JP7335757B2 - Photosensitive resin composition and etching method for glass substrate - Google Patents

Description

The present invention provides a photosensitive resin composition used for forming an etching mask on a glass substrate, and a method for etching a glass substrate comprising forming an etching mask on a glass substrate using the photosensitive resin composition. Regarding.

Glass substrates for displays, including glass substrates for touch panels, and glass substrates for package devices are often subjected to processing such as cutting and hole formation. Conventionally, physical methods have generally been used as such processing methods for glass substrates. However, the physical processing of glass substrates has problems that cracks are likely to occur in the glass substrates during processing, and that the strength of the glass substrates is reduced, resulting in a decrease in yield.

Therefore, in recent years, a chemical method has been proposed in which a glass substrate is etched using a resin pattern obtained by patterning a resist composition as a mask (see, for example, Patent Document 1). According to such a chemical method, cracks are less likely to occur in the glass substrate because no physical load is applied during processing.

In such a glass substrate etching method, it is easy to form an etching mask having high resistance to the etchant used for etching the glass substrate and excellent adhesion to the glass substrate. In addition, a patterned etching mask is often formed by curing a negative photosensitive composition containing a radically polymerizable compound or an epoxy compound by exposure.

JP-A-2008-076768

A glass substrate to be etched is often provided with metal wiring or provided with a resin layer made of a resin such as polyimide.
Further, as described in Patent Document 1, when forming a patterned etching mask using a negative photosensitive composition, an alkaline stripping solution is usually used when stripping the etching mask from the glass substrate. be done. However, when an alkaline stripping solution is used, the glass substrate itself, and the metal wiring and resin material attached to the glass substrate are likely to be damaged.

The present invention has been made in view of the above problems, and provides a photosensitive resin composition capable of forming an etching mask that has sufficient resistance to an etchant used for etching a glass substrate and that can be removed by an organic solvent-based remover. and a method for etching a glass substrate including forming an etching mask using the photosensitive resin composition.

The present inventors used a resin component (A) which has an acid-dissociable, dissolution-inhibiting group and increases alkali solubility under the action of an acid, and A photosensitive resin composition containing an acid generator (B) that generates a, a filler (C), and a plasticizer (D), or a resin component (A1) having a phenolic hydroxyl group and a phenolic hydroxyl group that reacts with By using a photosensitive resin composition containing a protective agent (A2) that provides an acid-dissociable, dissolution-inhibiting group, an acid generator (B), a filler (C), and a plasticizer (D), the above The present inventors have found that the problem can be solved and completed the present invention. More specifically, the present invention provides the following.

A first aspect of the present invention is
A resin component (A) having an acid-dissociable, dissolution-inhibiting group and increasing alkali solubility under the action of an acid, an acid generator (B) capable of generating an acid upon exposure to radiation, a filler (C), and a plasticizer. (D); or
A resin component (A1) having a phenolic hydroxyl group, a protective agent (A2) that reacts with the phenolic hydroxyl group to provide an acid-dissociable, dissolution-inhibiting group, an acid generator (B), a filler (C), and a plasticizer. and an agent (D),
The resin component (A) is a novolac resin or a polyhydroxystyrene resin in which at least part of the phenolic hydroxyl groups are protected with acid-dissociable, dissolution-inhibiting groups,
The resin component (A1) is a novolac resin or a polyhydroxystyrene resin in which at least a portion of the phenolic hydroxyl groups may be protected with an acid-dissociable, dissolution-inhibiting group,
A photosensitive resin composition used to form an etching mask on a glass substrate.

A second aspect of the present invention is
A coating film forming step of applying the photosensitive resin composition according to the first aspect to at least one main surface of a glass substrate to form a coating film on the main surface of the glass substrate;
an exposure step of position-selectively exposing the coating film;
an etching mask forming step of developing the exposed coating film with a developer to form an etching mask;
an etching step of etching a glass substrate provided with an etching mask;
a removing step of removing the etching mask;
A method for etching a glass substrate, comprising:

According to the present invention, a photosensitive resin composition having sufficient resistance to an etchant used for etching a glass substrate and capable of forming an etching mask that can be peeled off with an organic solvent-based stripping solution, and the photosensitive resin composition. and a method of etching a glass substrate comprising forming an etch mask using the method.

<<Photosensitive resin composition>>
A photosensitive resin composition is a composition used to form an etching mask on a glass substrate.
The photosensitive resin composition comprises a resin component (A) which has an acid-dissociable, dissolution-inhibiting group and increases alkali solubility under the action of an acid, an acid generator (B) which generates an acid when exposed to radiation, and a filler. (C) and a plasticizer (D), or
A resin component (A1) having a phenolic hydroxyl group, a protective agent (A2) that reacts with the phenolic hydroxyl group to provide an acid-dissociable, dissolution-inhibiting group, an acid generator (B), a filler (C), and a plasticizer. and an agent (D).
Hereinafter, the photosensitive resin composition containing the resin component (A), the acid generator (B), the filler (C), and the plasticizer (D) is referred to as a first photosensitive resin composition. .
Further, the resin component (A1) having the above phenolic hydroxyl group, the protective agent (A2) that provides an acid-dissociable, dissolution-inhibiting group by reacting with the phenolic hydroxyl group, the acid generator (B), and the filler (C ) and the plasticizer (D) is referred to as a second photosensitive resin composition.

<First photosensitive resin composition>
As described above, the first photosensitive resin composition contains the above resin component (A), acid generator (B), filler (C), and plasticizer (D). The essential or optional components of the first photosensitive resin composition are described below.

[Resin component (A)]
The resin component (A) is a novolak resin or polyhydroxystyrene resin in which at least part of the phenolic hydroxyl groups are protected with acid-dissociable, dissolution-inhibiting groups.
By using a resin derived from a novolac resin or a polyhydroxystyrene resin having an aromatic skeleton as the resin component (A), the etching mask formed using the first photosensitive resin composition can be formed using hydrofluoric acid. Excellent resistance to etchants such as aqueous solutions.

Since it is particularly easy to achieve both excellent resistance to the etchant of the etching mask and ease of peeling of the etching mask with an organic solvent, the resin component (A) is a novolak resin or a polyhydroxystyrene resin, and the formula (I) described later. It preferably contains a reactant with a divinyl ether compound represented by.
In the reaction product of the novolak resin or polyhydroxystyrene resin and the divinyl ether compound represented by formula (I) described later, the molecules of the novolak resin or polyhydroxystyrene resin are combined with the phenolic hydroxyl groups represented by formula (I). It is crosslinked with a divalent acid-dissociable, dissolution-inhibiting group by reaction with a divinyl ether compound.

The novolak resin protected by the acid-dissociable, dissolution-inhibiting group and the polyhydroxystyrene resin protected by the acid-dissociable, dissolution-inhibiting group are described below.

(novolac resin)
The novolac resin protected with an acid dissociable, dissolution inhibiting group is a novolak resin in which at least a portion of the phenolic hydroxyl groups is protected with an acid dissociable, dissolution inhibiting group. The novolak resin whose hydroxyl group is protected by the acid-dissociable, dissolution-inhibiting group is not particularly limited, and can be appropriately selected from well-known novolac resins.
For example, as a novolak resin protected by an acid-dissociable, dissolution-inhibiting group, a resin containing a structural unit having a phenolic hydroxyl group protected by an acid-dissociable, dissolution-inhibiting group represented by the following formula (a1) is used. be able to.

