info

Publication number: WO2014200028A1
Application number: PCT/JP2014/065493
Authority: WO
Inventors: 秀一板垣; 吉田　哲也; 恭子小澤
Original assignee: 日立化成株式会社
Priority date: 2013-06-14
Filing date: 2014-06-11
Publication date: 2014-12-18
Also published as: JPWO2014200028A1; TW201512779A

Abstract

The present invention provides a photosensitive resin composition containing a binder polymer (A) having a carboxyl group, a photopolymerizable monofunctional compound (B) having an ethylene-based unsaturated group, a photopolymerizable polyfunctional compound (C) having an ethylene-based unsaturated group, a urethane (meth)acrylate compound (D), and a photopolymerization initiator (E), wherein component (B) contains a (meth)acrylate compound represented by general formula (1) or a (meth)acrylate compound represented by general formula (2).

Description

Photosensitive resin composition, photosensitive element, mask material for sandblasting, and surface processing method for object to be processed

The present invention relates to a photosensitive resin composition, a photosensitive element using the photosensitive resin composition, a mask material for sandblasting, and a surface processing method for an object to be processed.

Conventionally, as a method for selectively cutting a predetermined portion of an object to be processed such as glass or ceramic, a resist layer is formed by providing a photosensitive layer made of a photosensitive resin composition as a mask material on the object to be processed, and then patterning the photosensitive layer. A method of selectively cutting an object to be processed by using a dry etching method or a wet etching method after forming a (mask portion) is known.

As a photosensitive resin composition used as a mask material for the wet etching method, for example, a photosensitive resin composition for hydrofluoric acid etching containing a specific silane compound has been proposed (see, for example, Patent Document 1).

As a dry etching method, for example, a method is known in which a non-mask portion is selectively cut (ie, sandblasted) by spraying an abrasive.

The photosensitive resin composition used as the mask material for sandblast treatment is used, for example, as a photosensitive element in which a photosensitive layer made of a photosensitive resin composition is provided on a support. As the photosensitive resin composition, a composition containing an alkali-soluble resin, urethane (meth) acrylate, and a photopolymerization initiator has been used. Examples of the alkali-soluble resin include carboxyl group-containing cellulose and carboxyl group-containing acrylic resin (see, for example, Patent Documents 2 and 3).

Such a conventional photosensitive resin composition has a problem that when a photosensitive element is produced, it is difficult to peel the photosensitive layer from the support due to stickiness of the photosensitive resin composition.

In order to solve this problem, for example, Patent Document 4 discloses a method of providing a water-soluble resin layer (peeling layer) obtained by adding ethylene glycol, propylene glycol, polyethylene glycol or the like to polyvinyl alcohol or the like. 5 discloses a method of providing a release layer containing an alkali-soluble cellulose derivative or the like between a support and a photosensitive resin layer.

Japanese Patent No. 4969154 Japanese Patent No. 3449572 Japanese Patent No. 3846958 Japanese Patent Laid-Open No. 6-161098 JP 2012-27357 A

However, the conventional photosensitive resin compositions described in Patent Documents 2 to 5 have insufficient adhesion to a base material such as a glass substrate, and it is difficult to form a pattern on such a base material. There's a problem. Therefore, when an adhesion assistant or the like is used to improve the adhesion, there is a problem that the alkali developability is lowered and the pattern formation becomes difficult.

Therefore, the present invention can easily peel the support from the photosensitive layer without providing a peeling layer, can form a good pattern on a substrate such as a glass substrate, and is a resist to be formed. An object of the present invention is to provide a photosensitive resin composition suitable for sandblasting, wherein the pattern has good blast resistance. Furthermore, an object of the present invention is to provide a photosensitive element, a sandblasting mask material using the photosensitive resin composition, and a surface processing method for a target object.

The present invention includes (A) a binder polymer having a carboxyl group, (B) a photopolymerizable monofunctional compound having an ethylenically unsaturated group, (C) a photopolymerizable polyfunctional compound having an ethylenically unsaturated group, (D ) A urethane (meth) acrylate compound and (E) a photopolymerization initiator, and the component (B) is represented by the following formula (1) (meth) acrylate compound or the following formula (2). Provided is a photosensitive resin composition comprising a (meth) acrylate compound.

[In General Formula (1), R ¹ represents an acryloyl group or a methacryloyl group. R ² represents an alkylene group having a hydroxyl group or a polyoxyalkylene group having a hydroxyl group. R ³ represents an alkyl group or an aryl group. ]

[In General Formula (2), R ⁴ represents an acryloyl group or a methacryloyl group. R ⁵ represents an alkylene group having a hydroxyl group or a polyoxyalkylene group having a hydroxyl group. R ⁶ represents a methyl group. ]

According to such a photosensitive resin composition, it is possible to easily peel the support from the photosensitive layer by having the above configuration, and a good pattern on a substrate such as a glass substrate, a silicon wafer, or a ceramic substrate. And a resist pattern having good blast resistance can be formed. Therefore, the photosensitive resin composition can be suitably used as a sandblast mask material. Moreover, the said photosensitive resin composition is excellent in adhesiveness with base materials, such as a glass substrate, a silicon wafer, and a ceramic substrate.

In addition, the photosensitive resin composition preferably further contains (F) a silane compound. And it is especially preferable that the (F) silane compound is a silane compound having a mercapto group represented by the following general formula (I).

[In the general formula (I), R represents an alkylene group having 1 to 6 carbon atoms, A represents an alkyl group, B represents an alkoxy group, a chloro group, an alkoxyalkoxy group, an acetoxy group or an alkenyloxy group, and n Represents an integer of 0-2. ]

When the photosensitive resin composition contains such a (F) silane compound, adhesion with a substrate such as a glass substrate, a silicon wafer, or a ceramic substrate is improved, and a better pattern can be formed. . When a silane compound having a mercapto group is used, the adhesiveness of the photosensitive resin composition with the substrate can be further improved, and the elastic modulus of the cured product does not increase. The formed resist pattern has better blast resistance.

