TW201627238A - Pretreatment method of glass substrate for forming etching mask - Google Patents

Abstract

To provide a pretreatment method of glass substrate, a method for forming an etching mask on the glass substrate having been subject to the pretreatment method, and an etching processing method for the glass substrate with etching mask formed using the etching mask forming method. In the pretreatment method of glass substrate, when forming an etching mask on the glass substrate with a surface having metal wire and non-conductive coating, the cross-sectional area at the planar direction of the glass substrate of the opening of the etching mask, the cross-sectional area difference between the lateral surface of the glass substrate and the opening on the etching mask surface can be reduced, and the etching mask which can be rapidly removed from whole surface of the glass substrate can be formed. Prior to forming the etching mask on the glass substrate having a surface with a non-conductive coating composed of metal wire and organic or inorganic material, an amine treatment is applied to the glass substrate surface which contains a treatment solution containing amine not having functional groups capable of forming chemical bond with the glass substrate surface.

Description

Processing method for forming a glass substrate for etching a mask

The present invention relates to a method for processing a glass substrate for forming an etching mask which is provided on a glass substrate having a metal wiring and a non-conductive film made of an organic or inorganic material, and has been subjected to the pretreatment method. A method of forming an etching mask on a glass substrate, and a processing method of etching on a glass substrate having an etching mask formed by the method.

The touch panel is formed by separately forming a transparent conductive material such as ITO on the opposite surface of the opposing glass substrate and the film via a spacer. In this touch panel, the contact position of the film is detected as coordinate information.

Moreover, there has recently been a touch panel integrated liquid crystal display. In this case, one of the two glass substrates constituting the liquid crystal display has a glass substrate of a touch panel, and is very effective in achieving reduction in thickness and weight.

In the past, as a method of processing such a glass substrate, it is generally a physical method, but cracks are likely to occur during processing, and strength is lowered. Low or poor yield.

For this reason, in recent years, a chemical method in which a resin pattern obtained by patterning a photoresist composition is used as a mask to etch a glass substrate has been proposed (for example, refer to Patent Documents 1 and 2). Since such a chemical method does not impose a physical load during processing, cracks are less likely to occur. Moreover, unlike the physical method, the glass substrate can be subjected to a punching process for a microphone or a speaker.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2008-076768

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-072518

However, in the methods described in Patent Documents 1 and 2, depending on the glass material constituting the glass substrate, it takes a long time to peel the etching mask formed using the photoresist composition from the surface of the glass substrate, or to peel off the etching mask. After the cover, there is a problem that a large amount of residue remains on the surface of the glass substrate. This problem is particularly remarkable when the polymer compound contained in the photoresist composition has a hydroxyl group or a carboxyl group.

Further, a metal wiring is formed in advance on the surface of the etched glass substrate, or a non-conductive material composed of an organic or inorganic material The film is a permanent film. However, in the case where a photoresist mask is formed on the glass substrate having the metal wiring and the permanent film on the surface, an etching mask is formed, and the etching process is performed. When the etching mask is peeled off, the surface state of the glass substrate, the metal wiring, and the permanent film is The difference is that there is a problem that a residue of a partially etched mask is generated on the surface of the glass substrate.

Regarding the problem of the peeling property of the etching mask, it is considered that the interaction of a functional group such as a sterol group existing on the surface of the glass substrate with a functional group having a polarity of the photoresist composition is one of the causes. As a method of maintaining the affinity (adhesion) of the etching mask on the surface of the glass substrate and suppressing the above interaction, it is considered that the surface of the glass substrate is treated with a decane coupling agent or the like to be hydrophobized. However, in this case, the cross-sectional area of the surface side of the glass substrate in the etched mask formed by using the photoresist composition in the direction of the surface of the glass substrate is likely to be larger than that of the etch mask. The cross-sectional area of the opening on the surface is problematic.

When the area on the side of the glass substrate becomes larger than the area of the opening on the surface of the etching mask in the opening portion in the etching mask, there is a problem in the dimensional accuracy of the etching process.

An object of the present invention is to provide a method for pretreating a glass substrate, a method for forming an etching mask on a glass substrate on which the pretreatment method has been applied, and an etching substrate provided on the glass substrate having the etching mask formed by the method. A method for processing a glass substrate, which is an opening in an etching mask when an etching mask is formed on a glass substrate having a metal wiring and a non-conductive coating made of an organic or inorganic material on the surface thereof. The cross-sectional area in the direction of the surface of the glass substrate can be reduced The difference between the cross-sectional area of the surface side of the glass substrate and the cross-sectional area of the opening on the surface of the etching mask, and the etching of the entire surface of the glass substrate can be formed without being different depending on the type of the surface material on the glass substrate. cover.

The present inventors have found that the surface of the glass substrate is coated with a non-functional glass substrate before the etching mask is formed on the surface of the glass substrate having the metal wiring and the non-conductive coating made of an organic or inorganic material. The amine treatment by the treatment liquid of the amine having a chemically bonded functional group on the surface can solve the above problems and further complete the present invention.