In formula (a1) above, R ^1a represents an acid dissociable, dissolution inhibiting group, and R ^2a and R ^3a each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Examples of the acid-dissociable, dissolution-inhibiting group represented by R ^1a include groups represented by the following formulas (a2) and (a3), linear, branched, or cyclic alkyl groups having 1 to 6 carbon atoms. is preferably a group, a vinyloxyethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.

In the above formulas (a2) and (a3), R ^4a and R ^5a each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to ⁶ carbon atoms; represents a linear, branched or cyclic alkyl group having 1 to 10 atoms, R ^7a represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; represents 0 or 1.

Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. . Moreover, a cyclopentyl group, a cyclohexyl group, etc. are mentioned as said cyclic alkyl group.

Here, specific examples of the acid dissociable, dissolution inhibiting group represented by the above formula (a2) include a methoxyethyl group, an ethoxyethyl group, an n-propoxyethyl group, an isopropoxyethyl group, an n-butoxyethyl group, isobutoxyethyl group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group and the like. Specific examples of the acid-dissociable, dissolution-inhibiting group represented by formula (a3) include a tert-butoxycarbonyl group and a tert-butoxycarbonylmethyl group. Examples of the trialkylsilyl group include groups having 1 to 6 carbon atoms in each alkyl group such as a trimethylsilyl group and a tri-tert-butyldimethylsilyl group.

As described above, the acid-dissociable, dissolution-inhibiting group represented by the formula (I) can be used as the acid-dissociable, dissolution-inhibiting group because it is particularly easy to achieve both excellent resistance to the etchant of the etching mask and ease of peeling of the etching mask with an organic solvent. A divalent acid-dissociable, dissolution-inhibiting group derived from a vinyl ether compound is preferred.

H ₂ C=CH—O—A ^a1 —O—CH=CH ₂ (I)
In formula (I), A ^a1 is an alkylene group having 1 to 10 carbon atoms which may have a substituent and may contain an ether bond in the main chain, or the following formula (II):
-(A ^a2 ) _na -A ^a3 -(A ^a2 ) _na - (II)
is a group represented by
In formula (II), A ^a2 is an optionally substituted alkylene group having 1 to 10 carbon atoms, A ^a3 is a cyclohexylene group, and na is 0 or 1.

When both ends of the divinyl ether compound represented by the formula (I) react with two of the phenolic hydroxyl groups possessed by the novolak resin, divalent acid dissociation derived from the divinyl ether compound represented by the formula (I) A dissolution-inhibiting group is generated.
The divalent acid-dissociable, dissolution-inhibiting group derived from the divinyl ether compound represented by formula (I) has the following formula (Ia):
—CH(CH ₃ )—OA ^a1 —O—CH(CH ₃ )— (Ia)
is a group represented by
Further, when only one end of the divinyl ether compound represented by formula (I) reacts with the phenolic hydroxyl group of the novolak resin, the following formula (Ib):
—CH(CH ₃ ) —OA ^a1 —O—CH=CH ₂ (Ib)
A monovalent acid-dissociable, dissolution-inhibiting group represented by is generated.
A ^a1 in formulas (Ia) and (Ib) is the same as A ^a1 in formula (I).

When A ^a1 in formula (I) is an alkylene group having 1 to 10 carbon atoms which may have a substituent and which may contain an ether bond in the main chain, the alkylene group has Suitable substituents include halogen atoms such as chlorine, bromine and fluorine atoms, and alkoxy groups such as methoxy and ethoxy groups.

The alkylene group as A ^a1 in formula (I) may contain an ether bond (--O--) in its chain.
When A ^a1 is an alkylene group which may have an ether bond in its main chain, the number of carbon atoms is 1 or more and 10 or less, preferably 1 or more and 8 or less, and more preferably 2 or more and 6 or less.
Preferred specific examples of the alkylene group optionally containing an ether bond in the main chain as A ^a1 include -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ -O-CH ₂ CH ₂ - , and —CH ₂ CH ₂ —O—CH ₂ CH ₂ —O—CH ₂ CH ₂ —.

A divalent group represented by the formula (II) is also preferred as A ^a1 . In formula (II), ^Aa3 is a cyclohexylene group. The cyclohexylene group may be a cyclohexane-1,4-diyl group, a cyclohexane-1,3-diyl group, or a cyclohexane-1,2-diyl group, preferably a cyclohexane-1,4-diyl group.
In formula (II), na is 0 or 1 independently.
In formula (II), ^Aa2 is an optionally substituted alkylene group having 1 to 10 carbon atoms. The number of carbon atoms in the alkylene group as A ^a2 is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, and still more preferably 1 or 2. Examples of substituents which the alkylene group as A ^a2 may have include halogen atoms such as chlorine, bromine and fluorine atoms, and alkoxy groups such as methoxy and ethoxy.
Preferred specific examples of ^Aa2 include a methylene group, an ethane-1,2-diyl group, an ethane-1,1,-diyl group, a propane-1,3-diyl group, and a butane-1,4-diyl group. etc.

A particularly preferred example of the divalent group represented by formula (II) is that two na are both 1, A ^a3 is a cyclohexane-1,4-diyl group, and two A ^a2 are both methylene groups. The group which is is mentioned.

Acid-dissociable, dissolution-inhibiting groups derived from the divinyl ether compound represented by the formula (I) represented by the above formula (Ia) and/or formula (Ib) for all the number of phenolic hydroxyl groups possessed by the novolak resin. The ratio of the number of protected hydroxyl groups (protection rate) is preferably in the range of 0.5% or more and 30% or less, more preferably 1% or more and 20% or less, from the viewpoint of the film properties of the etching mask. 2% or more and 10% or less is more preferable. The protection rate can be confirmed by proton NMR, for example.

[Polyhydroxystyrene resin]
The polyhydroxystyrene resin protected with acid-dissociable, dissolution-inhibiting groups is a polyhydroxystyrene resin in which at least part of the phenolic hydroxyl groups are protected with acid-dissociable, dissolution-inhibiting groups. The polyhydroxystyrene resin whose hydroxyl group is protected by the acid-dissociable, dissolution-inhibiting group is not particularly limited, and can be appropriately selected from well-known polyhydroxystyrene resins.
For example, the polyhydroxystyrene resin protected by an acid-dissociable, dissolution-inhibiting group includes a resin containing a structural unit having a phenolic hydroxyl group protected by an acid-dissociable, dissolution-inhibiting group represented by the following formula (a4). can be used.

In formula (a4) above, R ^8a represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ^9a represents an acid dissociable, dissolution inhibiting group.

The alkyl group having 1 to 6 carbon atoms is, for example, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Linear or branched alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. A cyclopentyl group, a cyclohexyl group, etc. are mentioned as a cyclic alkyl group.

As the acid dissociable, dissolution inhibiting group represented by ^R9a , the same acid dissociable, dissolution inhibiting groups as those exemplified in the above formulas (a2) and (a3) can be used.