The content of the photopolymerizable monofunctional compound (B) having an ethylenically unsaturated group is preferably 3 to 20% by mass based on the total solid content of the photosensitive resin composition.

(B) When the content of the photopolymerizable monofunctional compound having an ethylenically unsaturated group is 3% by mass or more based on the total solid content of the photosensitive resin composition, adhesion to various substrates is improved. However, when it is 20% by mass or less, fluidization is suppressed and the stickiness of the photosensitive resin composition tends to be weakened.

The weight average molecular weight of the (D) urethane (meth) acrylate compound is preferably 2000 to 45000. When the weight average molecular weight of the urethane (meth) acrylate compound is 2000 or more, the stickiness of the photosensitive resin composition tends to be further reduced, and when it is 45000 or less, the alkali developability is further improved and a resist residue is generated. The resolution tends to be improved.

The (D) urethane (meth) acrylate compound preferably has two ethylenically unsaturated groups. Thereby, the elasticity modulus of the film after hardening becomes low, and the blast tolerance of a resist pattern improves more.

The present invention also provides a photosensitive element comprising a support and a photosensitive layer formed on the support using the photosensitive resin composition.
According to such a photosensitive element, since the photosensitive layer formed using the photosensitive resin composition is provided, the stickiness of the photosensitive layer is small, and the support can be easily peeled from the photosensitive layer. Furthermore, according to the photosensitive element, a photosensitive layer having a uniform thickness can be obtained.

The present invention also provides a photosensitive layer forming step in which a photosensitive layer is formed on the object to be processed using the photosensitive resin composition, and an actinic ray is applied to the photosensitive layer to form a photocured portion at a predetermined location. An exposure step to perform, a development step to remove a portion other than the photocured portion to form a resist pattern, a sand blast treatment step to cut a portion of the object to be processed where the resist pattern is not formed by spraying an abrasive, The surface processing method of the to-be-processed object containing is provided.

Moreover, this invention provides the mask material for sandblast formed using the said photosensitive resin composition.
The photosensitive resin composition can form a good pattern on a substrate such as a glass substrate, and the formed resist pattern has good blast resistance. be able to. Moreover, the said photosensitive resin composition can be applied suitably for manufacture of the mask material for sandblasting.

According to the present invention, the support can be easily peeled from the photosensitive layer, exhibits good adhesion on a substrate such as a glass substrate, a silicon wafer, or a ceramic substrate, and forms a good pattern. And a photosensitive resin composition suitable for sand blasting, in which the resist pattern to be formed has good blast resistance. Furthermore, according to this invention, the photosensitive element using this photosensitive resin composition, the mask material for sandblasting, and the surface processing method of a to-be-processed object can be provided.

It is a schematic cross section which shows suitable one Embodiment of a photosensitive element. (A), (b) and (c) is a schematic cross section which shows suitable one Embodiment of a sandblasting process and a peeling process. It is a model perspective view which shows suitable one Embodiment of the surface processing method of a to-be-processed object. It is a model perspective view which shows suitable one Embodiment of the surface processing method of a to-be-processed object. It is a model perspective view which shows suitable one Embodiment of the surface processing method of a to-be-processed object. It is a model perspective view which shows suitable one Embodiment of the surface processing method of a to-be-processed object.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as occasion demands, but the present invention is not limited to the following embodiments. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. In the present specification, “˜” indicates a range including the numerical values described before and after the values as the minimum value and the maximum value, respectively. In the present specification, “(meth) acrylate” means at least one of “acrylate” and “methacrylate” corresponding thereto. The same applies to other similar expressions such as “(meth) acrylic acid”. In addition, in this specification, the term “step” not only means an independent step, but even if it cannot be clearly distinguished from other steps, the intended action of the step can be achieved. Included in this term. In this specification, the term “layer” includes not only a structure having a shape formed on the entire surface but also a structure having a shape formed on a part when observed as a plan view.

(Photosensitive resin composition)
The photosensitive resin composition of the present embodiment comprises (A) a binder polymer having a carboxyl group (hereinafter sometimes referred to as “component (A)”) and (B) a photopolymerizable monofunctional group having an ethylenically unsaturated group. A compound (hereinafter sometimes referred to as “component (B)”), (C) a photopolymerizable polyfunctional compound having an ethylenically unsaturated group (hereinafter sometimes referred to as “component (C)”), ( D) a urethane (meth) acrylate compound (hereinafter sometimes referred to as “component (D)”) and (E) a photopolymerization initiator (hereinafter sometimes referred to as “component (E)”). .

Hereinafter, each component contained in the photosensitive resin composition according to the present embodiment will be described.

<(A) component: binder polymer having a carboxyl group>
Examples of the component (A) include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, urethane resins, and cellulose derivatives having a carboxyl group. The component (A) preferably contains an acrylic resin having a carboxyl group or a cellulose derivative having a carboxyl group in terms of excellent alkali developability. These can be used alone or in combination of two or more.

Examples of the cellulose derivative having a carboxyl group include cellulose acetate phthalate, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose acetate phthalate, and hydroxypropylmethylcellulose acetate succinate.

Examples of the acrylic resin having a carboxyl group include acrylic resins containing (meth) acrylic acid and alkyl (meth) acrylate as monomer units. In such an acrylic resin, a carboxyl group can be introduced by using (meth) acrylic acid as a monomer unit.

Examples of alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth) acrylic. Examples include hexyl acid, heptyl (meth) acrylate, octyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. These can be used alone or in combination of two or more.

The acrylic resin having a carboxyl group is a copolymer using a monomer component (polymerizable monomer) having another ethylenically unsaturated group in addition to (meth) acrylic acid and alkyl (meth) acrylate as a monomer component. It may be a polymer. Examples of other polymerizable monomers include (meth) acrylic such as tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and glycidyl (meth) acrylate. Acid esters; maleic monomers such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate; N-vinylcaprolactam; N-vinylpyrrolidone; styrene; vinyltoluene, p- Examples thereof include styrene derivatives such as methylstyrene, p-ethylstyrene, p-chlorostyrene, and α-methylstyrene. These can be used alone or in combination of two or more.

