JP5792548B2 - Glass processing method - Google Patents

Description

  The present invention relates to a glass processing method for etching a glass substrate using a resin pattern obtained by patterning a photosensitive resin composition as a mask.

  The touch panel is configured by forming a transparent conductive material such as ITO on the opposing surfaces of a glass substrate and a film material facing each other via a spacer. In this touch panel, the contact position of the film material is detected as coordinate information.

  Recently, a liquid crystal display integrated with a touch panel has also been proposed. This is because one of the two glass substrates constituting the liquid crystal display also serves as the glass substrate of the touch panel, and is very effective in realizing a reduction in thickness and weight.

  Conventionally, a physical method is generally used as a processing method of such a glass substrate, but there is a problem that cracks are easily generated during processing, and the strength is lowered or the yield is deteriorated.

  Therefore, in recent years, a chemical method for etching a glass substrate using a resin pattern obtained by patterning a photosensitive resin composition as a mask has been proposed (see, for example, Patent Documents 1 and 2). According to such a chemical method, since no physical load is applied during processing, cracks are unlikely to occur. Further, unlike the physical method, it is also possible to perform drilling for a microphone or a speaker on a glass substrate.

JP 2008-0776768 A JP 2010-072518 A

  By the way, recently, tempered glass is often used as such a glass substrate. Accompanying this, the etching conditions become severe. For example, it has been studied to use an etching solution containing 15% by mass hydrofluoric acid and 15% by mass sulfuric acid by heating to 25 to 60 ° C.

  However, when the conventional photosensitive resin composition as described in Patent Documents 1 and 2 is used, there is a problem that the etching resistance is insufficient under the above severe etching conditions. Further, as a result of studies by the present inventors, it has been found that the addition of an inorganic filler to the photosensitive resin composition improves the etching resistance itself, but decreases the resolution and peelability.

  The present invention has been made in view of such a conventional situation, and provides a glass processing method using a photosensitive resin composition having high etching resistance and excellent resolution and peelability. With the goal.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by using a specific photosensitive resin composition, and the present invention has been completed.

  That is, the glass processing method according to the present invention includes a coating film forming step of forming a coating film of a photosensitive resin composition containing an alkali-soluble resin having a phenolic hydroxyl group on a glass substrate, and the coating film is selectively used. An exposure step of exposing, a developing step of developing the coating film after exposure to form a resin pattern, an etching step of etching the glass substrate using the resin pattern as a mask, and a peeling step of peeling off the resin pattern; Is included.

  According to the present invention, it is possible to provide a glass processing method using a photosensitive resin composition having high etching resistance and excellent resolution and peelability.

Hereinafter, embodiments of the present invention will be described in detail.
The glass processing method according to the present invention involves etching a glass substrate using a resin pattern obtained by patterning a photosensitive resin composition as a mask. Below, the photosensitive resin composition used by this invention is demonstrated first, and then the glass processing method which concerns on this invention is demonstrated.

≪Photosensitive resin composition≫
The photosensitive resin composition used in the present invention contains at least an alkali-soluble resin having a phenolic hydroxyl group. This photosensitive resin composition may be either a positive type or a negative type. Hereinafter, each component contained in the positive photosensitive resin composition and the negative photosensitive resin composition will be described in detail.

<Positive photosensitive resin composition>
The positive photosensitive resin composition contains (A) an alkali-soluble resin having a phenolic hydroxyl group and (B) a quinonediazide group-containing compound.

[(A) Alkali-soluble resin having phenolic hydroxyl group]
As an alkali-soluble resin having a phenolic hydroxyl group (hereinafter, also referred to as “component (A)”), for example, a polyhydroxystyrene resin can be used.
The polyhydroxystyrene resin has at least a structural unit derived from hydroxystyrene.
As used herein, “hydroxystyrene” refers to hydroxystyrene, and those obtained by substituting a hydrogen atom bonded to the α-position of hydroxystyrene with another substituent such as a halogen atom, an alkyl group, or a halogenated alkyl group, and derivatives thereof. The concept includes a hydroxystyrene derivative (monomer).
In the “hydroxystyrene derivative”, at least a benzene ring and a hydroxyl group bonded thereto are maintained. For example, a hydrogen atom bonded to the α-position of hydroxystyrene is a halogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom. A group substituted with another substituent such as an alkyl group, a benzene ring to which a hydroxyl group of hydroxystyrene is bonded, and a benzene ring to which an alkyl group having 1 to 5 carbon atoms is further bonded, or a benzene ring to which this hydroxyl group is bonded Further, it includes one having 1 to 2 hydroxyl groups bonded (the total number of hydroxyl groups is 2 to 3 at this time) and the like.
Examples of the halogen atom include a chlorine atom, a fluorine atom and a bromine atom, and a fluorine atom is preferable.
The “α-position of hydroxystyrene” means a carbon atom to which a benzene ring is bonded unless otherwise specified.

  The structural unit derived from this hydroxystyrene is represented by the following formula (a-1), for example.

In the formula (a-1), R ^a1 represents a hydrogen atom, an alkyl group, a halogen atom, or a halogenated alkyl group, R ^a2 represents an alkyl group having 1 to 5 carbon atoms, and p is an integer of 1 to 3. Q represents an integer of 0-2.