A first aspect of the present invention is a method for pretreating a glass substrate, which is a method for performing a treatment before the etching mask is formed on the surface of the glass substrate by photolithography using a photoresist composition, which comprises an amine treatment. a step of treating the surface of the glass substrate with an amine formed by the treatment liquid, and the treatment liquid contains an amine having no functional group capable of chemically bonding with the surface of the glass substrate; The glass substrate is provided with a metal wiring and a non-conductive film made of an organic or inorganic material on the surface thereof, and a portion where the glass is exposed, a portion where the metal wiring is exposed, and a portion where the film is exposed are present on the surface of the glass substrate. Sodium and / or potassium.

A second aspect of the present invention is a method of forming an etch mask, comprising: the foregoing glass substrate treated by a prior art processing method as in the first aspect a coating film forming step of coating a photoresist composition to form a coating film on the surface of the sheet; an exposure step of selectively exposing the coating film; and developing the exposed coating film to form an etching mask The imaging step.

A third aspect of the present invention provides a method of processing a glass substrate, comprising: ???the etch mask provided on the glass substrate having the etch mask formed by the method of forming the etch mask of the second aspect; An etching step of etching the portion of the glass on the surface of the cover; and a peeling step of peeling the etching mask from the surface of the glass substrate after the etching step.

The present invention can provide a method for pretreating a glass substrate, a method for forming an etching mask on a glass substrate on which the pretreatment method has been applied, and a method for etching a glass substrate having an etching mask formed by the method. The method for processing a glass substrate is to form an etching mask on a glass substrate having a metal wiring and a non-conductive coating made of an organic or inorganic material on the surface, and to form an etching mask in the etching mask. The cross-sectional area in the surface direction of the glass substrate can reduce the difference between the cross-sectional area of the surface side of the glass substrate and the cross-sectional area of the opening on the surface of the etching mask, and can be prevented from being different depending on the type of the surface material on the glass substrate. An etch mask capable of rapidly peeling off the entire surface of the glass substrate is formed.

Hereinafter, the present invention will be described in accordance with the order of the glass substrate to be processed, the photoresist composition used for forming the etching mask, the glass substrate pretreatment method, the etching mask forming method, and the glass substrate processing method.

Glass substrate

In the pretreatment method for a glass substrate, a glass substrate having a metal wiring and a non-conductive coating made of an organic or inorganic material (hereinafter also referred to as a permanent film) is used. The surface of the glass substrate includes a portion where the glass is exposed, a portion where the metal wiring is exposed, and a portion where the film is exposed. The material of the glass substrate is not particularly limited as long as it contains glass of sodium and/or potassium. The material of the glass substrate is selected from the previously known glasses in consideration of the strength, the manufacturing cost of the product, and the like.

The glass substrate is preferably a glass substrate having a Vickers hardness of 500 kgf/mm ² or more. The Vickers hardness of the substrate based glass to 600kgf / mm ² or more is preferred to 650kgf / mm ² or more is particularly preferred. The higher the Vickers hardness of the glass substrate, the better, but the Vickers strength of the glass substrate which can be obtained in reality is 2000 kgf/mm ² or less.

The type of the glass substrate having a Vickers hardness of 500 kgf/mm ² or more is not particularly limited. Typically, a glass substrate having a Vickers hardness of 500 kgf/mm ² or more is a chemically strengthened glass substrate. The chemically strengthened glass substrate refers to an ion exchanger that applies sodium ions and potassium ions to the surface layer of the glass substrate by bringing a glass substrate containing sodium in the surface layer into contact with a molten salt containing potassium. As the degree of strengthening, as long as the strength after the treatment has been increased before the ion exchange treatment, the strength is not particularly limited, and the ion exchange treatment is performed on the surface of the glass substrate. By compressing the layer, the strength of the glass substrate can be strengthened to, for example, 5 times or more.

The Vickers hardness of the glass substrate can be measured in accordance with JIS Z 2244. The thickness of the glass substrate at the time of measuring the Vickers hardness is not particularly limited as long as it is not damaged by the indentation of the indenter when the hardness is measured.

The glass substrate described above is provided with a metal wiring and a permanent film which is a non-conductive coating on the surface on the side to be etched. Therefore, the etching performed on the glass substrate having the metal wiring and the permanent film on the surface is performed on the exposed portion of the glass.

Most of the glass substrates to be etched are used as substrates for various devices in a state in which metal wiring and a permanent film are provided on the surface. However, when a large-sized glass substrate having a metal wiring and a permanent film is not cut by etching, and a plurality of glass substrates having a predetermined size are cut out, it is necessary to form metal wiring on the surface of the plurality of small glass substrates to be obtained. The complicated steps of permanent film.

On the other hand, when the metal wiring and the permanent film to be provided in the small-sized glass substrate are formed in advance on the surface of the large-sized glass substrate before the cutting, the small-sized glass substrate obtained by the etching process can be directly used as various devices. The substrate.