When the component (A) is an acrylic resin having a carboxyl group, the acid value of the component (A) is preferably 50 to 250 mgKOH / g, and preferably 70 to 230 mgKOH / g from the viewpoint of improving alkali developability. More preferably, it is more preferably 100 to 200 mgKOH / g.

Here, the acid value can be measured as follows. First, after precisely weighing 1 g of a solution containing a resin whose acid value is to be measured, 30 g of acetone is added to this resin solution to dissolve it. Next, an appropriate amount of phenolphthalein as an indicator is added to the solution, and titration is performed using a 0.1N aqueous KOH solution. Then, the acid value is calculated by the following formula (α).

A = 10 × Vf × 56.1 / (Wp × I) (α)
In the formula (α), A represents the acid value (mgKOH / g), Vf represents the titration amount (mL) of a 0.1N KOH aqueous solution, Wp represents the mass (g) of the measured resin solution, and I Indicates the ratio (mass%) of the non-volatile content in the measured resin solution.

The weight average molecular weight (Mw) of the component (A) is preferably 20000 to 150,000, more preferably 30000 to 120,000, from the viewpoint of reducing stickiness of the photosensitive resin composition and improving alkali developability. It is preferably 40,000 to 100,000. In addition, a weight average molecular weight (Mw) can be measured by performing conversion by standard polystyrene using gel permeation chromatography (GPC).

The content of the component (A) in the photosensitive resin composition is preferably 20 to 60% by mass, and preferably 30 to 50% by mass, based on the total solid content of the photosensitive resin composition. More preferred. When the component (A) is 20% by mass or more, the stickiness of the photosensitive resin composition tends to be further reduced, and when it is 60% by mass or less, a resist pattern formed using the photosensitive resin composition. There is a tendency for the blast resistance of to improve more.

<(B) component: Photopolymerizable monofunctional compound having an ethylenically unsaturated group>
(B) A component contains the (meth) acrylate compound represented by the following general formula (1) or the following general formula (2).

In formula (1), in R ² , the alkylene group having one or more hydroxyl groups is a hydrogen atom in an alkylene group represented by the general formula — (CH ₂ ) n— (n is an integer of 2 to 10). Examples include groups in which one or more of these groups are substituted with hydroxyl groups. Examples of the alkylene group include an ethylene group, a trimethylene group, and a tetramethylene group. N in the general formula is preferably 3-7. The number of hydroxyl groups is preferably 1 or 2. Examples of the polyoxyalkylene group having a hydroxyl group in R ² include groups in which one or more hydrogen atoms in the polyoxyalkylene group in which the above-described alkylene group is bonded by an ether bond are substituted with a hydroxyl group. The Incidentally, R ² is, if a polyoxyalkylene group having a hydroxyl group at both ends of R ² is a carbon atom.

In formula (1), in R ³ , examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, which are alkyl groups having 1 to 20 carbon atoms. In R ³ , examples of the aryl group include a phenyl group and a naphthyl group, which are aryl groups having 6 to 10 carbon atoms.

In formula (2), as R ⁵ , an alkylene group having one or more hydroxyl groups and a polyoxyalkylene group having one or more hydroxyl groups may be represented by the general formula — (CH ₂ ) n— (n is 2 to ₂ ). And a group in which one or more hydrogen atoms in the alkylene group represented by (integer of 10) are substituted with a hydroxyl group. Examples of the alkylene group include an ethylene group, a trimethylene group, and a tetramethylene group. When R ⁵ is an alkylene group having one or more hydroxyl groups, n in the general formula is preferably 2-7. When R ⁵ is a polyoxyalkylene group having one or more hydroxyl groups, n in the general formula is preferably 3-7. The number of hydroxyl groups is preferably 1 or 2. Examples of the polyoxyalkylene group having a hydroxyl group in R ² include groups in which one or more hydrogen atoms in the polyoxyalkylene group in which the above-described alkylene group is bonded by an ether bond are substituted with a hydroxyl group. The

Specific examples of the compound represented by the formula (1) include 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, and glycerin di (meth) acrylate. Etc. Specific examples of the compound represented by the formula (2) include 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and the like. Among these, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 2-hydroxy-3-propyl (meth) acrylate or 2-hydroxybutyl (meth) acrylate is preferable.

Examples of the photopolymerizable monofunctional compound having an ethylenically unsaturated group include KAYARAD R-128H (2-hydroxy-3-phenoxypropyl acrylate, trade name, manufactured by Nippon Kayaku Co., Ltd.), Aronix M-5700 ( 2-hydroxy-3-phenoxypropyl acrylate, manufactured by Toagosei Co., Ltd., trade name), light ester HOP (N) (2-hydroxypropyl methacrylate, manufactured by Kyoei Chemical Co., Ltd., trade name), light ester HOB (N) ( It is commercially available as 2-hydroxybutyl methacrylate, Kyoei Chemical Co., Ltd., trade name).

(B) As a component, the photopolymerizable monofunctional compound which has other ethylenically unsaturated groups other than the (meth) acrylate compound represented by the said general formula (1) or the following general formula (2) is included. Also good.

The content of the component (B) is preferably 3 to 20% by mass, more preferably 3 to 15% by mass based on the total solid content of the photosensitive resin composition. (B) When the content of the photopolymerizable monofunctional compound having an ethylenically unsaturated group is 3% by mass or more based on the total solid content of the photosensitive resin composition, the adhesion to various substrates is improved. If it is less than mass%, fluidization is suppressed and the stickiness of the photosensitive resin composition tends to be weakened.