Furthermore, the polyhydroxystyrene resin may contain constitutional units derived from other polymerizable compounds for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radically polymerizable compounds and anionically polymerizable compounds. Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethylsuccinic acid, 2- Methacrylic acid derivatives having a carboxyl group and an ester bond such as methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylic acid alkyl esters such as (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and other (meth) acrylic acid hydroxyalkyl esters; phenyl (meth) acrylate, (meth)acrylic acid aryl esters such as benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, vinyl group-containing aromatic compounds such as α-methylhydroxystyrene and α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide;

[Acid generator (B)]
The acid generator (B) is a compound that generates an acid upon exposure to radiation. The acid generator (B) is not particularly limited as long as it is a compound that directly or indirectly generates an acid upon exposure to light. As the acid generator (B), the first to fifth acid generators described below are preferred. The first to fifth acid generators are described below.

(First acid generator)
Examples of the first acid generator include compounds represented by the following formula (b1).

In formula (b1) above, X ^1b represents a sulfur atom or an iodine atom with a valence of g, where g is 1 or 2. h represents the number of repeating units of the structure in parentheses. R ^1b is an organic group bonded to X ^1b , and is an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, represents an alkenyl group having 2 to 30 carbon atoms or an alkynyl group having 2 to 30 carbon atoms, and R ^1b is alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthio at least one selected from the group consisting of carbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, and nitro groups, and halogen seeds may be substituted. The number of R ^1b is g+h(g−1)+1, and each R ^1b may be the same or different. Two or more R ^1b may be directly connected to each other, or -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^2b -, -CO-, -COO-, -CONH- , an alkylene group having 1 to 3 carbon atoms, or a phenylene group to form a ring structure containing X ^1b . ^R2b is an alkyl group having 1 to 5 carbon atoms or 5 or more carbon atoms or an aryl group having 6 to 10 carbon atoms.

^X2b is a structure represented by the following formula (b2).

In the above formula (b2), X ^4b is an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent group of a heterocyclic compound having 8 to 20 carbon atoms. X ^4b is selected from the group consisting of alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl having 6 to 10 carbon atoms, hydroxy, cyano and nitro groups, and halogen It may be substituted with at least one selected. X ^5b is -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^2b -, -CO-, -COO-, -CONH-, alkylene having 1 to 3 carbon atoms group, or a phenylene group. h represents the number of repeating units of the structure in parentheses. The h+1 X ^4b and the h X ^5b may be the same or different. ^R2b is the same as defined above.

X ^3b- is a counter ion of onium, and is a fluorinated alkylfluorophosphate anion represented by the following formula (b9), the following formula (b13), the following formula (b14), or the following formula (b17), or the following formula (b18 ), and the anion of the following formula (b9) is preferable from the viewpoint of the film properties of the etching mask.

In the above formula (b9), R ^20b is a group represented by the following formulas (b10), (b11) and (b12).

In the above formula (b10), x represents an integer of 1 or more and 4 or less. In the above formula (b11), R ^21b is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched chain having 1 to 6 carbon atoms. represents an alkoxy group, and y represents an integer of 1 or more and 3 or less. Among these, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred from the viewpoint of safety.

In the above formulas (b13) and (b14), X ^b represents a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the number of carbon atoms in the alkylene group is 2 or more and 6 or less, preferably 3 or more and 5 or less, most preferably 3 carbon atoms. Y ^b and Z ^b each independently represent a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the number of carbon atoms in the alkyl group is 1 or more and 10 or less. , preferably 1 or more and 7 or less, more preferably 1 or more and 3 or less.

The smaller the number of carbon atoms in the alkylene group of ^Xb or the number of carbon atoms in the alkyl groups of Yb ^{and Zb} , the better the solubility in organic solvents, which is preferable.

In addition, in the alkylene group of ^Xb or the alkyl group of Yb ^{or Zb} , the greater the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, which is preferable. The ratio of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70% or more and 100% or less, more preferably 90% or more and 100% or less, and most preferably all hydrogen atoms are fluorine It is an atom-substituted perfluoroalkylene group or perfluoroalkyl group.

In formula (b17) above, ^R3b represents an alkyl group in which 80% or more of the hydrogen atoms are substituted with fluorine atoms. j indicates the number and is an integer of 1 or more and 5 or less. j R ^3b may be the same or different.

In the above formula (b18), R ^4b to R ^7b each independently represent a fluorine atom or a phenyl group, and part or all of the hydrogen atoms in the phenyl group are selected from the group consisting of a fluorine atom and a trifluoromethyl group. may be substituted with at least one of

The onium ion in the compound represented by the above formula (b1) includes triphenylsulfonium, tri-p-tolylsulfonium, 4-(phenylthio)phenyldiphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl-2- Chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10 -thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4- (4-benzoylphenylthio)phenyldiphenylsulfonium, diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, phenyl[4- (4-biphenylthio)phenyl]4-biphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]3-biphenylsulfonium, [4-(4-acetophenylthio)phenyl]diphenylsulfonium, octadecylmethylphenacylsulfonium , diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxyphenyl)phenyliodonium, bis(4-decyloxy)phenyliodonium, 4- (2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium, 4-isobutylphenyl(p-tolyl)iodonium, and the like.

In the fluorinated alkylfluorophosphate anion represented by the above formula (b17), R ^3b represents an alkyl group substituted with a fluorine atom, preferably has 1 or more and 8 or less carbon atoms, more preferably 1 or more carbon atoms. 4 or less. Specific examples of alkyl groups include straight chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; further cyclopropyl, cyclobutyl and cyclopentyl. , cycloalkyl groups such as cyclohexyl, etc., and the ratio of hydrogen atoms in the alkyl groups substituted with fluorine atoms is usually 80% or more, preferably 90% or more, more preferably 100%. If the substitution rate of fluorine atoms is less than 80%, the acid strength of the onium fluorinated alkylfluorophosphate represented by the formula (b1) is lowered.

Particularly preferred R ^3b is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and having a fluorine atom substitution rate of 100%, and specific examples thereof include CF ₃ and CF ₃ CF. _{2 ,} ( _{CF3 ) 2CF} , _{CF3CF2CF2 , CF3CF2CF2CF2 ,} ( _{CF3 ) 2CFCF2 , CF3CF2} ( _CF3 )CF, ( _{CF3 ) 3C} mentioned. The number j of ^R3b is an integer of 1 or more and 5 or less, preferably 2 or more and 4 or less, and particularly preferably 2 or 3.

Specific examples of preferred fluorinated alkylfluorophosphate anions include [(CF ₃ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ⁻ , [(( _CF3 ) _{2CFCF2 ) 2PF4} ] ^- _{, [} ( ⁽ _{CF3 ) 2CFCF2} ) _3PF3 ] _{- , [} (CF3CF2CF2CF2) _{2PF4 ] -} ^, or [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , among which [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ , or [(( CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^- is particularly preferred.

Preferred specific examples of the borate anion represented by the above formula (b18) include tetrakis(pentafluorophenyl)borate ([B(C ₆ F ₅ ) ₄ ] ⁻ ), tetrakis[(trifluoromethyl)phenyl]borate ( [B(C ₆ H ₄ CF ₃ ) ₄ ] ⁻ ), difluorobis(pentafluorophenyl)borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ⁻ ), trifluoro(pentafluorophenyl)borate ([(C ₆ F ₅ )BF ₃ ] ⁻ ), tetrakis(difluorophenyl)borate ([B(C ₆ H ₃ F ₂ ) ₄ ] ⁻ ), and the like. Among these, tetrakis(pentafluorophenyl)borate ([B(C ₆ F ₅ ) ₄ ] ⁻ ) is particularly preferred.