The alkyl group for R ^a1 preferably has 1 to 5 carbon atoms. Moreover, a linear or branched alkyl group is preferable, and a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc. Can be mentioned. Among these, a methyl group is preferable industrially.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
As the halogenated alkyl group, a part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms described above are substituted with a halogen atom. Among these, those in which all of the hydrogen atoms are substituted with fluorine atoms are preferable. Further, a linear or branched fluorinated alkyl group is preferable, and a trifluoromethyl group, a hexafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, and the like are more preferable, and a trifluoromethyl group (—CF ₃ ). Is most preferred.
R ^a1 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

^Examples of the alkyl group having 1 to 5 carbon atoms for R ^a2 include the same as those for R ^a1 .
q is an integer of 0-2. Among these, 0 or 1 is preferable, and 0 is particularly preferable industrially.
The substitution position of R ^a2 may be any of the ortho-position, meta-position and para-position when q is 1, and when q is 2, any substitution position can be combined.
p is an integer of 1 to 3, preferably 1.
The substitution position of the hydroxyl group may be any of the ortho, meta and para positions when p is 1, but the para position is preferred because it is readily available and inexpensive. Furthermore, when p is 2 or 3, arbitrary substitution positions can be combined.

  The structural unit represented by the above formula (a-1) may be used alone or in combination of two or more.

  In the polyhydroxystyrene resin, the proportion of the structural unit derived from hydroxystyrene is preferably 60 to 100 mol%, and preferably 70 to 100 mol% with respect to all the structural units constituting the polyhydroxystyrene resin. Is more preferable, and it is further more preferable that it is 80-100 mol%. By setting it within the above range, the alkali solubility of the photosensitive resin composition can be made moderate.

It is preferable that the polyhydroxystyrene resin further has a structural unit derived from styrene.
Here, the “structural unit derived from styrene” includes a structural unit obtained by cleaving an ethylenic double bond of styrene and a styrene derivative (not including hydroxystyrene).
“Styrene derivatives” are those in which the hydrogen atom bonded to the α-position of styrene is substituted with other substituents such as a halogen atom, an alkyl group, a halogenated alkyl group, and the hydrogen atom of the phenyl group of styrene is carbon Those substituted with substituents such as alkyl groups of 1 to 5 are included.
Examples of the halogen atom include a chlorine atom, a fluorine atom and a bromine atom, and a fluorine atom is preferable.
The “α-position of styrene” means a carbon atom to which a benzene ring is bonded unless otherwise specified.

The structural unit derived from styrene is represented by the following formula (a-2), for example. In formula, R ^<a1> , R ^<a2> , q is synonymous with the said Formula (a-1).

The R ^a1 and ^{R a2,} include those similar to respectively ^{R a1} and ^{R a2} in the above formula (a1).
q is an integer of 0-2. Among these, 0 or 1 is preferable, and 0 is particularly preferable industrially.
The substitution position of R ^a2 may be any of the ortho-position, meta-position and para-position when q is 1, and when q is 2, any substitution position can be combined.

  The structural unit represented by the above formula (a-2) may be used alone or in combination of two or more.

  In the polyhydroxystyrene resin, the proportion of structural units derived from styrene is preferably 40 mol% or less, more preferably 30 mol% or less, based on all the structural units constituting the polyhydroxystyrene resin. Preferably, it is more preferably 20 mol% or less. By setting it as said range, the alkali solubility of the photosensitive resin composition can be made moderate, and the balance with another structural unit also becomes favorable.

  In addition, the polyhydroxystyrene resin may have a structural unit other than the structural unit derived from hydroxystyrene or the structural unit derived from styrene. More preferably, the polyhydroxystyrene resin is a polymer composed only of a structural unit derived from hydroxystyrene, or a copolymer composed of a structural unit derived from hydroxystyrene and a structural unit derived from styrene.

  The mass average molecular weight of the polyhydroxystyrene-based resin is not particularly limited, but is preferably 1500 to 40000, and more preferably 2000 to 8000.

  A novolak resin can also be used as the alkali-soluble resin having a phenolic hydroxyl group. This novolac resin can be obtained by addition condensation of phenols and aldehydes in the presence of an acid catalyst.

Examples of phenols include cresols such as phenol, o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4 -Xylenols such as xylenol and 3,5-xylenol; o-ethylphenol, m-ethylphenol, p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol Alkylphenols such as p-butylphenol and p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; resorcinol, catechol, hydroquinone, hydride Polyhydric phenols such as quinone monomethyl ether, pyrogallol and phloroglicinol; alkyl polyhydric phenols such as alkylresorcin, alkylcatechol and alkylhydroquinone (all alkyl groups have 1 to 4 carbon atoms); α-naphthol, β-naphthol, hydroxydiphenyl, bisphenol A and the like can be mentioned. These phenols may be used alone or in combination of two or more.
Among these phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol in combination. In this case, various characteristics such as sensitivity can be adjusted by adjusting the blending ratio of the two.

  Examples of aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of two or more.

  Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethylsulfuric acid, and paratoluenesulfonic acid; and metal salts such as zinc acetate. It is done. These acid catalysts may be used alone or in combination of two or more.

  Specific examples of the novolak resin thus obtained include phenol / formaldehyde condensed novolak resin, cresol / formaldehyde condensed novolak resin, phenol-naphthol / formaldehyde condensed novolak resin, and the like.

  The mass average molecular weight of the novolak resin is not particularly limited, but is preferably 1000 to 30000, and more preferably 3000 to 25000.

  Moreover, as an alkali-soluble resin having a phenolic hydroxyl group, a phenol-xylylene glycol condensed resin, a cresol-xylylene glycol condensed resin, a phenol-dicyclopentadiene condensed resin, or the like can be used.