<(C) Component: Photopolymerizable polyfunctional compound having an ethylenically unsaturated group>
Examples of the component (C) include compounds obtained by reacting polyhydric alcohols with α, β-unsaturated carboxylic acids, bisphenol A (meth) acrylate compounds, trimethylolpropane tri (meth) acrylate, ethylene oxide ( EO) modified trimethylolpropane tri (meth) acrylate, propylene oxide (PO) modified trimethylolpropane tri (meth) acrylate, ethylene oxide and propylene oxide modified trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate , Tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, represented by the following general formula (3) Compound etc. are mentioned. (C) A component removes (D) urethane (meth) acrylate mentioned later among photopolymerizable polyfunctional compounds which have an ethylenically unsaturated group.

[In General Formula (3), R ⁷ represents an acryloyl group or a methacryloyl group. R ⁸ represents an alkylene group having a hydroxyl group or a polyoxyalkylene group having a hydroxyl group. R ⁹ represents an acryloyl group or a methacryloyl group. ]

In formula (3), as R ⁸ , examples of the alkylene group having one or more hydroxyl groups and the polyoxyalkylene group having a hydroxyl group include the same groups as those in R ² in general formula (1).

Examples of bisphenol A-based (meth) acrylate compounds include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolypropoxy). ) Phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, etc. Can be mentioned.

Examples of 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2- Examples thereof include bis (4-((meth) acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, and the like.

Among the above-mentioned compounds, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is, for example, BPE-500 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) or FA-321M (Hitachi Chemical Co., Ltd.). 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is commercially available as, for example, BPE-1300NH (manufactured by Shin-Nakamura Chemical Co., Ltd., product) Name).

The content of component (C) is preferably 10 to 40% by mass, more preferably 15 to 20% by mass based on the total solid content of the photosensitive resin composition. When the component (C) is 10% by mass or more, pattern formation becomes easier, and when it is 40% by mass or less, the stickiness of the photosensitive resin composition tends to be further reduced.

<(D) component: urethane (meth) acrylate compound>
As a urethane (meth) acrylate compound, for example, a reaction product of a compound having a terminal isocyanate group obtained by reacting a diol compound and a diisocyanate compound and a (meth) acrylate compound having a hydroxyl group can be used.

Examples of the diol compound include polyesters having a hydroxyl group at the terminal, polyethers, polycarbonates, and the like. Examples of polyesters are obtained by condensation reaction of alkylene glycol such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and dipropylene glycol with dicarboxylic acid such as maleic acid, fumaric acid, glutaric acid, and adipic acid. And polyesters obtained by ring-opening polymerization of lactones.

Examples of the lactones include δ-valerolactone, ε-caprolactone, β-propiolactone, α-methyl-β-propiolactone, β-methyl-β-propiolactone, α, α-dimethyl-β. -Propiolactone, β, β-dimethyl-β-propiolactone and the like.

Examples of the polycarbonates include reaction products of diols such as bisphenol A, hydroquinone, and dihydroxycyclohexanone with carbonyl compounds such as diphenyl carbonate, phosgene, and succinic anhydride. Examples of the polyethers include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polypentamethylene glycol.

Examples of the diisocyanate compound include dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, 2,2-dimethylpentane-1,5-diisocyanate, octamethylene diisocyanate, 2 , 5-dimethylhexane-1,6-diisocyanate, 2,2,4-trimethylpentane-1,5-diisocyanate, nanomethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, isophorone diisocyanate And an aliphatic or alicyclic diisocyanate compound. These can be used alone or in combination of two or more.

Examples of the (meth) acrylate compound having a hydroxyl group include hydroxymethyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, and the like. These can be used alone or in combination of two or more.

In addition, the urethane (meth) acrylate compound is obtained by adding an alkyl (meth) acrylate to a reaction product of a compound having a terminal isocyanate group obtained by reacting a diol compound and a diisocyanate compound and a (meth) acrylate compound having a hydroxyl group. It may be reacted.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.

The weight average molecular weight of the urethane (meth) acrylate compound is preferably 2000 to 45000, more preferably 5000 to 43000, and still more preferably 10,000 to 40000.

The glass transition point after curing of the urethane (meth) acrylate compound is preferably 50 ° C. or lower.

The urethane (meth) acrylate compound preferably has two ethylenically unsaturated groups. The ethylenically unsaturated group can be derived from, for example, the (meth) acrylate compound having a hydroxyl group.

Examples of the urethane (meth) acrylate compound include “KAYARAD UX-3204”, “KAYARAD UXF-4001-M35”, “KAYARAD UXF-4002” (trade name, manufactured by Nippon Kayaku Co., Ltd.), “Suriko UV- 3000B "(trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).

The content of the urethane (meth) acrylate compound is preferably 15 to 60% by mass, more preferably 30 to 50% by mass based on the total solid content of the photosensitive resin composition.

<(E) component: Photopolymerization initiator>
Examples of the photopolymerization initiator that is component (E) include anthraquinone derivatives such as 2-methylanthraquinone, benzophenone derivatives such as 3,3-dimethyl-4-methoxy-benzophenone, and 4,4′-bis (diethylamino) benzophenone. 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer Imidazole derivatives such as isomers, acetophenone derivatives such as 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, and benzoins such as benzoinpropyl ether Alkyl ether derivatives, thioxanthone derivatives such as diethyl thioxanthone, Larsketone, 9-phenylacridine, dimethylbenzyl ketal, trimethylbenzoyldiphenylphosphine oxide, tribromomethylphenylsulfone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2, Examples include 4,6-trimethylbenzoyl diphenylphosphine oxide. These can be used alone or in combination of two or more.

The content of the component (E) is preferably 0.1 to 10% by mass and preferably 0.2 to 5% by mass based on the total solid content of the photosensitive resin composition from the viewpoint of photosensitivity. It is more preferable.

<(F) component: Silane compound>
Examples of the silane compound as the component (F) include a silane compound having a mercapto group, ureido group, vinyl group, allyl group, styryl group, amino group, sulfide group, isocyanate group, epoxy group, (meth) acryloyl group, and the like. Can be used. Among these, from the point of improving the adhesion with the base material and suppressing the elastic modulus of the cured product and improving the blast resistance, a mercapto group, a ureido group, a vinyl group, an allyl group, a styryl group, an amino group, It is preferable to use a silane compound having a sulfide group or an isocyanate group. From the viewpoint of further improving the adhesion to the substrate, it is more preferable to use a mercapto group.