(Second acid generator)
As the second acid generator, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(2-furyl ) ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6 -[2-(5-ethyl-2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-propyl-2-furyl)ethenyl]-s-triazine , 2,4-bis(trichloromethyl)-6-[2-(3,5-dimethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5 -diethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dipropoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloro methyl)-6-[2-(3-methoxy-5-ethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-propoxyphenyl) ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-methylenedioxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6 -(3,4-methylenedioxyphenyl)-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-(2-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis -trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2 -(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(2-furyl)ethenyl]-4,6-bis(trichloromethyl)-1 ,3,5-triazine, 2-[2-(5-methyl-2-furyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3, 5-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl) )-1,3,5-triazine, 2-(3,4-methylenedioxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, tris(1,3-dibromopropyl) Halogen-containing triazine compounds such as -1,3,5-triazine, tris(2,3-dibromopropyl)-1,3,5-triazine, and tris(2,3-dibromopropyl) isocyanurate, etc. of the following formula ( Halogen-containing triazine compounds represented by b3) can be mentioned.

In formula (b3) above, R ^9b , R ^10b , and R ^11b each independently represent a halogenated alkyl group.

(Third acid generator)
As the third acid generator, α-(p-toluenesulfonyloxyimino)-phenylacetonitrile, α-(benzenesulfonyloxyimino)-2,4-dichlorophenylacetonitrile, α-(benzenesulfonyloxyimino)-2, 6-dichlorophenylacetonitrile, α-(2-chlorobenzenesulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, and the following formula (b4) containing an oximesulfonate group compounds represented.

In the above formula (b4), R ^12b represents a monovalent, divalent, or trivalent organic group, and R ^13b is a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic group. and n represents the number of repeating units of the structure in parentheses.

In the above formula (b4), examples of the aromatic group include aryl groups such as phenyl group and naphthyl group, and heteroaryl groups such as furyl group and thienyl group. These may have one or more suitable substituents such as halogen atoms, alkyl groups, alkoxy groups, nitro groups, etc. on the ring. Further, R ^13b is particularly preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group and a butyl group. Particularly preferred are compounds in which R ^12b is an aromatic group and R ^13b is an alkyl group having 1 to 4 carbon atoms.

As the acid generator represented by the above formula (b4), when n=1, R ^12b is any one of a phenyl group, a methylphenyl group, or a methoxyphenyl group, and R ^13b is a methyl group. Specifically, α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, α-(methylsulfonyloxyimino)-1-(p- methoxyphenyl)acetonitrile, [2-(propylsulfonyloxyimino)-2,3-dihydroxythiophen-3-ylidene](o-tolyl)acetonitrile and the like. When n=2, the acid generator represented by the above formula (b4) specifically includes an acid generator represented by the following formula.

(Fourth acid generator)
As the fourth acid generator, bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, etc. bissulfonyl diazomethanes; 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitrobenzyl carbonate, dinitrobenzyl carbo Nitrobenzyl derivatives such as phosphate; pyrogallol trimesylate, pyrogallol tritosylate, benzyl tosylate, benzylsulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, N-methylsulfonyl Sulfonic acid esters such as oxyphthalimide; N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)-1,8-naphthalimide, N-(trifluoromethylsulfonyloxy)-4-butyl -Trifluoromethanesulfonic acid esters such as 1,8-naphthalimide; diphenyliodonium hexafluorophosphate, (4-methoxyphenyl)phenyliodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate , triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate and other onium salts; benzoin tosylate, α-methylbenzoin tosylate benzoin tosylate such as lacto; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, benzyl carbonate and the like.

The acid generator (B) may be used alone or in combination of two or more. The content of the acid generator (B) is preferably 0.1 to 30 parts by mass, particularly 1 to 20 parts by mass, based on 100 parts by mass of the component (A) of the photosensitive resin composition. The following are preferred. By adjusting the amount of the acid generator (B) to be used within the above range, it is easy to prepare a photosensitive resin composition that has good sensitivity, is a uniform solution, and has excellent storage stability.
When two or more acid generators (B) are used in combination, the first acid generator and one or more selected from the second to fourth acid generators can be combined from the viewpoint of the film properties of the etching mask. Preferably, the first acid generator and one selected from the second to fourth acid generators are combined, more preferably, the first acid generator and the third acid generator are combined. preferable.
In the component (B), the ratio (mass ratio) of the first acid generator and the other acid generator (one or more selected from the second to fourth acid generators) is First acid generator): (other acid generator) = preferably in the range of 99:1 to 1:99, more preferably 5:95 to 50:50, 10:90 to 40:60 is more preferred, and 10:90 to 30:70 is most preferred.

[Filler (C)]
The photosensitive resin composition contains a filler (C). When the photosensitive resin composition contains the filler (C), it is easy to form an etching mask excellent in hardness, mechanical properties, heat resistance, etc. using the photosensitive resin composition. The filler (C) may be an inorganic filler or an organic filler, preferably an inorganic filler.
In terms of high resistance to etchants such as hydrofluoric acid, the filler (C) includes, for example, mica, talc, clay, bentonite, montmorillonite, kaolinite, wollastonite, alumina, aluminum hydroxide, barium sulfate, and titanium. barium oxide, potassium titanate, and the like.

The content of the filler (C) in the photosensitive resin composition is not particularly limited as long as the object of the present invention is not impaired. The content of the filler (C) in the photosensitive resin composition is appropriately determined in consideration of the film thickness of the etching mask to be formed, the depth of engraving of the glass by etching, and the like.
For example, the content of the filler (C) in the photosensitive resin composition is 30 parts by mass or more and 70 parts by mass with respect to a total of 100 parts by mass of the mass of the resin component (A) and the acid generator (B). Part or less is preferable, and 35 to 60 parts by mass is more preferable.
In particular, when the glass substrate is etched to a depth of 300 μm or more, the content of the filler (C) is preferably within the above range.
Further, when the depth of engraving of the glass substrate by etching is less than 300 μm, the content of the filler (C) in the photosensitive resin composition is determined by the mass of the resin component (A) and the acid generator (B). It may be 1 part by mass or more and less than 30 parts by mass with respect to a total of 100 parts by mass.

[Plasticizer (D)]
The photosensitive resin composition contains a plasticizer (D). By including the plasticizer (D) in the photosensitive resin composition, it is possible to suppress the occurrence of cracks in the etching mask formed using the photosensitive resin composition. A crack-free etching mask has excellent resistance to the etchants used to etch glass substrates.

Specific examples of the plasticizer (D) include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl alkyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl phenol, and copolymers thereof. mentioned. Among these, polyvinyl alkyl ether is preferable because it is easy to form an etching mask having excellent resistance to the etchant.

The number of carbon atoms in the alkyl portion of the polyvinyl alkyl ether is preferably 1 or more and 5 or less, more preferably 1 or 2. That is, polyvinyl methyl ether and polyvinyl ethyl ether are more preferable as polyvinyl alkyl ether.

The weight average molecular weight of polyvinyl alkyl ether is not particularly limited. The weight average molecular weight of the polyvinyl alkyl ether is preferably 10,000 or more and 200,000 or less, more preferably 50,000 or more and 100,000 or less.