  The content of the component (A) is preferably 50 to 95% by mass and more preferably 60 to 90% by mass with respect to the solid content of the positive photosensitive resin composition. By setting it as the above range, there is a tendency that developability is easily balanced.

[(B) Quinonediazide group-containing compound]
Although it does not specifically limit as a quinone diazide group containing compound (henceforth "(B) component"), The complete esterification thing and partial esterification thing of the compound which has one or more phenolic hydroxyl groups, and a quinonediazide group containing sulfonic acid Is preferred. Such a quinonediazide group-containing compound is obtained by combining a compound having one or more phenolic hydroxyl groups and a quinonediazide group-containing sulfonic acid in an appropriate solvent such as dioxane with an alkali such as triethanolamine, alkali carbonate, or alkali hydrogencarbonate. It can be obtained by condensation in the presence and complete esterification or partial esterification.

Examples of the compound having one or more phenolic hydroxyl groups include polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,3,4,4′-tetrahydroxybenzophenone;
Tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, Bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5- Dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3-hydroxyphenylmethane, Bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyl Nylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4- Hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) ) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenyl Methane, bis (5-cyclohexyl-4-hydro Shi-2-methylphenyl) -3,4-trisphenol compounds such dihydroxyphenyl methane;
Linear type 3 such as 2,4-bis (3,5-dimethyl-4-hydroxybenzyl) -5-hydroxyphenol, 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4-methylphenol Nuclear phenolic compounds;
1,1-bis [3- (2-hydroxy-5-methylbenzyl) -4-hydroxy-5-cyclohexylphenyl] isopropane, bis [2,5-dimethyl-3- (4-hydroxy-5-methylbenzyl) ) -4-hydroxyphenyl] methane, bis [2,5-dimethyl-3- (4-hydroxybenzyl) -4-hydroxyphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl)- 4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl) -4-hydroxy-5-ethylphenyl] methane, bis [3- (3,5-diethyl- 4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4- Loxy-5-ethylphenyl] methane, bis [2-hydroxy-3- (3,5-dimethyl-4-hydroxybenzyl) -5-methylphenyl] methane, bis [2-hydroxy-3- (2-hydroxy-) 5-methylbenzyl) -5-methylphenyl] methane, bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane, bis [2,5-dimethyl-3- ( Linear tetranuclear phenolic compounds such as 2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane;
2,4-bis [2-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4-bis [4-hydroxy-3- (4-hydroxybenzyl) -5 Linear type 5 such as -methylbenzyl] -6-cyclohexylphenol and 2,6-bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxybenzyl] -4-methylphenol Nuclear phenolic compounds;
Bis (2,3-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4′-hydroxyphenylmethane, 2- (2,3,4- Trihydroxyphenyl) -2- (2 ′, 3 ′, 4′-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ′, 4′-dihydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (4′-hydroxyphenyl) propane, 2- (3-fluoro-4-hydroxyphenyl) -2- (3′-fluoro-4′-hydroxyphenyl) propane, 2- ( 2,4-dihydroxyphenyl) -2- (4′-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4′-hydroxypheny) ) Propane, 2- (2,3,4-trihydroxyphenyl) -2- (4′-hydroxy-3 ′, 5′-dimethylphenyl) propane, 4,4 ′-[1- [4- [1- Bisphenol type compounds such as (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol;
1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl]- Polynuclear branched compounds such as 4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene;
And a condensed phenol compound such as 1,1-bis (4-hydroxyphenyl) cyclohexane.
These compounds may be used alone or in combination of two or more.

  Examples of the quinonediazide group-containing sulfonic acid include naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, and orthoanthraquinonediazidesulfonic acid.

  The content of the component (B) is preferably 5 to 50 parts by mass and more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the component (A). By setting it as said range, the sensitivity of positive photosensitive resin composition can be made favorable.

[(C) polyvinyl alkyl ether]
The positive photosensitive resin composition may contain polyvinyl alkyl ether (hereinafter also referred to as “component (C)”) as a plasticizer. By containing polyvinyl alkyl ether as a plasticizer, the etching resistance of the positive photosensitive resin composition can be improved.

  The alkyl portion of the polyvinyl alkyl ether preferably has 1 to 5 carbon atoms, and more preferably 1 or 2 carbon atoms. That is, the polyvinyl alkyl ether is more preferably polyvinyl methyl ether or polyvinyl ethyl ether.

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

  It is preferable that content of (C) component is 1-100 mass parts with respect to 100 mass parts of (A) component. By setting it as the above range, the etching resistance of the positive photosensitive resin composition can be appropriately adjusted.

[(S) Organic solvent]
The positive photosensitive resin composition preferably contains an organic solvent for dilution (hereinafter also referred to as “component (S)”).
It does not specifically limit as an organic solvent, The organic solvent currently used widely by this field | area can be used. For example, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether Alkyl ethers; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monoalkyl ether acetates such as pyrene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as butyl carbitol; methyl lactate, ethyl lactate, n-propyl lactate Lactic acid esters such as isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate, etc. Aliphatic carboxylic acid esters of methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate Other esters such as methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; N-dimethylformamide, N- And amides such as methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ-butyrolacun; and the like.
These organic solvents may be used alone or in combination of two or more.

  The content of the component (S) is not particularly limited, but in general, the solid content concentration of the positive photosensitive resin composition is preferably 10 to 60% by mass, and more preferably 20 to 50% by mass. .