As the silane compound having a mercapto group, a compound represented by the following general formula (I) is preferably used.

In general formula (I), R represents an alkylene group having 1 to 6 carbon atoms. Specific examples thereof include a propylene group. A represents an alkyl group. Specific examples thereof include a methyl group and an ethyl group. B represents an alkoxy group, a chloro group, an alkoxyalkoxy group, an acetoxy group or an alkenyloxy group. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the alkoxyalkoxy group include a methoxyethoxy group. Examples of the alkenyloxy group include an isopropenoxy group. N represents an integer of 0 to 2, and is preferably 0 or 1 from the viewpoint of adhesion to the substrate.

As the component (F), a silane compound having a mercaptoalkyl group and an alkoxy group (mercaptoalkylalkoxysilane) is preferable. Examples of such component (F) include mercaptopropylmethyldimethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, and the like. Among these, mercaptopropyltrimethoxysilane which is easily hydrolyzed and can be cross-linked at three points is preferable from the viewpoint of improving the adhesion to the substrate.

The silane compound having a mercapto group is commercially available, and examples thereof include Z-6062, Z-6862, Z-6911 (trade name, manufactured by Toray Dow Corning Co., Ltd.) and the like. These can be used alone or in combination of two or more.

As the silane compound having a ureido group, for example, 3-ureidopropyltriethoxysilane can be used.

The content of (F) silane compound is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total solid content of the photosensitive resin composition, The content is more preferably 1 to 3% by mass, and particularly preferably 0.3 to 3% by mass.

(F) When the content rate of a silane compound is 0.01 mass% or more on the basis of the solid content whole quantity of the photosensitive resin composition, adhesiveness with a base material will improve more and it can form a more favorable pattern. Tend. On the other hand, when the content is 10% by mass or less, there is a tendency that resist residues are not easily generated during alkali development. Even when a silane compound having a mercapto group is used as the component (F), the content is preferably in the same range as the above content.

In addition, the photosensitive resin composition according to the present embodiment includes a dye such as malachite green, a photochromic agent such as leuco crystal violet, a thermochromic inhibitor, a plasticizer such as p-toluenesulfonamide, if necessary. Phthalocyanine-based organic pigments such as phthalocyanine blue, azo-based organic pigments, inorganic pigments such as titanium dioxide, silica, alumina, talc, calcium carbonate, barium sulfate and other fillers (excluding the aforementioned inorganic pigments), antifoaming agents, and stability Agents, adhesion-imparting agents, leveling agents, antioxidants, fragrances, imaging agents and the like. When these components are contained, it is preferably contained in an amount of about 0.01 to 20% by mass based on the total solid content of the photosensitive resin composition. Moreover, said component can be used individually by 1 type or in combination of 2 or more types.

Furthermore, the photosensitive resin composition according to the present embodiment may contain a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether as necessary. It can be dissolved in these mixed solvents and used as a solution having a solid content of about 30 to 70% by mass.

The photosensitive resin composition according to the present embodiment can form a good pattern on a substrate such as a glass substrate, a silicon wafer, a ceramic substrate, and the like, and a resist pattern formed using the photosensitive resin composition Can be suitably used as a mask material for sand blasting. Moreover, the photosensitive resin composition which concerns on this embodiment can also be used with the form of the photosensitive element obtained by forming a photosensitive layer on a support body.

(Photosensitive element)
Next, the photosensitive element using the photosensitive resin composition which concerns on this embodiment mentioned above is demonstrated. FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of a photosensitive element according to this embodiment. The photosensitive element 1 shown in FIG. 1 includes a support 10 and a photosensitive layer 14 provided on the support 10. The photosensitive layer 14 is a layer formed using the photosensitive resin composition according to this embodiment described above. Moreover, the photosensitive element 1 which concerns on this embodiment may coat | cover the surface F1 on the opposite side to the surface which touches the support body 10 on the photosensitive layer 14 with a protective film.

The photosensitive layer 14 can be formed by applying a solution of the above-described photosensitive resin composition onto the support 10 and drying it. The application can be performed by a known method using, for example, a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, a bar coater or the like. The drying can be performed by heating and / or spraying with hot air at 70 to 150 ° C. for about 5 to 30 minutes.

The thickness of the photosensitive layer 14 varies depending on the use, but the thickness after drying is preferably 10 to 120 μm, more preferably 20 to 100 μm. When the thickness is within the above range, it tends to be industrially easy to apply. When the thickness is 10 μm or more, the resist pattern tends to have better blast resistance, and when it is 120 μm or less, the resolution tends to be further improved.

Examples of the support 10 provided in the photosensitive element 1 include heat-resistant and solvent-resistant polymer films such as polyethylene terephthalate, polypropylene, polyethylene, and polyester.

The thickness of the support 10 is preferably 5 to 100 μm, and more preferably 10 to 30 μm. When the thickness is 5 μm or more, the support tends to be hardly broken when the support is peeled before development, and when the thickness is 100 μm or less, the resolution tends to be further improved.

The photosensitive element 1 composed of two layers of the support 10 and the photosensitive layer 14 as described above or the photosensitive element composed of three layers of the support 10, the photosensitive layer 14 and the protective film can be stored as it is, for example. Alternatively, the protective film may be interposed and wound around the core in a roll shape and stored.

(Surface processing method of workpiece)
The surface processing method of the to-be-processed object which concerns on this embodiment is a photosensitive layer formation process which forms a photosensitive layer on the to-be-processed object using the above-mentioned photosensitive resin composition, and actinic rays are irradiated to the said photosensitive layer. An exposure step for forming a photocured portion at a predetermined location, a development step for removing a portion other than the photocured portion by development to form a resist pattern, and a portion where a resist pattern is not formed by spraying an abrasive. And a sandblasting process for cutting the object to be processed. Moreover, the surface processing method of the to-be-processed object which concerns on this embodiment may include the peeling process of removing a resist pattern from a cut to-be-processed object using a peeling liquid after a sandblasting process.