The method of forming the metal wiring on the surface of the glass substrate is not particularly limited. The metal wiring system can be formed by a known method of forming a metal wiring on the surface of a glass substrate. Further, the material of the metal wiring is also not particularly limited. Typical examples of the metal wiring material include a transparent electrode material such as ITO, SnO ₂ or ZnO, a reflective electrode material such as AgPdCu, or a Mo-Al-Mo laminate. Further, general metal wiring materials such as copper, nickel, gold, silver, chromium, aluminum, and the like can be used.

The permanent film formed on the surface of the glass substrate is a non-conductive film composed of an organic or inorganic material. Here, the non-conductive property of the permanent film means that the surface resistance is 1.0 × 10 ¹² Ω/cm ² or more.

Examples of the permanent film formed on the surface of the glass substrate include an overcoat layer, a spacer, a black matrix, and an insulating film. When the permanent film is an outer cover or a transparent spacer, high transparency is required for the permanent film. In this case, it is preferred to form a permanent film by using a photosensitive resin composition containing an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator of a specific structure described later. The formation of a permanent film system using a photosensitive resin composition is carried out in accordance with a general photolithography method.

As the alkali-soluble resin contained in such a photosensitive resin composition, a unit containing (a1) derived from an unsaturated carboxylic acid and (a2) derived from an alicyclic skeleton-containing unsaturated compound having no epoxy group can be used. Copolymer of the unit. By using the (A) alkali-soluble resin containing the unit (a1) and the unit (a2), it is possible to easily obtain a cured film which can impart excellent transparency, and the radiation which is excessively dissolved in the exposed portion during development after exposure is irradiated. Resin composition.

Examples of the unsaturated carboxylic acid which produces the unit (a1) include monocarboxylic acids such as (meth)acrylic acid and crotonic acid; maleic acid and fumar Dicarboxylic acids such as acid, citraconic acid, mesaconic acid, and itaconic acid; and anhydrides of such dicarboxylic acids. From the viewpoints of copolymerization reactivity, alkali solubility of the obtained resin, ease of availability, and the like, (meth)acrylic acid and anhydrous maleic acid are preferred among these. The alkali-soluble resin may also contain (a1) units derived by combining two or more kinds of such unsaturated carboxylic acids.

Examples of the alicyclic group-containing unsaturated compound having no epoxy group in the (a2) unit include compounds represented by the following formulas (a2-1) to (a2-7). Among these, from the viewpoint of easily obtaining a photosensitive resin composition having good developability, a compound represented by the following formulas (a2-3) to (a2-8) is preferable, and the following formula (a2-3) or The compound represented by (a2-4) is preferred.

In the above formula, R ¹⁰¹ represents a hydrogen atom or a methyl group, R ¹⁰² represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ¹⁰³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ¹⁰² is a single bond, a linear chain or a branched chain alkyl group, such as methylene, ethyl, propyl, tetramethylene, ethyl ethyl, pentamethylene, and hexa Methyl is preferred. R ¹⁰³ is preferably a methyl group or an ethyl group.

The mass average molecular weight of the alkali-soluble resin (Mw: the measurement value of the gel permeation chromatography (GPC) in terms of polystyrene. The same applies in the present specification.) It is preferably 2000 to 200000, and 2000 to 18000. Good, with 3000~15000 as the best.

As the photopolymerizable compound contained in the photosensitive resin composition for imparting the highly transparent permanent film, the same compound as the photopolymerizable compound described later can be used as the second negative for forming the etching mask. A component of a photoresist composition. The content of the photopolymerizable compound is preferably from 5 to 60% by mass, and preferably from 10 to 50% by mass, based on the solid content of the photosensitive resin composition.

The photopolymerization initiator to be contained in the photosensitive resin composition for imparting the high transparency permanent film is not particularly limited, and a conventionally known photopolymerization initiator can be used.

Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-[4-(2-hydroxyl group). Ethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one , 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, double (4-Dimethylaminophenyl) ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2- Dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-indole Zyrid-3-yl], 1-(O-ethylindenyl), 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzylindenyl)], 2,4,6-trimethylbenzylidenediphenylphosphine oxide, 4-benzylindolyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, 4-dimethyl Amino benzoic acid methyl, 4-dimethylamino benzoic acid ethyl, 4-dimethylamino benzoic acid butyl, 4-dimethylamino-2-ethylhexyl benzoic acid, 4- Dimethylamino-2-isopentylbenzoic acid, benzyl- β -methoxyethyl acetal, benzyldimethylketal, 1-benzene 1,2-propanedione-2-(O-ethoxycarbonyl)anthracene, o-benzylindenylbenzoic acid methyl, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-Dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropyl thioxanthene, 2-ethyl hydrazine, octamethyl hydrazine, 1,2-benzopyrene, 2,3-diphenyl fluorene, azobisisobutyronitrile, benzyl peroxide Sulfhydryl, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-di(m-甲Oxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdiethyl Aminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl Ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylphenyl Ketone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyl Acetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxy Acetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, pentyl-4-dimethylaminobenzoate, 9- Phenyl acridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl) Propane, p-methoxytriazine, 2,4,6-parade(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine 2-[2-(5-Methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl) Vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6- Bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis (three Chloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethane 5--6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloro 6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styryl Phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, and the like. These photopolymerization initiators can be used singly or in combination of two or more.