[Other ingredients]
The positive photosensitive resin composition may contain an additional resin, a stabilizer, a colorant, a surfactant, an inorganic filler, a silane coupling agent, and the like as desired.

  Although it does not specifically limit as an inorganic filler, Barium sulfate etc. are used suitably. By containing an inorganic filler, etching resistance, physical stress resistance, and thermal stress resistance can be improved.

  A conventionally known silane coupling agent can be used as the silane coupling agent, but it is preferably not contained. By not containing a silane coupling agent, the temporal stability can be improved.

<Negative photosensitive resin composition>
The negative photosensitive resin composition contains (A) an alkali-soluble resin having a phenolic hydroxyl group, (D) a crosslinking agent, and (E) an acid generator.

[(A) Alkali-soluble resin having phenolic hydroxyl group]
As the alkali-soluble resin having a phenolic hydroxyl group (hereinafter, also referred to as “component (A)”), those exemplified in the positive photosensitive resin composition can be used.

  The content of the component (A) is preferably 50 to 99% by mass and more preferably 60 to 95% by mass with respect to the solid content of the negative photosensitive resin composition. By setting it as the above range, there is a tendency that developability is easily balanced.

[(D) Crosslinking agent]
Although it does not specifically limit as a crosslinking agent (henceforth "(D) component"), For example, an amino compound, for example, a melamine resin, urea resin, guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, ethylene urea -Formaldehyde resin or the like can be used.

  Among these, alkoxymethylated amino resins such as alkoxymethylated melamine resins and alkoxymethylated urea resins are preferable. Alkoxymethylated amino resin is, for example, etherified with a condensate obtained by reacting melamine or urea with formalin in a boiling aqueous solution with lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, and isopropyl alcohol. And then the reaction solution is cooled and precipitated. Examples of alkoxymethylated amino resins include methoxymethylated melamine resins, ethoxymethylated melamine resins, propoxymethylated melamine resins, butoxymethylated melamine resins, methoxymethylated urea resins, ethoxymethylated urea resins, propoxymethylated urea resins, Examples include butoxymethylated urea resin.

  These cross-linking agents may be used alone or in combination of two or more.

  The content of the component (D) is preferably 5 to 50 parts by mass and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the component (A). By setting it as said range, sclerosis | hardenability and patterning characteristic of a negative photosensitive resin composition become favorable.

[(E) Acid generator]
It does not specifically limit as an acid generator (henceforth "(E) component"), A conventionally well-known acid generator can be used.

  Specific examples of the acid generator include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, halogen-containing triazine compounds, diazomethane acid generators, nitrobenzyl sulfonate acid generators (nitro Benzyl derivatives), iminosulfonate acid generators, disulfone acid generators and the like.

  As a preferable sulfonium salt acid generator, for example, a compound represented by the following formula (e-1) may be mentioned.

In the above formula (e-1), R ^e1 and R ^e2 may each independently have a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group that may have a halogen atom, or a substituent. Represents an alkoxy group, R ^e3 represents a halogen atom or a p-phenylene group optionally having an alkyl group, R ^e4 represents a hydrocarbon group optionally having a hydrogen atom, an oxygen atom or a halogen atom, substituted A benzoyl group which may have a group or a polyphenyl group which may have a substituent, and A ⁻ represents a counter ion of an onium ion.

Specific examples of A ⁻ include SbF ₆ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , BF ₄ ⁻ , SbCl ₆ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , FSO ₃ ⁻ and F _2. Examples thereof include PO ₂ ⁻ , p-toluenesulfonate, nonafluorobutanesulfonate, adamantanecarboxylate, tetraarylborate, and a fluorinated alkylfluorophosphate anion represented by the following formula (e-2).

  In the above formula (e-2), Rf represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. n is the number and represents an integer of 1 to 5. The n Rf's may be the same or different.

  Examples of the acid generator represented by the above formula (e-1) include 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio). ) Phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-) Benzoylphenylthio) phenylbis (4-methylphenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4- (β-hydroxyethoxy) phenyl) sulfonium hexafluoroantimonate, 4- ( -Methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (3-methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-Fluoro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoro Antimonate, 4- (2,3,5,6-tetramethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,6-dichloro-4-benzoi Ruphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,6-dimethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2, 3-dimethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (3-Methyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-fluoro-4-benzoylphenylthio) phenylbis (4-chloro Phenyl) sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,3,5,6-tetramethyl-4- Benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,6-dichloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2, 6-dimethyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,3-dimethyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfoni Hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoroantimony 4- (2-chloro-4- (4-fluorobenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoroantimonate 4- (2-chloro-4-dodecanoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenylbis ( 4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4 -(4-Fluorobenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexa Fluoroantimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenylbis ( -Chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4 -Fluorobenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4 -(2-Chloro-4-dodecanoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfone Nitrohexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium perchlorate, 4- (2-chloro -4-benzoylphenylthio) phenyldiphenylsulfonium trifluoromethanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoyl) Phenylthio) phenylbis (4-fluorophenyl) sulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfoniu Muphalolate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium trifluoromethanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) ) Sulfonium p-toluenesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium camphorsulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4- Fluorophenyl) sulfonium nonafluorobutanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylpheny) Thio) phenylbis (4-chlorophenyl) sulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium perchlorate, 4- (2-chloro-4-benzoylphenylthio) ) Phenylbis (4-chlorophenyl) sulfonium trifluoromethanesulfonate, diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotrispentafluoroethyl phosphate, diphenyl [4- (p-terphenylthio) phenyl] sulfonium hexafluoroantimonate And diphenyl [4- (p-terphenylthio) phenyl] sulfonium trifluorotrispentafluoroethyl phosphate.