In the photosensitive layer forming step, the photosensitive layer can be formed by laminating the above-described photosensitive elements on the substrate in the order of the photosensitive layer and the support from the substrate side. In addition, before the said lamination | stacking, a protective film can also be removed from the photosensitive element mentioned above as needed.

Examples of the laminating method include a method of laminating by pressing the photosensitive layer on the substrate while heating.

The heating temperature of the photosensitive layer at the time of the above lamination is preferably 70 to 130 ° C., and the pressing pressure is preferably about 0.1 to 1.0 MPa, but these conditions are not particularly limited. In addition, if the photosensitive layer is heated to 70 to 130 ° C. as described above, it is not necessary to pre-heat the base material in advance. However, in order to further improve the lamination property, the base material may be pre-heated. it can.

In the photosensitive layer forming step, the photosensitive layer may be formed by directly applying the above-described photosensitive resin composition onto a target object and drying it.

After forming the photosensitive layer in this way, a photocured portion is formed by irradiating a predetermined portion of the photosensitive layer with actinic rays in the exposure step. Examples of the method for forming the photocured portion include a method of irradiating actinic rays in an image form through a negative mask pattern called an artwork. At this time, when the support on the photosensitive layer is transparent, it can be irradiated with actinic rays as it is, but when it is opaque, it is irradiated with actinic rays after removing the support.

As the actinic ray light source, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp can be used. Moreover, what can radiate | emit visible light effectively, such as a flood bulb for photography, a solar lamp, can also be used.

Next, after the exposure, when a support is present on the photosensitive layer, after removing the support, in the development process, the photosensitive layer other than the photocured portion is removed by wet development, dry development, etc. A pattern is formed.

In the case of wet development, development is performed by a known method such as spraying, rocking immersion, brushing, scraping, or the like, using a developer such as an alkaline aqueous solution. As the developer, a developer that is safe and stable and has good operability is used. For example, a dilute solution of sodium carbonate (1 to 5% by mass aqueous solution) at 20 to 50 ° C. is used.

In the sandblasting process, the obtained resist pattern is used as a mask material, and an abrasive is sprayed to cut a portion of the object to be processed on which the resist pattern is not formed. As a polishing agent (blasting material) used for sandblasting, various known ones are used. For example, fine particles of about 2 to 100 μm such as glass beads, SiC, SiO ₂ , Al ₂ O ₃ , and ZrO are used. As a to-be-processed object, base materials, such as a glass substrate, a silicon wafer, and a ceramic substrate, are mentioned, for example. The thickness of the object to be processed can be adjusted as appropriate depending on the material of the object to be processed and the like, and can be, for example, 0.01 mm to 10 mm.

After cutting the object to be processed with an abrasive, a peeling process is performed to remove the resist pattern from the object to be processed using a peeling solution. Examples of the stripping solution used in the stripping step include aqueous alkali solutions such as a sodium hydroxide aqueous solution and a potassium hydroxide aqueous solution. The resist pattern according to the present embodiment is difficult to peel off from the object to be processed at the time of development, and can be easily peeled off from the object to be processed by the alkali treatment in the peeling process. In addition, a resist pattern can also be removed by providing the process of burning off a resist pattern at high temperature instead of a peeling process.

FIG. 2 is a schematic cross-sectional view showing a preferred embodiment of a sandblasting process and a peeling process. First, in the sand blasting process, the abrasive 18 is sprayed onto the object 16 through the resist pattern 19 to cut the portion of the object 16 where the resist pattern 19 is not formed (FIG. 2 (a)). The to-be-processed object 20 separated into pieces is obtained (FIG.2 (b)). Furthermore, the resist pattern 19 on the to-be-processed object 20 separated by the peeling process is peeled off (FIG. 2C).

As an example of the surface processing method of the object to be processed according to the present embodiment, an example in which the photosensitive resin composition described above is used as a mask material for sandblasting for separating a large glass into a cover glass is shown in FIGS. 6 will be described. 3 to 6 are schematic perspective views showing a process of dividing a large glass into a cover glass.

First, as shown in FIG. 3, a photosensitive layer 21 according to this embodiment is provided on a large glass (object to be processed) 22 (photosensitive layer forming step). Next, exposure and development are performed on the photosensitive layer provided on the large format glass 22 to form a resist pattern 24 having a desired shape as shown in FIG. 4 (exposure process and development process). Then, sand blasting is performed using the resist pattern 24 as a mask material, and the non-mask portion is cut to obtain a cover glass 26 in which the large glass 22 is separated into pieces as shown in FIG. 5 (sand blasting process). Finally, as shown in FIG. 6, the outer edge of each cover glass 26 is mechanically polished to smooth the cut surface. Such a processing method can be suitably used particularly for manufacturing a cover glass for a smartphone.

Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.

(Examples 1 to 8, Comparative Examples 1 to 4)
First, by blending 30 parts by mass of methyl ethyl ketone and the following components at the mass ratio shown in Table 1 (however, when the component is blended as a solution, the mass ratio in terms of solid content), A solution containing a functional resin composition was obtained.