Among these, on the surface of the sensitivity, it is also preferable to use a photopolymerization initiator which is a lanthanide. Among the photopolymerization initiators of the lanthanoid series, as a particularly preferred one, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole-3-, Base], 1-(O-ethylindenyl), and 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzylindenyl).

The content of the photopolymerization initiator in the photosensitive resin composition is preferably 0.1 to 50 parts by mass, and preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the total of the solid content of the photosensitive resin composition.

The photosensitive resin composition which imparts the above-mentioned highly transparent permanent film may contain an organic solvent as needed. As the organic solvent, an organic solvent similar to the organic solvent described later can be used as a component of the positive-type photoresist composition used for forming the etching mask.

The content of the organic solvent in the photosensitive resin composition is not particularly limited, and is appropriately set in accordance with the coating film thickness at a level in which the photosensitive resin composition can be applied to a substrate or the like. The viscosity of the photosensitive resin composition is preferably 0.9 to 500 cp, preferably 1 to 50 cp, more preferably 1 to 30 cp. Moreover, the solid content concentration of the photosensitive resin composition is 1 to 80% by mass is preferred, and 5 to 50% by mass is preferred.

≪ photoresist composition ≫

When the glass substrate is processed by the method described later, etching is performed. Therefore, an etching mask is formed on the surface of the glass substrate before etching. This etch mask is formed by photolithography using a photoresist composition.

The photoresist composition is not particularly limited as long as it is a photoresist composition used in the formation of an etching mask during etching. Among such photoresist compositions, a photoresist composition containing a polymer compound having a hydroxyl group or a carboxyl group is preferred. The etching mask formed using such a photoresist composition is excellent in adhesion to a substrate and is not easily peeled off from the substrate during etching, so that it is advantageous in the precision of etching.

On the other hand, the etching mask formed on the surface of the glass substrate used in the past using a photoresist composition containing a polymer compound having a hydroxyl group or a carboxyl group is difficult to be peeled off from the surface of the substrate in a short time after the etching process. The residue of the etching mask is not left. However, when the pretreated glass substrate is used by the method described later, the residue of the etching mask can be left and the etching mask can be peeled off from the surface of the substrate in a short time.

Hereinafter, a suitable specific example of the photoresist composition will be described. Still, the photoresist composition is not limited to the photoresist composition specifically described below.

<Positive photoresist composition>

The positive photoresist composition contains at least (A1) a base having a phenolic hydroxyl group. a soluble resin, and (B1) a compound containing a quinonediazide group.

[(A1) Alkali-soluble resin having a phenolic hydroxyl group]

As the alkali-soluble resin having a phenolic hydroxyl group (hereinafter also referred to as "(A) component)", for example, a polyhydroxystyrene resin can be used. The polyhydroxystyrene resin has at least a constituent unit derived from hydroxystyrene.

Here, "hydroxystyrene" means a hydroxystyrene group, and a hydrogen atom bonded to the α-position of the hydroxystyrene is replaced by another substituent such as a halogen atom, an alkyl group, a halogenated alkyl group or the like, and And the concept of hydroxystyrene derivatives (monomers) of such derivatives.

The "hydroxystyrene derivative" is composed of at least a benzene ring and a hydroxyl group bonded thereto, and is meant to include, for example, a hydrogen atom bonded to the α-position of the hydroxystyrene by a halogen atom, and having 1 to 5 carbon atoms. a substituent substituted with an alkyl group, a halogenated alkyl group or the like, and an alkyl group having 1 to 5 carbon atoms bonded to a benzene ring bonded to a hydroxyl group of the hydroxystyrene, or the hydroxyl group The bonded benzene ring is further bonded to 1 to 2 hydroxyl groups (in this case, the total number of hydroxyl groups is 2 to 3).

The halogen atom may, for example, be a chlorine atom, a fluorine atom or a bromine atom, and a fluorine atom is preferred.

The "alpha position of hydroxystyrene", when not specifically defined, means a carbon atom bonded to a benzene ring.

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

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, p represents an integer of 1 to 3, and q represents 0. An integer of ~2.

The number of carbon atoms of the alkyl group of R ^a1 is preferably from 1 to 5. Further, a linear or branched chain alkyl group is preferred, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, and a pentyl group. , isoamyl, neopentyl and the like. Among these, methyl is preferred in the industry.

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom is preferred.

As the halogenated alkyl group, one or all of the hydrogen atoms of the above-mentioned alkyl group having 1 to 5 carbon atoms are partially or completely substituted by a halogen atom. In this case, it is preferred that all of the hydrogen atoms are replaced by fluorine atoms. Further, a linear or branched chain fluorinated alkyl group is preferred, and a trifluoromethyl group, a hexafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group or the like is preferred, and a trifluoromethyl group is preferred. -CF ₃₎ is the best.