The content of the plasticizer (D) in the photosensitive resin composition is not particularly limited as long as the desired effect is obtained by using the plasticizer (D). The content of the plasticizer (D) in the photosensitive resin composition is preferably 10 parts by mass or more and 100 parts by mass or less, more preferably 20 parts by mass or more and 80 parts by mass or less, relative to 100 parts by mass of the resin component (A). , more preferably 30 parts by mass or more and 60 parts by mass or less.

[Solvent (S)]
The photosensitive resin composition generally preferably contains a solvent (S) for the purpose of adjusting coatability. The type of solvent (S) is not particularly limited as long as it does not impair the object of the present invention, and can be appropriately selected from solvents conventionally used in positive photosensitive resin compositions.

Specific examples of the solvent (S) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1 , 3-butylene glycol, glycols such as hexylene glycol; polyols such as glycerin; monools such as benzyl alcohol and terpineol; ethylene glycol monoacetate, diethylene glycol monoacetate, triethylene glycol monoacetate, propylene glycol monoacetate, Monoacetates of glycols such as dipropylene glycol monoacetate, tripropylene glycol monoacetate, and 1,3-butylene glycol monoacetate; ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate, di Diacetates of glycols such as propylene glycol diacetate, tripropylene glycol diacetate, and 1,3-butylene glycol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, Ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monopropyl ether Ethylene glycol monobutyl ether, triethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono Ethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tri Propylene glycol monophenyl ether, 1,3-butylene glycol monomethyl ether, 1,3-butylene glycol monoethyl ether, 1,3-butylene glycol monopropyl ether, 1,3-butylene glycol monobutyl ether, and 1,3-butylene Monoethers of glycols such as glycol monophenyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monopropyl ether acetate, triethylene glycol mono Butyl ether acetate, triethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monophenyl ether acetate, dipropylene glycol monomethyl ether acetate , dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, dipropylene glycol monophenyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monopropyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol monophenyl ether acetate, 1,3-butylene glycol monomethyl ether acetate (3-methoxybutyl acetate), 1,3-butylene glycol monoethyl ether acetate, 1, 3-butylene glycol monopropyl ether acetate, 1,3-butylene glycol monobutyl ether acetate, 1,3-butylene glycol monophenyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, and 4 - monoether acetate of glycols such as methyl-4-methoxypentyl acetate; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, ethylene glycol diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di Propyl ether, diethylene glycol dibutyl ether, diethylene glycol diphenyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, triethylene glycol diphenyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol Dipropyl ether, propylene glycol dibutyl ether, propylene glycol diphenyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, dipropylene glycol diphenyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dipropyl ether, tripropylene glycol dibutyl ether, tripropylene glycol diphenyl ether, 1,3-butylene glycol dimethyl ether, 1,3-butylene glycol diethyl ether, 1,3-butylene glycol dipropyl ether, 1, Diethers of glycols such as 3-butylene glycol dibutyl ether and 1,3-butylene glycol diphenyl ether; ethers such as dioxane and dihexyl ether; ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, benzyl acetate, ethyl benzoate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate , Esters such as ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, diethyl maleate, cyclohexanol acetate, gamma-butyrolactone; aromatic hydrocarbons such as toluene and xylene; can be mentioned. These may be used alone or in combination of two or more.

The photosensitive resin composition has a boiling point of 170 under atmospheric pressure because it easily forms a coating film having a uniform thickness when the photosensitive resin composition is applied to a glass substrate. C. or higher, preferably containing a high boiling point solvent (S1).
Preferred examples of the high boiling point solvent (S1) in the above specific examples of the solvent (S) include the good solubility of each component contained in the photosensitive resin composition and the ease of availability. Ethylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, glycerin, benzyl alcohol, terpineol, propylene glycol diacetate, 1,3-butylene glycol diacetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono Butyl ether, diethylene glycol monophenyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, dipropylene glycol monomethyl ether acetate, 1,3-butylene glycol monomethyl ether acetate (3-methoxybutyl acetate), 3-methyl-3-methoxybutyl acetate, 3-ethyl-3- Methoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dihexyl ether benzyl acetate, ethyl benzoate, diethyl maleate, cyclohexanol acetate, and gamma-butyrolactone.

The content of the high boiling point solvent (S1) in the photosensitive resin composition is not particularly limited as long as the desired effect is obtained by using the high boiling point solvent (S1). The content of the high boiling solvent (S1) in the photosensitive resin composition is 1 part by mass or more and 50 parts by mass when the total mass of the solvent (S) in the photosensitive resin composition is 100 parts by mass from the viewpoint of coating properties. It is preferably less than 1 part by mass, and more preferably 1 part by mass or more and 20 parts by mass or less.
Moreover, it is preferably 0.5% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, and particularly preferably 2% by mass or more and 10% by mass or less, relative to the total mass of the photosensitive resin composition. .

The content of the solvent (S) in the photosensitive resin composition is not particularly limited as long as an etching mask having a desired film thickness can be formed. For the solvent (S), for example, the solid content concentration of the photosensitive resin composition is preferably 40% by mass or more and 70% by mass or less, and more preferably 50% by mass or more and 65% by mass in terms of the manufacturing process such as etching margin. % or less.
In the case of the step of applying the photosensitive resin composition from the vertically upward side to the vertically downward side using a contact-type coating device on both of the two main surfaces of the glass substrate, which will be described later, the photosensitive resin The viscosity of the composition is preferably adjusted to 1000 cp or more, more preferably 1400 cp or more, and even more preferably 2000 cp or more. There is no particular upper limit as long as the photosensitive resin composition has fluidity.

[Other ingredients]
The photosensitive resin composition may contain various components conventionally blended in positive photosensitive compositions.

For example, the photosensitive resin composition may further contain a surfactant in order to improve coating properties, defoaming properties, leveling properties, and the like. As the surfactant, for example, fluorine-based surfactants and silicone-based surfactants are preferably used.
Specific examples of fluorosurfactants include BM-1000, BM-1100 (all manufactured by BM Chemie), Megafac F142D, Megafac F172, Megafac F173, and Megafac F183 (all from Dainippon Ink and Chemicals). company), Florado FC-135, Florado FC-170C, Florard FC-430, Florard FC-431 (all manufactured by Sumitomo 3M), Surflon S-112, Surfon S-113, Surfon S-131, Surfon S- 141, Surflon S-145 (both manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (both manufactured by Toray Silicone Co., Ltd.) and other commercially available fluorine-based surfactants include, but are not limited to.
Examples of silicone-based surfactants include unmodified silicone-based surfactants, polyether-modified silicone-based surfactants, polyester-modified silicone-based surfactants, alkyl-modified silicone-based surfactants, aralkyl-modified silicone-based surfactants, and A reactive silicone surfactant or the like can be preferably used.
A commercially available silicone surfactant can be used as the silicone surfactant. Specific examples of commercially available silicone surfactants include Paintad M (manufactured by Dow Corning Toray Co., Ltd.), Topica K1000, Topica K2000, Topica K5000 (all manufactured by Takachiho Sangyo Co., Ltd.), XL-121 (polyether-modified silicone surfactant, manufactured by Clariant), BYK-088 (silicone antifoaming agent, manufactured by BYK-Chemie), BYK-310 (polyester-modified silicone-based surfactant, manufactured by BYK-Chemie), and the like.

Moreover, the photosensitive resin composition may further contain an acid or an acid anhydride in order to finely adjust the solubility in the developer.