(A) -1: Toluene / methyl cellosolve (mass ratio = 2/3) of acrylic resin obtained by copolymerization of methacrylic acid / ethyl acrylate / methyl methacrylate / styrene (mass ratio: 26/20/34/20) ) A solution (weight average molecular weight: 50000, solid content acid value: 170 mgKOH / g, solid content: 43% by mass) obtained by polymerization in a conventional manner.
In addition, the weight average molecular weight in this invention can be obtained by measuring with the gel permeation chromatography method and converting with the analytical curve produced using standard polystyrene. The measurement conditions in GPC are as follows.
Column: Gelpack GL-R440 + GL-R450 + GL-R400M (three in total, manufactured by Hitachi Chemical Co., Ltd., trade name)
Flow rate: 2.05 mL / min
Concentration: 120 mg / 5 mL
Injection volume: 200 μL
Eluent: THF
(B) -1: 2-hydroxy-3-phenyloxypropyl acrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: “KAYARAD R-128H”)
(B) -2: Nonylphenoxy polyethylene glycol acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name: “FA-314A”)
(B) -3: Nonylphenoxypolyethylene glycol acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name: “FA-318A”)
(B) -4: γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate (trade name: MECHPP, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
(B) -5: 2-hydroxypropyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: light ester HOP (N))
(B) -6: 2-hydroxybutyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: light ester HOB (N))
(C) -1: 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (manufactured by Hitachi Chemical Co., Ltd., trade name: “FA-321M”)
(C) -2: 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “BPE-1300NH”)
(D) -1: Urethane acrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD UX-3204”) weight average molecular weight: 13000, number of ethylenically unsaturated groups: 2, glass transition point after curing at −14 ° C.
(D) -2: Urethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “purple UV-3000B”) weight average molecular weight: 18000, number of ethylenically unsaturated groups: 2, glass transition point after curing −39 ℃
In addition, the glass transition point after hardening can be measured with the following method. 100 g of urethane (meth) acrylate compound and 4 g of Irgacure 184 (trade name, manufactured by BASF) as a photopolymerization initiator are mixed, and a coating film is prepared so that the thickness becomes 100 μm. After exposure at 500 mJ / cm ² , TMA The glass transition point was measured by the method.
(E) -1: 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole (E) -2: 4,4′-bis (Diethylamino) benzophenone (F) -1: 3-mercaptopropyltrimethoxysilane (trade name “Z-6062” manufactured by Toray Dow Corning Co., Ltd.)
(F) -2: 3-Ureidopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBE-585”)
(X) -1: leuco crystal violet

Note) The symbol “-” in Table 1 indicates that the relevant component is not contained.

[Production of photosensitive element]
The obtained solution containing the photosensitive resin composition was separately applied on a 16 μm-thick polyethylene terephthalate film (trade name “G2-16”, manufactured by Teijin Limited) as a support so that the thickness was uniform. As a result, a photosensitive layer was formed. The obtained photosensitive layer was dried at 100 ° C. for 10 minutes using a hot air convection dryer. The thickness of the photosensitive layer after drying was 50 μm.

Next, a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name “NF-13”) is bonded as a protective film on the surface of the photosensitive layer opposite to the surface in contact with the support to obtain a photosensitive element. It was.

[Preparation of evaluation laminate]
Next, using a manual laminator (manufactured by Hitachi Chemical Co., Ltd., trade name “HLM-3000”), photosensitivity was performed under conditions of a roll temperature of 110 ° C., a laminating speed of 1.0 m / min, and a roll pressure of 0.4 MPa. While peeling the polyethylene film of the conductive element, the photosensitive layer was pressure-bonded onto the glass substrate heated at 80 ° C. for 10 minutes to obtain a laminate for evaluation.

[Evaluation of light sensitivity]
A phototool having a stove 21-step tablet as a negative was brought into close contact with the obtained laminate for evaluation, and an EXM-1201 type exposure machine manufactured by Oak Manufacturing Co., Ltd. was used. Exposure was performed with an energy amount such that the number of steps remaining after development was 8.0 to form a photocured portion.

Next, after the polyethylene terephthalate film was peeled off, the photosensitive layer was developed by spraying a 1.0% by mass aqueous sodium carbonate solution for 40 seconds under the conditions of a liquid temperature of 30 ° C. and a spray pressure of 0.16 MPa. The value of the energy amount at the time of exposure was evaluated as photosensitivity. The lower this value, the higher the photosensitivity. The results are shown in Table 2.

[Resolution evaluation]
Lamination for evaluation: Photo tool with stove 21-step tablet and photo tool with wiring pattern with line width / space width of 30/30 to 200/200 (unit: μm) in 10 μm increments as negative for resolution evaluation Using a light exposure unit as described above, the photocured portion was formed by performing exposure with an energy amount such that the number of remaining steps after development of the stove 21-step tablet was 8.0.

Next, after the polyethylene terephthalate film was peeled off, development was carried out by spraying the photosensitive layer with a 1.0 mass% sodium carbonate aqueous solution for 40 seconds under the conditions of a liquid temperature of 30 ° C. and a spray pressure of 0.16 MPa. Here, the smallest value (unit: μm) of the space width between the line widths in which a rectangular resist shape was obtained by development processing was evaluated as the resolution. It shows that it is excellent in the resolution, so that this value is small. The results are shown in Table 2.

[Evaluation of tackiness]
The polyethylene terephthalate film on the laminate was peeled off from the evaluation laminate without exposure, and the ease of peeling was evaluated according to the following criteria. The results are shown in Table 2.
“A”: A polyethylene terephthalate film that can be easily peeled off from the photosensitive layer.
“B”: The polyethylene terephthalate film and the photosensitive layer have a slightly strong adhesion but can be peeled off.
“C”: Strong adhesion between the polyethylene terephthalate film and the photosensitive layer, making it difficult to peel.

[Evaluation of glass adhesion]
Using the EXM-1201 type exposure machine manufactured by Oak Manufacturing Co., Ltd., the entire surface of the evaluation laminate was exposed with an energy amount such that the number of remaining steps after development of the stove 21-step tablet was 8.0. A photocured part was formed. Thereafter, a cross-cut test according to JIS-K5400 was performed, and the difficulty of peeling the photocured portion from the glass substrate was evaluated according to the following criteria. The results are shown in Table 2.
“A”: No photocured part peeled off.
“B”: 10 to 50% peeling of the photocured portion is observed.
“C”: A photocured portion almost completely peeled off.