  As other onium salt-based acid generators, the cation moiety of the above formula (e-1) may be selected from, for example, triphenylsulfonium, (4-tert-butoxyphenyl) diphenylsulfonium, bis (4-tert-butoxyphenyl) phenyl. Sulfonium, tris (4-tert-butoxyphenyl) sulfonium, (3-tert-butoxyphenyl) diphenylsulfonium, bis (3-tert-butoxyphenyl) phenylsulfonium, tris (3-tert-butoxyphenyl) sulfonium, (3 4-ditert-butoxyphenyl) diphenylsulfonium, bis (3,4-ditert-butoxyphenyl) phenylsulfonium, tris (3,4-ditert-butoxyphenyl) sulfonium, diphenyl (4-thiophenoxy) Phenyl) sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl) diphenylsulfonium, tris (4-tert-butoxycarbonylmethyloxyphenyl) sulfonium, (4-tert-butoxyphenyl) bis (4-dimethylaminophenyl) sulfonium, Tris (4-dimethylaminophenyl) sulfonium, 2-naphthyldiphenylsulfonium, dimethyl-2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthyl Sulfonium cations such as sulfonium and tribenzylsulfonium, diphenyliodonium, bis (4- ert- butyl phenyl) iodonium, include those replaced with (4-tert- butoxyphenyl) phenyliodonium, (4-methoxyphenyl) iodonium cation aryl iodonium cations such as iodonium.

Examples of the oxime sulfonate acid generator include [2- (propylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] (o-tolyl) acetonitrile, 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 like can be mentioned.
In addition to the above, a compound represented by the following formula (e-3) can be given.

In the above formula (e-3), R ^e5 represents a monovalent, divalent, or trivalent organic group, and R ^e6 represents a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromaticity. A compound group is shown, r shows the integer of 1-6.
R ^e5 is particularly preferably an aromatic compound group. Examples of such an aromatic compound group include aromatic hydrocarbon groups such as a phenyl group and a naphthyl group, and heterocyclic rings such as a furyl group and a thienyl group. Groups and the like. These may have one or more suitable substituents such as a halogen atom, an alkyl group, an alkoxy group, and a nitro group on the ring. R ^e6 is particularly preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. R is preferably an integer of 1 to 3, and more preferably 1 or 2.

As an acid generator represented by the above formula (e-3), when r = 1, R ^e5 is any one of a phenyl group, a methylphenyl group, and a methoxyphenyl group, and R ^e6 is The compound which is a methyl group is mentioned. More specifically, the acid generator represented by the above formula (e-3) includes α- (methylsulfonyloxyimino) -1-phenylacetonitrile, α- (methylsulfonyloxyimino) -1- (p- Methylphenyl) acetonitrile, and α- (methylsulfonyloxyimino) -1- (p-methoxyphenyl) acetonitrile.

  Examples of the acid generator represented by the general formula (e-3) include an acid generator represented by the following formula when r = 2.

  Examples of halogen-containing triazine compounds include 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-di Ethoxypheny ) Ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dipropoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -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-triazine Loromethyl-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-Zime Toxiphenyl) 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) -1 , 3,5-triazine, halogen-containing triazine compounds such as tris (2,3-dibromopropyl) -1,3,5-triazine, and tris (2,3-dibromopropyl) isocyanurate -4) is a halogen-containing triazine compound.

In said formula (e-4), R ^<e7> , R ^{<e8 >} , R ^{< e9 >} shows a C1-C6 halogenated alkyl group each independently.

  Other acid generators include bis (p-toluenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1- (1,1-dimethylethylsulfonyl) diazomethane, bis (1, 1-dimethylethylsulfonyl) diazomethane, bis (1-methylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (4-ethylphenylsulfonyl) diazomethane, bis (3 -Methylphenylsulfonyl) diazomethane, bis (4-methoxyphenylsulfonyl) diazomethane, bis (4-fluorophenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazome Bissulfonyldiazomethanes such as bis (4-tert-butylphenylsulfonyl) diazomethane; 2-methyl-2- (p-toluenesulfonyl) propiophenone, 2- (cyclohexylcarbonyl) -2- (p-toluenesulfonyl) ) Sulfonylsulfonyl alkanes such as propane, 2-methanesulfonyl-2-methyl- (p-methylthio) propiophenone, 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one; -Toluenesulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-methylsulfonyl-4-phenyl-2-butanone, 1-cyclohexylsulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-cyclohexylsulfonyl-3,3 -Dimethyl 2-butanone, 1-diazo-1- (1,1-dimethylethylsulfonyl) -3,3-dimethyl-2-butanone, 1-acetyl-1- (1-methylethylsulfonyl) diazomethane, 1-diazo-1 -(P-toluenesulfonyl) -3,3-dimethyl-2-butanone, 1-diazo-1-benzenesulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1- (p-toluenesulfonyl)- 3-methyl-2-butanone, 2-diazo-2- (p-toluenesulfonyl) acetate cyclohexyl, 2-diazo-2-benzenesulfonylacetate-tert-butyl, 2-diazo-2-methanesulfonylacetate isopropyl, 2- Diazo-2-benzenesulfonyl acetate cyclohexyl, 2-diazo-2- (p-toluenesulfonyl) acetate-tert-butyl, etc. Sulfonylcarbonyldiazomethanes; nitrobenzyl derivatives such as p-toluenesulfonic acid-2-nitrobenzyl, p-toluenesulfonic acid-2,6-dinitrobenzyl, p-trifluoromethylbenzenesulfonic acid-2,4-dinitrobenzyl Methanesulfonate of pyrogallol, benzenesulfonate of pyrogallol, p-toluenesulfonate of pyrogallol, p-methoxybenzenesulfonate of pyrogallol, mesitylene sulfonate of pyrogallol, benzyl sulfonate of pyrogallol, gallic acid Alkyl methanesulfonate ester, alkyl gallate benzenesulfonate ester, alkyl gallate p-toluenesulfonate ester, alkyl gallate (carbon of alkyl group) 1 to 15) esters of polyhydroxy compounds such as p-methoxybenzenesulfonic acid ester, alkyl gallate mesitylenesulfonic acid ester, alkyl gallic acid benzylsulfonic acid ester and aliphatic or aromatic sulfonic acid And the like.