Specific examples of acids and acid anhydrides include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; lactic acid, 2-hydroxybutyric acid, Hydroxy monocarboxylic acids such as 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid and syringic acid Acids; oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid Polyvalent carboxylic acids such as acids, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, anhydride succinic acid, citraconic anhydride, dodecenylsuccinic anhydride, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, acid anhydrides such as cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis anhydride trimellitate, glycerol tris anhydride trimellitate; can.

The first photosensitive resin composition is obtained by uniformly mixing the components described above in a desired ratio.

<Second photosensitive resin composition>
As described above, the second photosensitive resin composition comprises a resin component (A1) having a phenolic hydroxyl group, a protective agent (A2) that reacts with the phenolic hydroxyl group to provide an acid-dissociable, dissolution-inhibiting group, and an acid It contains a generator (B), a filler (C) and a plasticizer (D).
The acid generator (B), filler (C), plasticizer (D) and other components are the same as in the first photosensitive resin composition.

In the second photosensitive resin composition, the resin component (A1) having phenolic hydroxyl groups and the protective agent (A2) reacting with the phenolic hydroxyl groups to provide acid-dissociable, dissolution-inhibiting groups will be described below.

[Resin component (A1) having phenolic hydroxyl group]
The resin component (A1) having phenolic hydroxyl groups is a novolac resin or polyhydroxystyrene resin in which at least part of the phenolic hydroxyl groups may be protected by the acid-dissociable, dissolution-inhibiting groups. The novolac resin or polyhydroxystyrene resin having phenolic hydroxyl groups and at least a portion of the phenolic hydroxyl groups being protected by the acid-dissociable, dissolution-inhibiting groups has been described in the first photosensitive resin composition. It is the same as the resin component (A). As the novolak resin and the polyhydroxystyrene resin, a novolak resin in which the phenolic hydroxyl group protected with the acid-dissociable, dissolution-inhibiting group is deprotected in the resin component (A) described for the first photosensitive resin composition. and polyhydroxystyrene resins can be used.

[Protective agent (A2)]
The protective agent (A2) is a compound that gives an acid-dissociable, dissolution-inhibiting group by reacting with a phenolic hydroxyl group.
As the protective agent (A2), the methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n-butoxy ethyl group, isobutoxyethyl group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group, tert- The compound is not particularly limited as long as it provides an acid-dissociable, dissolution-inhibiting group such as a butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl group, and a tri-tert-butyldimethylsilyl group.

As the protective agent, the divinyl ether compound represented by the above formula (I) is preferable because it is particularly easy to achieve both excellent resistance to the etchant of the etching mask and ease of peeling of the etching mask with an organic solvent.

The amount of the protective agent (A2) used is 0.5 parts by mass or more and 30 parts by mass or less, based on 100 parts by mass of the resin component (A1) having a phenolic hydroxyl group, from the viewpoint of the film properties of the etching mask. , more preferably 1 part by mass or more and 20 parts by mass or less, and even more preferably 2 parts by mass or more and 10 parts by mass or less.

The second photosensitive resin composition is obtained by uniformly mixing the above-described components in a desired ratio.

<<Method for etching glass substrate>>
The etching method of the glass substrate is
A coating film forming step of applying the photosensitive resin composition described above to at least one main surface of a glass substrate to form a coating film on the main surface of the glass substrate;
an exposure step of position-selectively exposing the coating film;
an etching mask forming step of developing the exposed coating film with a developer to form an etching mask;
an etching step of etching a glass substrate provided with an etching mask;
a removing step of removing the etching mask;
is a method that includes

The following describes each step related to the method of etching a glass substrate.

<Coating film forming process>
In the coating film forming step, the photosensitive resin composition is applied to at least one main surface of the glass substrate to be etched to form a coating film on the main surface of the glass substrate.
The type of glass substrate is not particularly limited, and examples thereof include alkali-free glass, borosilicate glass, tempered glass, and quartz. Also, the type of shape of the glass substrate is not particularly limited. The shape of the glass substrate may be an uneven shape or a shape having through holes.

The depth of etching into the glass substrate is not particularly limited. The engraving depth of the glass substrate is the total depth of etching in both main surfaces of the glass substrate when etching is performed from both main surfaces of the glass substrate.
By forming an etching mask using the photosensitive resin composition of the present invention, the etching depth of the glass substrate can be increased to, for example, about 2000 μm. The value on the lower limit side can be appropriately set in the processing range of the digging depth.
Considering the above digging depth, the thickness of the glass substrate is preferably 10 μm or more, more preferably 200 μm or more and 3000 μm or less, still more preferably 250 μm or more and 2300 μm or less, and particularly preferably 300 μm or more and 2000 μm or less.

The film thickness of the etching mask is not particularly limited as long as the etching process can be performed without problems. Typically, the film thickness of the etching mask is preferably 5 μm or more and 200 μm or less, and more preferably 5 μm or more and 200 μm or less in double-sided coating. The film thickness of the etching mask is preferably 0.08 times or more and 0.25 times or less, more preferably 0.1 times or more and 0.2 times or less, with respect to the etching depth of the glass substrate. more preferred.

In the coating film forming step, for example, a contact transfer type coating device such as a roll coater, a reverse coater, and a bar coater, or a non-contact type coating device such as a spinner, curtain flow coater, or slit coater is used to apply the above-described photosensitive material onto the glass substrate. A coating film can be formed by applying a flexible resin composition. The formed coating film may be heated (pre-baked) as necessary.

Pre-baking conditions vary depending on the type of each component in the photosensitive resin composition, the mixing ratio, the coating film thickness, etc., but are usually 70° C. or higher and 200° C. or lower, preferably 80° C. or higher and 150° C. or lower, for 2 minutes or more. About 120 minutes or less.

For example, when cutting a glass substrate with a thickness of 200 μm or more by etching, or when forming a through hole in a glass substrate with a thickness of 200 μm or more by etching, the etching time can be shortened and damage to the etching mask can be suppressed. Therefore, it is preferable to bring the etchant into contact with both main surfaces of the glass substrate for etching.
When etching is performed by bringing an etchant into contact with both main surfaces of the glass substrate, etching masks are formed on both main surfaces of the glass substrate.

When the photosensitive resin composition is applied to both main surfaces of the glass substrate, a coating film having a uniform thickness can be efficiently formed, so the main surface of the glass substrate is perpendicular to the vertical direction or substantially vertical direction. In the state where the glass substrate is arranged as above, the photosensitive resin composition is applied from the vertically upper side to the vertically lower side using a contact type coating device on both of the two main surfaces of the glass substrate. is preferred.
In addition, in a state in which the glass substrate is arranged so that the surface direction of the main surface of the glass substrate is horizontal or substantially horizontal, both of the two main surfaces of the glass substrate are coated with a photosensitive resin by a contact coating device. Application of the composition can also be carried out.

When performing the double-sided coating, the contact-type coating device may be moved while the position of the glass substrate is fixed, and the glass substrate may be coated while the position of the contact-type coating device is fixed. Application may be performed by moving.

When performing the double-sided coating, it is preferable to use a contact transfer type coating device such as a roll coater, a reverse coater and a bar coater, and more preferably a roll coater.

<Exposure process>
In the exposure step, the coating film on the glass substrate is exposed selectively according to the shape of the etching mask to be formed.
Specifically, the coating film is selectively irradiated (exposed) with actinic rays or radiation such as ultraviolet rays or visible rays with a wavelength of 300 nm or more and 500 nm or less through a mask having a predetermined pattern.