[Evaluation of blast resistance]
A phototool having a stove 21-step tablet and a phototool having a wiring pattern with a line width / space width of 300/300 (unit: μm) as an evaluation negative were brought into close contact with each other on the evaluation laminate. Using an exposure machine, exposure was performed with an energy amount such that the number of remaining step stages after development of the stove 21-step step tablet was 8.0 to form a photocured portion.

Next, after the polyethylene terephthalate film was peeled off, development was carried out by spraying the photosensitive layer with a 1.0 mass% sodium carbonate aqueous solution for 40 seconds under the conditions of a liquid temperature of 30 ° C. and a spray pressure of 0.16 MPa.

Next, sand blasting equipment (trade name “ELP-5TR”, manufactured by Elfotec Co., Ltd.), SiC (silicon carbide) # 800 as an abrasive, blast pressure: 0.15 MPa, nozzle movement width: 300 mm, nozzle movement speed : 8 m / min Conveyor speed: 15 mm / min. The resist pattern after development was sandblasted 5 times. Here, blast resistance was evaluated according to the following criteria. The results are shown in Table 2.
“A”: The resist pattern was not chipped or peeled after sandblasting, and the line width change of the resist pattern after blasting was within 20% of the negative value.
“B”: The resist pattern was partially chipped or peeled after sandblasting, and the line width change of the resist pattern after blasting was more than 20% and 50% or less with respect to the negative value.
“C”: The resist pattern was chipped or peeled after sandblasting, and the line width change of the resist pattern after blasting exceeded 50% with respect to the negative value.

[Evaluation of peelability]
Using the EXM-1201 type exposure machine manufactured by Oak Manufacturing Co., Ltd., the entire surface of the evaluation laminate was exposed with an energy amount such that the number of remaining steps after development of the stove 21-step tablet was 8.0. A sample in which a photocured portion was formed was prepared. The obtained sample was cut into a 40 mm × 50 mm rectangle. Next, after peeling the polyethylene terephthalate film, the photosensitive layer was developed by spraying a 1.0 mass% aqueous sodium carbonate solution for 40 seconds under the conditions of a liquid temperature of 30 ° C. and a spray pressure of 0.16 MPa. The prepared sample was immersed in a 3.0 mass% NaOH aqueous solution at 50 ° C., and the peeling time for the photocured portion to peel from the glass substrate was measured and evaluated according to the following criteria. The results are shown in Table 2.
“A”: one that can be peeled in 1 minute or more and less than 3 minutes,
"B": A material that can be removed in 3 minutes or more and less than 5 minutes,
“C”: A material that can be peeled off in 5 minutes or more and less than 10 minutes.

As is clear from the results shown in Table 2, the comparative example is inferior in glass adhesion, peelability, and the like. In contrast to these comparative examples, according to the photosensitive resin compositions of Examples 1 to 6, sufficient photosensitivity and resolution can be obtained, and the support can be easily peeled off from the photosensitive layer. It was confirmed that the resist pattern formed using the photosensitive resin composition has excellent blast resistance. The resist pattern obtained using the photosensitive resin composition of the example was excellent in releasability from the glass substrate. Moreover, when the silane compound which has a mercapto group was used as a silane compound of (F) component, blast tolerance became more favorable.

DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 10 ... Support body, 14 ... Photosensitive layer, 16 ... To-be-processed object, 18 ... Polishing agent, 19 ... Resist pattern, 20 ... Divided object to be processed, 21 ... Photosensitive layer, 22 ... Large format glass (object to be processed), 24 ... resist pattern, 26 ... cover glass.

Claims

(A) a binder polymer having a carboxyl group,
(B) a photopolymerizable monofunctional compound having an ethylenically unsaturated group,
(C) a photopolymerizable polyfunctional compound having an ethylenically unsaturated group,
(D) contains a urethane (meth) acrylate compound and (E) a photopolymerization initiator,
The photosensitive resin composition in which the (B) component includes a (meth) acrylate compound represented by the following general formula (1) or a (meth) acrylate compound represented by the following general formula (2).

[In General Formula (1), R 1 represents an acryloyl group or a methacryloyl group. R 2 represents an alkylene group having a hydroxyl group or a polyoxyalkylene group having a hydroxyl group. R 3 represents an alkyl group or an aryl group. ]

[In General Formula (2), R 4 represents an acryloyl group or a methacryloyl group. R 5 represents an alkylene group having a hydroxyl group or a polyoxyalkylene group having a hydroxyl group. R 6 represents a methyl group. ]
The photosensitive resin composition according to claim 1, further comprising (F) a silane compound.
(F) The photosensitive resin composition of Claim 2 whose silane compound is a compound represented by the following general formula (I).

[In the general formula (I), R represents an alkylene group having 1 to 6 carbon atoms, A represents an alkyl group, B represents an alkoxy group, a chloro group, an alkoxyalkoxy group, an acetoxy group or an alkenyloxy group, and n Represents an integer of 0-2. ]
The content of the photopolymerizable monofunctional compound having (B) an ethylenically unsaturated group is 3 to 20% by mass based on the total solid content of the photosensitive resin composition. A photosensitive resin composition according to claim 1.
The photosensitive resin composition according to any one of claims 1 to 4, wherein the weight average molecular weight of the (D) urethane (meth) acrylate compound is 2000 to 45000.
The photosensitive resin composition according to any one of Claims 1 to 5, wherein the (D) urethane (meth) acrylate compound has two ethylenically unsaturated groups.
A photosensitive element comprising: a support; and a photosensitive layer formed on the support using the photosensitive resin composition according to any one of claims 1 to 6.
A photosensitive layer forming step of forming a photosensitive layer on the workpiece using the photosensitive resin composition according to any one of claims 1 to 6;
An exposure step of irradiating the photosensitive layer with actinic rays to form a photocured portion at a predetermined location; a developing step of removing a portion other than the photocured portion to form a resist pattern;
And a sandblasting step of cutting a portion of the object to be processed on which a resist pattern is not formed by spraying an abrasive.
A sandblast mask material formed using the photosensitive resin composition according to any one of claims 1 to 6.