  These acid generators may be used alone or in combination of two or more.

  The content of the component (E) is preferably 0.05 to 30 parts by mass and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A). By setting it as said range, sclerosis | hardenability of a negative photosensitive resin composition becomes favorable.

[(C) polyvinyl alkyl ether]
The negative photosensitive resin composition may contain polyvinyl alkyl ether (hereinafter also referred to as “component (C)”) as a plasticizer. By containing polyvinyl alkyl ether as a plasticizer, the etching resistance of the negative photosensitive resin composition can be improved. As this polyvinyl alkyl ether, what was illustrated in the positive photosensitive resin composition can be used.

  It is preferable that content of (C) component is 1-100 mass parts with respect to 100 mass parts of (A) component. By setting it as said range, the etching tolerance of a negative photosensitive resin composition can be adjusted moderately.

[(S) Organic solvent]
The negative photosensitive resin composition preferably contains an organic solvent for dilution (hereinafter also referred to as “component (S)”). As this organic solvent, those exemplified in the positive photosensitive resin composition can be used.

  The content of the component (S) is not particularly limited, but in general, the amount of the negative photosensitive resin composition in which the solid content concentration is 10 to 60% by mass is preferable, and the amount of 20 to 50% by mass is more preferable. .

[Other ingredients]
The negative photosensitive resin composition may contain an additional resin, a stabilizer, a colorant, a surfactant, an inorganic filler, a silane coupling agent, and the like as desired.

  Although it does not specifically limit as an inorganic filler, Barium sulfate etc. are used suitably. By containing an inorganic filler, etching resistance, physical stress resistance, and thermal stress resistance can be improved.

  A conventionally known silane coupling agent can be used as the silane coupling agent, but it is preferably not contained. By not containing a silane coupling agent, the temporal stability can be improved.

≪Glass processing method≫
The glass processing method according to the present invention includes a coating film forming step of forming a coating film of a photosensitive resin composition containing an alkali-soluble resin having a phenolic hydroxyl group on a glass substrate, and selectively exposing the coating film. An exposure step, a development step for developing the coated film after exposure to form a resin pattern, an etching step for etching the glass substrate using the resin pattern as a mask, and a peeling step for peeling the resin pattern. It is a waste.

First, in the coating film forming step, for example, the above-described photosensitive property on a glass substrate using a contact transfer type coating apparatus such as a roll coater, a reverse coater, or a bar coater, or a non-contact type coating apparatus such as a spinner or a curtain flow coater. A resin film is applied and heated (prebaked) to form a coating film. Although the film thickness of a coating film is not specifically limited, For example, it is about 20-200 micrometers. Although heating conditions are not specifically limited, For example, it is about 2 to 60 minutes at 70-150 degreeC.
In addition, you may repeat application | coating and prebaking of the photosensitive resin composition in multiple times so that a desired film thickness may be obtained.

  In the coating film forming step, the above-described photosensitive resin composition is applied onto a release film, and then dried. After forming a dry film by a conventional method, the coating film is formed by sticking to a glass substrate. You can also.

Next, in the exposure step, the coating film is selectively exposed by irradiating active energy rays such as ultraviolet rays through the light shielding pattern. For the exposure, a light source that emits ultraviolet rays such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used. Although the energy dose to be irradiated varies depending on the composition of the photosensitive resin composition, it is preferably about 30 to 3000 mJ / cm ² , for example.

  The glass processing method according to the present invention may include a heating (PEB) step after the exposure step. Although heating conditions are not specifically limited, For example, it is about 3 to 20 minutes at 80-150 degreeC.

  Next, in the development step, the coated film after exposure is developed to form a resin pattern. The development method is not particularly limited, and an immersion method, a spray method, a shower method, a paddle method, or the like can be used. Examples of the developer include 0.25 to 3% by mass of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, organic amine, tetramethylammonium hydroxide, triethanolamine, N-methylpyrrolidone, dimethyl sulfoxide and the like. The development time is not particularly limited, but is, for example, about 1 to 120 minutes. In addition, you may heat a developing solution to about 25-40 degreeC.

  In addition, the glass processing method which concerns on this invention may include the heating (post-baking) process after the image development process. Although heating conditions are not specifically limited, For example, it is about 2-120 minutes at 70-300 degreeC.

  Moreover, when the photosensitive resin composition is a positive type, an after-cure process of heating while irradiating active energy rays such as ultraviolet rays may be included after the development process. In this after-cure process, the quinonediazide group-containing compound contained in the photosensitive resin composition forms an intermediate (indeneketene) by active energy rays, which binds to an alkali-soluble resin having a phenolic hydroxyl group or a quinonediazide group-containing compound. To polymerize.