R ^a1 is preferably a hydrogen atom or a methyl group, and a hydrogen atom is preferred.

The alkyl group having 1 to 5 carbon atoms of R ^a2 may be the same as the case of R ^a1 .

q is an integer from 0 to 2. Among them, 0 or 1 is preferred, and industrially preferred is 0.

The substitution position of R ^a2 may be any of the ortho, meta and para positions when q is 1, and any substitution position may be combined when q is 2.

p is an integer of 1 to 3, preferably 1. The position at which the hydroxyl group is substituted may be any of the ortho, meta and para positions when p is 1, but it is preferably from the viewpoint of being easily available and having a low price. Further, when p is 2 or 3, any substitution position can be combined.

The constituent units represented by the formula (a-1) may be used singly or in combination of two or more kinds.

In the polyhydroxystyrene resin, the ratio of the constituent units derived from the hydroxystyrene is preferably 60 to 100 mol%, and 70 to 100, based on the total constituent unit of the polyhydroxystyrene resin. Molar% is preferred, preferably 80 to 100 mol%. By making the above range, the alkali solubility of the positive resist composition can be made moderate.

The polyhydroxystyrene resin is preferably a constituent unit derived from styrene. Here, the "constituting unit derived from styrene" means a constituent unit including a crack of an ethylene double bond including styrene and a styrene derivative (but not including hydroxystyrene).

"Styrene derivative" means a hydrogen atom including a hydrogen atom bonded to the alpha position of styrene substituted with a halogen atom, an alkyl group, a halogenated alkyl group or the like, and a phenyl group of styrene. The atom is replaced by a substituent such as an alkyl group having 1 to 5 carbon atoms.

The halogen atom may, for example, be a chlorine atom, a fluorine atom or a bromine atom, but a fluorine atom is preferred. Still, "the alpha position of styrene" is When not specifically defined, it means a carbon atom to which a benzene ring is bonded.

The constituent unit derived from styrene is, for example, represented by the following formula (a-2). In the formula, R ^a1 , R ^a2 , and q are synonymous with the above formula (a-1).

As R ^a1 and R ^a2, R may be the same as mentioned above are of formula (a1) of ^a1 and R ^a2 are. q is an integer from 0 to 2. Among them, 0 or 1 is preferred, and industrially preferred is 0. The substitution position of R ^a2 may be any of the ortho, meta, and para positions when q is 1, and any substitution position may be combined when q is 2.

The constituent units represented by the above formula (a-2) may be used singly or in combination of two or more kinds.

In the polyhydroxystyrene resin, the ratio of the constituent units derived from styrene is preferably 40 mol% or less, and 30 mol% or less, based on the total constituent unit of the polyhydroxystyrene resin. Preferably, it is more preferably 20 mol% or less. By setting the above range, the alkali solubility of the positive resist composition can be made moderate, and the balance with other constituent units is also good.

The polyhydroxystyrene resin may have a constituent unit derived from hydroxystyrene or a constituent unit derived from a constituent unit of styrene. Preferably, the polyhydroxystyrene resin is a polymer composed only of constituent units derived from hydroxystyrene, or a structure derived from hydroxystyrene. A copolymer composed of a unit and a constituent unit derived from styrene.

The mass average molecular weight of the polyhydroxystyrene resin is not particularly limited, and is preferably 1,500 to 40,000, more preferably 2,000 to 8,000.

Further, as the alkali-soluble resin having a phenolic hydroxyl group, a phenol resin can be used. This phenol resin can be obtained by addition-condensation of a phenol and an aldehyde in the presence of an acid catalyst.

Examples of the phenols include cresols such as phenol, o-cresol, m-cresol, and p-cresol; 2,3-nonanol, 2,4-nonanol, 2,5-nonanol, 2,6-nonanol, 3,4-nonanol, 3,5-nonanol and other indophenols; o-ethylphenol, m-ethylphenol, p-ethylphenol, 2-isopropylphenol, Alkyl phenols such as 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, p-tert-butylphenol; 2,3,5 - trialkylphenols such as trimethylphenol and 3,4,5-trimethylphenol; resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, benzenetriol, phloroglucinol Polyvalent phenols; alkyl polyphenols such as alkyl resorcinol, alkyl catechol, alkyl hydroquinone (all alkyl groups are 1 to 4 carbon atoms); α-naphthol , β -naphthol, hydroxydiphenyl, bisphenol A, and the like. These phenols may be used singly or in combination of two or more. Among these phenols, m-cresol and p-cresol are preferred, and m-cresol and p-cresol are preferably used in combination. In the meantime, by adjusting the blending ratio of the two, various characteristics such as sensitivity can be adjusted.