Low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, and the like can be used as radiation sources. Radiation includes microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, γ-rays, electron beams, proton beams, neutron beams, ion beams, and the like. Although the dose of radiation varies depending on the composition of the photosensitive composition, the film thickness of the photosensitive layer, and the like, it is 100 mJ/cm ² or more and 10000 mJ/cm ² or less when using an ultra-high pressure mercury lamp, for example.

After exposure, the coating film is heated by a known method to promote diffusion of the acid, thereby changing the solubility of the coating film in a developer such as an alkaline developer in the exposed portions of the coating film. Let

<Etching mask forming process>
In the etching mask forming step, the exposed coating film is developed with a developer to form an etching mask.

Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3, Aqueous solutions of alkalis such as 0]-5-nonane can be used. Further, an aqueous solution prepared by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of the above alkalis can be used as a developer.

The development time varies depending on the composition of the photosensitive resin composition, the film thickness of the coating film, etc., but is usually between 1 minute and 30 minutes. The developing method may be any of a liquid-filling method, a dipping method, a puddle method, a spray developing method, and the like.

After development, if necessary, the film is washed with running water for 30 seconds or more and 90 seconds or less, and dried using an air gun, an oven, or the like. Thus, an etching mask patterned into a desired shape is formed on the glass substrate.

<Etching process>
In the etching step, the glass substrate provided with the etching mask is etched.

The etching process may be a process of cutting the glass substrate or forming a hole penetrating the glass substrate in the thickness direction, or may be a process of forming grooves or trenches in the glass substrate.

The etching method is not particularly limited as long as it can bring the etchant and the glass substrate into contact with each other. Examples of the etching method include wet etching in which an etchant is sprayed onto the glass substrate or the glass substrate is immersed in the etchant.
Etching may be performed by bringing the etchant into contact with only one main surface of the glass substrate, or may be carried out by bringing the etchant into contact with both of the main surfaces of the glass substrate.

When the etchant is brought into contact with only one main surface of the glass substrate, it is preferable to cover the main surface of the glass substrate which is not in contact with the etchant with a protective film. The protective film is not particularly limited as long as it has resistance to the etchant.
The protective film may be formed by attaching a sheet made of a material resistant to an etchant to the glass substrate, or may be formed by applying the above-described photosensitive resin composition and then heating the coating film. .

As described above, when cutting a glass substrate with a thickness of 200 μm or more by etching, or when forming a through hole in a glass substrate with a thickness of 200 μm or more by etching, the etching time is shortened to reduce damage to the etching mask. Since it can be suppressed, it is preferable to carry out etching by bringing an etchant into contact with both main surfaces of the glass substrate.

Examples of the etchant include hydrofluoric acid alone, hydrofluoric acid and ammonium fluoride, mixed acids of hydrofluoric acid and other acids (hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc.). The etching treatment time is not particularly limited, but is, for example, about 10 minutes to 10 hours. The etchant may be heated to about 25° C. or higher and 60° C. or lower. In addition, the concentration of the etching treatment liquid may be appropriately adjusted in consideration of the etching rate and treatment time. For example, the concentration of hydrofluoric acid is preferably 1% by mass or more and 20% by mass or less, and more The following are more preferred. The concentration of the other acid is preferably 1% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 20% by mass or less.

<Removal process>
Following the etching process, the etching mask is removed from the glass substrate in a removing step.

A method for removing the etching mask is not particularly limited, but a method of bringing the etching mask into contact with an organic solvent is preferable because it hardly damages the glass substrate and the metal wiring and resin material attached to the glass substrate. The method of bringing the etching mask into contact with the organic solvent is not particularly limited. For example, an organic solvent may be sprayed onto the etching mask, or a glass substrate provided with the etching mask may be immersed in the organic solvent.

The organic solvent is not particularly limited as long as it can remove the etching mask, and may be appropriately selected from the above solvents (S). The organic solvent is preferably a polar solvent (particularly monoethers of ketones or glycols in the above solvent (S)) from the viewpoint of the process after the removal step. N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, etc., from the point of margin of the removal step aprotic polar organic solvents and the like are more preferably used. These organic solvents may be used in combination of two or more.

The temperature of the organic solvent used for stripping the etching mask is not particularly limited, and may be heated to improve stripping properties. The temperature of the organic solvent is, for example, preferably 5° C. or higher and 80° C. or lower, more preferably 10° C. or higher and 50° C. or lower, and considering the influence on the glass substrate and the metal wiring and resin material attached to the glass substrate, it is 20° C. or higher. 25° C. or lower is more preferable.

The contact time between the etching mask and the organic solvent is not particularly limited as long as the etching mask can be removed satisfactorily. The contact time is, for example, preferably 1 minute or longer and 60 minutes or shorter, more preferably 1 minute or longer and 15 minutes or shorter.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

[Examples 1 to 4]
Each component was mixed in the ratio shown in the table below to obtain a photosensitive resin composition. The usage amount of each component shown in Table 1 is in parts by mass. The following components in Table 1 are as follows. Further, the viscosity of each composition of Examples 1 to 4 was about 1500 cp. Examples 5-7 were about 2000 cp.

<Resin component (A)>
(A)-1: Novolac resin in which 7.5% of all phenolic hydroxyl groups are protected with acid-dissociable, dissolution-inhibiting groups derived from 1,4-cyclohexanedimethanoldivinyl ether. (Mw: 40000, m-cresol/p-cresol = 6/4 (molar ratio) for novolac resin before protection.)
(A)-2: A novolac resin in which 15% of all phenolic hydroxyl groups are protected with acid-dissociable, dissolution-inhibiting groups derived from 1,4-cyclohexanedimethanoldivinyl ether. (Mw: 15000, m-cresol/p-cresol = 6/4 (molar ratio) for novolak resin before protection.)
(A)-3: A novolac resin in which 6% of all phenolic hydroxyl groups are protected with acid-dissociable, dissolution-inhibiting groups derived from 1,4-cyclohexanedimethanoldivinyl ether. (Mw: 25000, m-cresol/p-cresol = 6/4 (molar ratio) for novolac resin before protection.)

<Protective agent (A2)>
(A2)-1: 1,4-cyclohexanedimethanol divinyl ether

（Ｂ）－３：２，４－ビス（トリクロロメチル）－６－ピペロニル－１，３，５－トリ
アジン
（Ｂ）－４：下記式の化合物

<Acid generator (B)>
(B)-1: triphenylsulfonium nonafluorobutanesulfonate (B)-2: compound of the following formula

(B)-3: 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine (B)-4: compound of the following formula

<Filler (C)>
(C)-1: barium sulfate powder <plasticizer (D)>
(D)-1: Polyvinyl methyl ether (mass average molecular weight 100,000)

<Solvent (S)>
(S)-1: propylene glycol monomethyl ether acetate (S)-2: butyl acetate (S)-3: methoxybutyl acetate

<Other additives (O)>
(O)-1: tri-n-decylamine and 0.1 parts by mass and a surfactant (trade name: XR-104, manufactured by Dainippon Ink and Chemicals) 0.1 parts by mass (O)-2: silicone-based Defoamer (trade name: BYK-088, manufactured by BYK-Chemie)