  Next, in the etching step, the glass substrate is etched using the resin pattern as a mask. Examples of the etching method include wet etching that is generally performed and is immersed in an etching solution. Examples of the etching solution include hydrofluoric acid alone, hydrofluoric acid and ammonium fluoride, mixed acid of hydrofluoric acid and other acids (hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and the like). The etching processing time is not particularly limited, but is, for example, about 10 to 60 minutes. In addition, you may heat an etching liquid to about 25-60 degreeC.

  Among these etching conditions, the glass processing method according to the present invention is particularly an etching solution containing 25 to 60 ° C. containing hydrofluoric acid and sulfuric acid, more specifically 5 to 30 mass% hydrofluoric acid and 5 to 30 mass. This is particularly effective when etching is performed using an etching solution at 25 to 60 ° C. containing 1% sulfuric acid. The photosensitive resin composition used in the present invention exhibits high etching resistance even under such severe etching conditions.

Next, in the peeling step, the resin pattern is peeled off. The peeling method is not particularly limited, and an immersion method, a spray method, a shower method, a paddle method, or the like can be used. Examples of the stripping solution include a 3 to 15% by mass aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an organic amine, tetramethylammonium hydroxide, triethanolamine, N-methylpyrrolidone, and dimethyl sulfoxide. The peeling treatment time is not particularly limited, but is, for example, about 1 to 120 minutes. The stripping solution may be heated to about 25 to 60 ° C.
In this way, the glass substrate can be processed.

  Examples of the present invention will be described below, but the scope of the present invention is not limited to these examples.

<Examples 1-8, Comparative Examples 1-6>
According to the formulation shown in Table 1 (unit is part by mass), an alkali-soluble resin having a phenolic hydroxyl group, a quinonediazide group-containing compound, a polyvinyl alkyl ether, and an organic solvent are mixed, and the positive photosensitivity of Examples 1 to 4. A resin composition was prepared.
Moreover, according to the prescription (a unit is a mass part) of Table 2, the alkali-soluble resin which has a phenolic hydroxyl group, a crosslinking agent, an acid generator, polyvinyl alkyl ether, and an organic solvent are mixed, and Examples 5-8 are mixed. A negative photosensitive resin composition was prepared.
Further, according to the formulation shown in Table 3 (unit is part by mass), an alkali-soluble resin, a polymerizable monomer, a radical polymerization initiator, a silane coupling agent, an inorganic filler, and an organic solvent were mixed, and Comparative Examples 1 to 6 A negative photosensitive resin composition was prepared.
The detail of each component in Tables 1-3 is as follows.

Alkali-soluble resin A having a phenolic hydroxyl group: obtained by mixing m-cresol and p-cresol at m-cresol / p-cresol = 60/40 (mass ratio), adding formalin, and adding and condensing by a conventional method. Cresol novolak resin (mass average molecular weight 15000)
Alkali-soluble resin B having phenolic hydroxyl group: polyhydroxystyrene (mass average molecular weight 6000)
Quinonediazide group-containing compound A: 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide- Condensation product with 4-sulfonic acid chloride (2 mol) (4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2- Naphthoquinonediazide-5-sulfonic acid ester)
Crosslinking agent A: 2,4,6-tris [bis (methoxymethyl) amino] -1,3,5-triazine (manufactured by Sanwa Chemical Co., Mw-100LM)
Acid generator A: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine Polyvinyl alkyl ether A: Polyvinyl methyl ether (mass average molecular weight 100,000) (manufactured by BASF Corp., Rutonal)
Organic solvent A: Propylene glycol monomethyl ether acetate

Alkali-soluble resin A: benzyl methacrylate / methacrylic acid = 80/20 (molar ratio) copolymer (mass average molecular weight 60000)
Alkali-soluble resin B: copolymer of benzyl methacrylate / methacrylic acid = 80/20 (molar ratio) (mass average molecular weight 90000)
Alkali-soluble resin C: Resin in which an epoxy group of 3,4-epoxycyclohexylmethyl acrylate is reacted with a carboxyl group of a copolymer of (meth) acrylic acid and (meth) acrylic acid ester (mass average molecular weight 16000, acid value 110 mg KOH / mg) (Daicel Cytec, Cyclomer ACA Z250)
Polymerizable monomer A: trimethylolpropane triacrylate (manufactured by Toa Gosei Co., Ltd., Aronix M309)
Polymerizable monomer B: Tricyclodecane methanol diacrylate (manufactured by Kyoeisha Chemical Co., TCP-A)
Polymerizable monomer C: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
Polymerizable monomer D: Polyfunctional polyester acrylate (Aronix M9050, manufactured by Toagosei Co., Ltd.)
Radical polymerization initiator A: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (manufactured by BASF, Irgacure 369)
Silane coupling agent A: 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone, KBM903)
Inorganic filler A: precipitated barium sulfate (manufactured by Sakai Chemical Co., B-30)

<Development evaluation>
The positive photosensitive resin compositions of Examples 1 to 4 were coated on a glass substrate (Corning Co., Eagle-XG) with a spin coater, and heated (prebaked) at 90 ° C. for 5 minutes. After repeating the same coating and heating again, heating (prebaking) was performed at 110 ° C. for 40 minutes to obtain a coating film having a film thickness of 45 to 50 μm. Next, the coating film was irradiated with ultraviolet rays at a dose of 3000 mJ / cm ² through a mask on which a line pattern having a line width of 200 μm was formed. Then, the exposed portion was dissolved and removed by immersing the glass substrate in a 1% by mass aqueous sodium hydroxide solution heated to 30 ° C. for 5 minutes to form a line and space pattern. The developability was evaluated by measuring the time (break point) until the exposed portion was completely removed. The results are shown in Table 4.