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

Examples of the acid catalyst include hydrochloric acid, sulfuric acid, and nitric acid. Inorganic acids such as phosphoric acid and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethylsulfonic acid, and p-toluenesulfonic acid; and metal salts such as zinc acetate. These acid catalysts may be used singly or in combination of two or more.

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

The mass average molecular weight of the phenol resin is not particularly limited, and is preferably from 1,000 to 30,000, more preferably from 3,000 to 25,000.

As the alkali-soluble resin having a phenolic hydroxyl group, a phenol-nonanediol condensation resin, a cresol-nonanediol condensation resin, a phenol-dicyclopentadiene condensation resin, or the like can also be used.

The content of the component (A) is preferably from 50 to 95% by mass, and preferably from 60 to 90% by mass, based on the solid content of the positive resist composition. By making the above range, there is a tendency to easily obtain a balance of development.

[(B) Compound containing quinonediazide]

The compound containing a quinonediazide group (hereinafter also referred to as "component (B)") is not particularly limited, and is a complete compound having one or more phenolic hydroxyl groups and a sulfonic acid containing quinonediazide group. Ester esters or partial esters are preferred. The quinonediazide-containing compound can be obtained by using a compound having one or more phenolic hydroxyl groups and a sulfonic acid containing a quinonediazide group in a suitable solvent such as dioxane, in triethanolamine or a carbonate base. It is obtained by condensation in the presence of a base such as a hydrogencarbonate base and complete esterification or partial esterification.

As the above compound having one or more phenolic hydroxyl groups, For example, 2,3,4-trihydroxybenzophenone, and polyhydroxybenzophenones such as 2,3,4,4'-tetrahydroxybenzophenone; and (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-hydroxyphenylmethane, 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, double (5 -cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, double (5-cyclohexyl-4-hydroxy-2-methylbenzene -2-hydroxyphenylmethane, and bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenylmethane isophenol-type compound; 2,4-double ( 3,5-Dimethyl-4-hydroxybenzyl)-5-hydroxyphenol, and 2,6-bis(2,5-dimethyl-4-hydroxybenzyl)-4-methylphenol, etc. Nucleophenolic compound; 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-hydroxyl) Benzyl)-4-hydroxy-5- Ethylphenyl]methane, bis[3-(3,5-diethyl-4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane, bis[3-(3,5-di Ethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane, bis[2-hydroxy-3-(3,5-dimethyl-4-hydroxybenzyl)-5- Phenyl]methane, bis[2-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methylphenyl]methane, bis[4-hydroxy-3-(2-hydroxy-5) -Methylbenzyl)-5-methylphenyl]methane, and bis[2,5-dimethyl-3-(2-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane Linear 4-nucleoside phenolic compound; 2,4-bis[2-hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol, 2,4-bis[4- Hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol, and 2,6-bis[2,5-dimethyl-3-(2-hydroxy-5-) Linear 5-nuclear phenolic compound such as methylbenzyl)-4-hydroxybenzyl]-4-methylphenol; 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'-three Hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(4' -hydroxybenzene 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'-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl) -2-(4'-hydroxy-3',5'-dimethylphenyl)propane, and 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methyl a bisphenol type compound such as ethyl]phenyl]ethylene]bisphenol; 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl) Ethyl]benzene, and 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyphenyl)ethyl Multi-core branching a condensed phenol compound such as 1,1-bis(4-hydroxyphenyl)cyclohexane. These compounds may be used singly or in combination of two or more.

The sulfonic acid containing quinonediazide group may, for example, be naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, orthoquinone醌Diazide sulfonic acid and the like.

The content of the component (B) is preferably 5 to 50 parts by mass, and preferably 5 to 25 parts by mass, based on 100 parts by mass of the component (A). By making the above range, the sensitivity of the positive resist composition can be made good.

[(C) polyvinyl alkyl ether]

The positive resist composition may also contain a polyvinyl alkyl ether (hereinafter also referred to as "(C1) component") as a plasticizer. By containing a polyvinyl alkyl ether as a plasticizer, the etching resistance of the positive photoresist composition can be improved.

The alkyl group of the polyvinyl alkyl ether is preferably one having 5 to 5 carbon atoms, and preferably one or two carbon atoms. That is, the polyvinyl alkyl ether is preferably polyvinyl methyl ether or polyvinyl ethyl ether.

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

The content of the component (C) is preferably from 1 to 100 parts by mass based on 100 parts by mass of the component (A). By setting the above range, the etching resistance of the positive resist composition can be appropriately adjusted.

[(S) organic solvent]

The positive resist composition is preferably an organic solvent for dilution (hereinafter also referred to as "(S) component").