<Evaluation 1>
Using the obtained photosensitive resin compositions of Examples 1 to 4, an etching mask was formed on a glass substrate according to the following method.
First, a photosensitive resin composition was applied onto a 400 μm-thick glass substrate partially including a polyimide film and metal wiring. Next, the coating film was heated at 90° C. for 3 minutes, and then heated at 150° C. for 3 minutes. The coated film after heating was exposed through a positive mask at an exposure amount of 1200 mJ/cm ² . The coated film after exposure was heated at 115° C. for 3 minutes. The coated film after heating was brought into contact with an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass at 22° C. for 7 minutes for development. The developed coating film was heated at 120° C. for 60 minutes to form an etching mask with a thickness of 70 μm.
A glass substrate provided with an etching mask was etched at room temperature under the following conditions.
Etching solution (1:1 mixed acid solution of 10% by mass of hydrofluoric acid aqueous solution and 20% by mass of nitric acid aqueous solution)
・Etching time: 1 hour

The etched glass substrate was immersed in a mixed solvent of N-methyl-2-pyrrolidone (NMP) and dimethylsulfoxide (DMSO) (NMP/DMSO (mass ratio) = 40/60) at room temperature for 10 minutes. The etch mask was completely dissolved away in less than 1 hour.
The surface of the glass substrate after removing the etching mask was observed with a microscope, but no residue was observed on the glass substrate after removing the etching mask. In addition, no loss of the polyimide film or damage to the metal wiring was observed.
<Evaluation 2>
Using the obtained photosensitive resin compositions of Examples 5 to 7, an etching mask was formed on a glass substrate according to the following method.
First, 70 μm of a photosensitive resin composition was applied onto a 400 μm-thick glass substrate partially including a polyimide film and metal wiring, and dried by heating at 90° C. for 3 minutes. Then, using the same photosensitive resin composition, a second coating and drying (heating at 90° C. for 3 minutes) were performed on the dried coating film to obtain a coating film with a thickness of 140 μm. After that, the coating film was heated at 150° C. for 3 minutes. The coating film after drying (heating) was exposed through a positive mask at an exposure amount of 1200 mJ/cm ² . The coated film after exposure was heated at 115° C. for 3 minutes. The coated film after heating was brought into contact with an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass at 22° C. for 7 minutes for development. The developed coating film was heated at 120° C. for 60 minutes to form an etching mask with a thickness of about 140 μm.
When the obtained etching mask was confirmed with an ultrasonic microscope (C-SAM D9600), it was found to be an etching mask without pinholes or cracks.
A glass substrate provided with an etching mask was etched at room temperature under the following conditions.
Etching solution (1:1 mixed acid solution of 10% by mass of hydrofluoric acid aqueous solution and 20% by mass of nitric acid aqueous solution)
・Etching time: 1 hour

The etched glass substrate was immersed in a mixed solvent of N-methyl-2-pyrrolidone (NMP) and dimethylsulfoxide (DMSO) (NMP/DMSO (mass ratio) = 40/60) at room temperature for 10 minutes. The etch mask was completely dissolved away in less than 1 hour.
The surface of the glass substrate after removing the etching mask was observed with a microscope, but no residue was observed on the glass substrate after removing the etching mask. In addition, no loss of the polyimide film or damage to the metal wiring was observed.

[Comparative example]
<Peelability evaluation>
Using a commercially available negative photosensitive composition, coating, exposure, and development are performed in the usual manner, and a 70 μm thick etching mask is formed on a 400 μm thick glass substrate partially including a polyimide film and metal wiring. formed. After the same etching treatment as in the example, the glass substrate provided with the etching mask was treated at room temperature with a mixed solvent of N-methyl-2-pyrrolidone (NMP) and dimethylsulfoxide (DMSO) (NMP/DMSO (mass ratio) = 40 /60), the etching mask could not be removed by immersion for 10 minutes.
Further, the glass substrate provided with the etching mask was immersed in a mixed solvent of monoethanolamine (MEA) and dimethylsulfoxide (DMSO) (MEA/DMSO (mass ratio) = 70/30) at 50°C for 30 minutes. Although the etching mask could be removed, a large amount of post-removal residue was generated on the glass substrate. In addition, film reduction was observed in the polyimide film, and corrosion was observed in the metal wiring.

Claims (6)

A resin component (A) having an acid-dissociable, dissolution-inhibiting group and increasing alkali solubility under the action of an acid, an acid generator (B) capable of generating an acid upon exposure to radiation, a filler (C), and a plasticizer. (D); or
A resin component (A1) having a phenolic hydroxyl group, a protective agent (A2) that reacts with the phenolic hydroxyl group to provide an acid-dissociable, dissolution-inhibiting group, the acid generator (B), and the filler (C). and the plasticizer (D),
The resin component (A) is a novolac resin or a polyhydroxystyrene resin in which at least part of the phenolic hydroxyl groups are protected by the acid-dissociable, dissolution-inhibiting groups,
The resin component (A1) is a novolac resin or polyhydroxystyrene resin in which at least part of the phenolic hydroxyl groups are protected by the acid-dissociable, dissolution-inhibiting groups , or at least part of the phenolic hydroxyl groups are the acid-dissociable. A novolac resin or polyhydroxystyrene resin that is not protected by a dissolution-inhibiting group ,
A photosensitive resin composition used to form an etching mask on a glass substrate ,
When the photosensitive resin composition contains the resin component (A), the acid generator (B), the filler (C), and the plasticizer (D), the resin component (A) contains the reaction product of the novolac resin or polyhydroxystyrene resin and the compound represented by formula (I),
When the photosensitive resin composition contains the resin component (A1), the protective agent (A2), the acid generator (B), the filler (C), and the plasticizer (D) In, the protective agent (A2) contains the compound represented by formula (I),
The formula (I) is the following formula:
H ₂ C=CH—O—A ^a1 —O—CH=CH ₂ (I)
is represented by
In the above formula (I), A ^a1 is an alkylene group having 1 to 10 carbon atoms which may have a substituent and may contain an ether bond in the main chain, or the following formula (II):
-(A ^a2 ) _na -A ^a3 -(A ^a2 ) _na - (II)
is a group represented by
In the above formula (II), A ^a2 is an optionally substituted alkylene group having 1 to 10 carbon atoms, A ^a3 is a cyclohexylene group, and na is 0 or 1, A photosensitive resin composition . 2. The photosensitive resin composition according to claim 1 , wherein said plasticizer (D) comprises a polyvinyl alkyl ether. The photosensitive resin composition according to claim 1 or 2 , comprising a solvent (S), wherein the solvent (S) comprises a high-boiling solvent (S1) having a boiling point of 170°C or higher under atmospheric pressure. Coating film formation in which the photosensitive resin composition according to any one of claims 1 to 3 is applied to at least one main surface of a glass substrate to form a coating film on the main surface of the glass substrate. process and
an exposure step of position-selectively exposing the coating film;
an etching mask forming step of developing the exposed coating film with a developer to form an etching mask;
an etching step of etching the glass substrate provided with the etching mask;
a removing step of removing the etching mask;
A method of etching a glass substrate, comprising: 5. The method of etching a glass substrate according to claim 4 , wherein the etching process is a drilling process for forming a hole penetrating through the glass substrate in the thickness direction. forming the etching mask on both of the two main surfaces of the glass substrate;
6. The method of etching a glass substrate according to claim 4 , wherein the etching process is applied to both of the two main surfaces of the glass substrate.