Moreover, the negative photosensitive resin composition of Examples 5-8 was apply | coated with the spin coater on the glass substrate (Corning company make, Eagle-XG), and it heated at 90 degreeC for 5 minutes, and 110 degreeC for 20 minutes (prebaking). And a coating film having a film thickness of 60 μm was obtained. Next, the coating film was irradiated with ultraviolet rays at a dose of 150 mJ / cm ² through a mask on which a line pattern having a line width of 200 μm was formed, and then heated (PEB) at 110 ° C. for 6 minutes. Next, the glass substrate was immersed in a 1% by mass sodium hydroxide aqueous solution heated to 30 ° C. for 5 minutes to dissolve and remove unexposed portions, thereby forming a line and space pattern. And developability was evaluated by measuring time (breakpoint) until an unexposed part is removed completely. The results are shown in Table 4.

Further, development was performed in the same manner as in Examples 5 to 8 except that the negative photosensitive resin compositions of Comparative Examples 1 to 6 were used. However, since development was not possible with a 1% by mass sodium hydroxide aqueous solution heated to 30 ° C., spray development was performed using a 1% by mass sodium carbonate aqueous solution heated to 30 ° C. under the conditions of 1 kg / cm ^2. An and space pattern was formed. And developability was evaluated by measuring time (breakpoint) until an unexposed part is removed completely. The results are shown in Table 5.

<Evaluation of resolution>
Except for using a mask on which a line pattern with a line width of 40 to 200 μm was formed, the coating film was exposed and developed in the same manner as in the above <evaluation of developability> to form a line and space pattern. Then, the resolution was evaluated based on the minimum resolvable mask dimension. The results are shown in Tables 4 and 5.

<Evaluation of etching resistance>
Except for using a mask on which a line pattern having a line width of 200 μm was used, the coating film was exposed and developed in the same manner as in the above <evaluation of resolution> to form a line and space pattern. About the line and space pattern obtained using the negative photosensitive resin composition of Comparative Examples 1-6, it heated at 200 degreeC for 20 minutes (post-baking) further.
Next, the glass substrate was etched using this line and space pattern as a mask. The etching treatment was performed by heating an etching solution of hydrofluoric acid / sulfuric acid / water = 15/15/70 (mass ratio) to 55 ° C. and swinging the glass substrate in the etching solution. Then, the etching resistance was evaluated by measuring the time until the line and space pattern peeled and the etching amount up to that point. The results are shown in Tables 4 and 5.

<Evaluation of peelability>
A line and space pattern was formed in the same manner as in the above <Evaluation of etching resistance>. Subsequently, the line and space pattern was peeled and removed by immersing the glass substrate in a 10% by mass sodium hydroxide aqueous solution heated to 55 ° C. And peelability was evaluated by measuring time until a line and space pattern completely peeled. The results are shown in Tables 4 and 5.

  As can be seen from Table 4, the positive photosensitive resin compositions of Examples 1 to 4 and the negative photosensitive resin compositions of Examples 5 to 8 containing an alkali-soluble resin having a phenolic hydroxyl group are 1% by mass. Development was possible with an aqueous sodium hydroxide solution, and the resolution was excellent at 40 μm or less. Further, even under severe etching conditions using an etching solution at 50 ° C. containing 15% by mass of hydrofluoric acid and 15% by mass of sulfuric acid, it showed excellent etching resistance and good peelability.

On the other hand, as can be seen from Table 5, the negative photosensitive resin compositions of Comparative Examples 1 to 6 not containing an alkali-soluble resin having a phenolic hydroxyl group could be developed with a 1% by mass aqueous sodium carbonate solution. The resolution was inferior to Examples 1-8. Moreover, etching resistance was also inferior to Examples 1-8, and it was inversely proportional to etching resistance improving, and peelability deteriorated. In addition, when an inorganic filler was contained as in Comparative Example 6, the etching resistance was improved to the same extent as in Examples 1 to 8, but the developability and resolution were significantly deteriorated.

Claims (6)

A coating film forming step of forming a coating film of a photosensitive resin composition containing an alkali-soluble resin having a phenolic hydroxyl group and a polyvinyl alkyl ether as a plasticizer on a glass substrate;
An exposure step of selectively exposing the coating film;
A development step of developing the coating film after exposure to form a resin pattern;
An etching step of etching the glass substrate using the resin pattern as a mask;
The glass processing method including the peeling process which peels the said resin pattern.   The glass processing method of Claim 1 which etches the said glass substrate using the etching liquid of 25-60 degreeC containing a hydrofluoric acid and a sulfuric acid in the said etching process.   The glass processing method according to claim 1, further comprising a heating step of heating the resin pattern before the etching step. The glass processing method according to any one of claims 1 to 3, wherein the polyvinyl alkyl ether has a mass average molecular weight of 10,000 to 200,000. The glass processing method of any one of Claim 1 to 4 in which the said photosensitive resin composition further contains a quinonediazide group containing compound. The glass processing method of any one of Claim 1 to 4 in which the said photosensitive resin composition further contains a crosslinking agent and an acid generator.