The organic solvent is not particularly limited, and an organic solvent widely used in the art can be used. For example, ethylene glycol monoalkyl ether acetate such as ethylene glycol monomethyl ether acetate or ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, a propylene glycol monoalkyl ether such as propylene glycol monopropyl ether or propylene glycol monobutyl ether; propylene glycol dialkyl ether such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether or propylene glycol dibutyl ether; Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc.; propylene glycol monoalkyl ether acetate; , butyl acesulfame and other celluloids; butyl carbitol and other carbitol; methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate and other 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 Aliphatic carboxylic acid esters such as esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Other esters such as methyl ketone and ethyl pyruvate; aromatic hydrocarbons such as toluene and hydrazine; ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; N-dimethyl a decylamine such as carbamide, N-methylacetamide, N,N-dimethylacetamide or N-methylpyrrolidone; or a lactone such as γ-butyrolactone. These organic solvents may be used singly or in combination of two or more.

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

[Other ingredients]

The positive resist composition may further contain an addition resin, a stabilizer, a colorant, a surfactant, an inorganic filler, a decane coupling agent, and the like, as needed.

The inorganic filler is not particularly limited, and inorganic fine particles such as barium sulfate and ceria are preferably used. By containing an inorganic filler, etching resistance, physical stress resistance, and thermal stress resistance can be made good.

As the decane coupling agent, a conventionally known decane coupling agent can be used, but it is preferably not contained. By not containing a decane coupling agent, it is possible to make the stability over time good.

<First negative photoresist composition>

The first negative photoresist composition contains at least (A) an alkali-soluble resin having a phenolic hydroxyl group, (D) a crosslinking agent, and (E) an acid generator.

[(A) Alkali-soluble resin having a phenolic hydroxyl group]

As the alkali-soluble resin having a phenolic hydroxyl group (hereinafter also referred to as "(A) component)", those exemplified in the positive-type photoresist composition can be used.

The content of the component (A) is preferably 50 to 99% by mass, and is 60 to 95% by mass based on the solid content of the first negative photoresist composition. % is preferred. By setting the above range, it is easy to obtain a balance of development.

[(D) Crosslinker]

The crosslinking agent (hereinafter also referred to as "(D) component)" is not particularly limited, and an amine compound such as melamine resin, urea resin, guanamine resin, acetylene urea-formaldehyde resin, succinimide- Formaldehyde resin, ethylene urea-formaldehyde resin, and the like.

Among these, an alkoxymethylated amine-based resin such as an alkoxymethylated melamine resin or an alkoxymethylated urea resin is also preferred. The alkoxymethylated amine-based resin is, for example, a condensate obtained by reacting melamine or urea with a formaldehyde solution in a boiling aqueous solution, with methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol. A lower alcohol such as isopropyl alcohol is etherified, and then the reaction liquid is cooled and precipitated to produce. The alkoxymethylated amine-based resin may, for example, be a methoxymethylated melamine resin, an ethoxymethylated melamine resin, a propoxymethylated melamine resin or a butoxymethylated melamine resin. A methoxymethylated urea resin, an ethoxymethylated urea resin, a propoxymethylated urea resin, a butoxymethylated urea resin, or the like. These crosslinking agents may be used singly or in combination of two or more.

The content of the component (D) is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, per 100 parts by mass of the component (A). By setting the above range, the first negative-type photoresist composition has good curability and patterning properties.

[(E) acid generator]

The acid generator (hereinafter also referred to as "(E) component)" is not particularly limited, and a conventionally known acid generator can be used.

Specific examples of the acid generator include a phosphonium salt generator such as a phosphonium salt or a phosphonium salt, an oxime sulfonate acid generator, a halogen-containing triazine compound, a diazomethane acid generator, and a nitro group. A benzyl sulfonate acid generator (nitrobenzyl derivative), an imidosulfonate acid generator, a diterpenoid generator, and the like.

The compound represented by the following formula (e-1) is mentioned as a preferable hydrazine-acid generator.

In the formula (e-1), R ^e1 and R ^e2 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group which may have an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent, and R ^e3 represents a halogen atom. Or an alkyl p-phenylene group, R ^e4 represents a hydrogen atom, a hydrocarbon group which may have an oxygen atom or a halogen atom, a benzinyl group which may have a substituent or a polyphenyl group which may have a substituent, and A ^- represents a phosphonium cation Relative ions.

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 ^- , F ₂ PO ₂ ^- , p-tosylate, nonafluorobutane sulfonate, adamantane carboxylate, tetraaryl borate, fluorinated alkyl fluorophosphate represented by the following formula (e-2) Anion, etc.

[6] [(Rf) _n PF _5-n ] ^-    (e-2)

In the formula (e-2), Rf represents an alkyl group in which 80% or more of a hydrogen atom is substituted by a fluorine atom. n represents the number and is an integer from 1 to 5. The Rf of n may be the same or different.

The acid generator represented by the formula (e-1) may, for example, be 4-(2-chloro-4-benzylindenylphenylthio)phenyldiphenylphosphonium hexafluoroantimonate or 4-(2). -Chloro-4-benzylsulfonylphenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-benzylsulfonylphenylthio)phenyl bis (4 -Chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-benzylsulfonylphenylthio)phenylbis(4-methylphenyl)phosphonium hexafluoroantimonate, 4-(2 -Chloro-4-benzylsulfonylphenylthio)phenylbis(4-( β -hydroxyethoxy)phenyl)phosphonium hexafluoroantimonate, 4-(2-methyl-4-benzylnonylbenzene Thio)phenyl bis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(3-methyl-4-benzylsulfonylphenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluorophosphate Citrate, 4-(2-fluoro-4-benzylmercaptophenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-methyl-4-benzylindenylbenzene Thio)phenyl bis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2,3,5,6-tetramethyl-4-benzylsulfonylphenylthio)phenyl bis(4- Fluorophenyl)phosphonium hexafluoroantimonate, 4-(2,6-dichloro-4-benzylsulfonylphenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-( 2,6-Dimethyl-4-benzylsulfonylphenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2,3-dimethyl-4-benzyl Phenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-methyl-4-benzylindolylphenylthio)phenylbis(4-chlorophenyl)indole Hexafluoroantimonate, 4-(3-methyl-4-benzylsulfonylphenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-fluoro-4-benzidine Phenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-methyl-4-benzylindolylphenylthio)phenylbis(4-chlorophenyl)indole Hexafluoroantimonate, 4-(2,3,5,6-tetramethyl-4-benzylsulfonylphenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-( 2,6-Dichloro-4-benzylsulfonylphenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2,6-dimethyl-4-benzylnonylbenzene Thio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2,3-dimethyl-4-benzylindolylphenylthio)phenylbis(4-chlorophenyl) Hexafluoroantimonate, 4-(2-chloro-4-ethenylphenylthio)phenyldiphenylphosphonium hexafluoroantimonate, 4-(2-chloro-4-(4-methylbenzyl) Mercapto)phenylthio)phenyldiphenylphosphonium hexafluoroantimonate, 4-(2-chloro-4-(4-fluorobenzyl)phenylthio)phenyldiphenylphosphonium hexafluoroantimonate Salt, 4-(2-chloro-4-(4-methoxybenzyl)phenylthio)phenyldiphenylphosphonium hexafluoroantimonate, 4-(2-chloro-4-oxime Phenylthio)phenyldiphenylphosphonium hexafluoroantimonate, 4-(2-chloro-4-ethinylphenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4 -(2-chloro-4-(4-methylbenzyl)phenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-(4- Fluorobenzyl phenyl)phenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-(4-methoxybenzyl)phenylthio)benzene Bis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-dodecylphenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-ethenylphenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-(4-methylbenzyl) Phenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-(4-fluorobenzyl)phenylthio)phenyl bis(4-chloro Phenyl) indole hexafluoroantimonate, 4-(2-chloro-4-(4-methoxybenzyl)phenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-dodecylphenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-benzylindenylphenylthio) Phenyldiphenylphosphonium hexafluorophosphate, 4-(2-chloro-4-benzylindolylthio)phenyldiphenylphosphonium tetrafluoroborate, 4-(2-chloro-4-benzylindolyl) benzene Phenyldiphenylphosphonium perchlorate, 4-(2-chloro-4-benzylsulfonylphenylthio)phenyldiphenylphosphonium trifluoromethanesulfonate, 4-(2-chloro-4 -benzylbenzylphenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluorophosphate, 4-(2-chloro-4-benzylindolylphenylthio)phenylbis(4-fluorophenyl) Tetrafluoroborate, 4-(2-chloro-4-benzylsulfonylphenylthio)phenylbis(4-fluorophenyl)phosphonium perchlorate, 4-(2-chloro-4-benzylindolyl) Phenylthio)phenylbis(4-fluorophenyl)indole trifluoromethanesulfonate, 4-(2-chloro-4-benzylsulfonylphenylthio)phenylbis(4-fluorophenyl)indole -tosylate, 4-(2-chloro-4-benzylsulfonylphenylthio)phenylbis(4-fluorophenyl)camphorsulfonate, 4-(2-chloro-4-benzylindenyl) Phenylthio)phenylbis(4-fluorophenyl)fluorene nonafluorobutanesulfonate, 4-(2-chloro-4-benzylindolylphenylthio)phenylbis(4-chlorophenyl)indole Hexafluorophosphate, 4-(2-chloro-4-benzylsulfonylphenylthio)phenylbis(4-chlorophenyl)phosphonium tetrafluoroborate, 4-(2-chloro-4-benzylnonylbenzene Thio)phenylbis(4-chlorophenyl)phosphonium perchlorate, 4-(2-chloro-4-benzylindenylphenylthio)phenylbis(4-chlorophenyl)phosphonium trifluoromethanesulfonate Acid salt, diphenyl[4-(phenylthio)phenyl]phosphonium trifluoropentafluoroethyl phosphate, diphenyl [4- (p- terphenyl) phenyl] sulfonium hexafluoroantimonate, diphenyl [4- (p- terphenyl) phenyl] sulfonium trifluoro reference pentafluoroethyl phosphate.

The other sulfonate-based acid generator may be, for example, a cation moiety of the above formula (e-1) substituted with, for example, triphenylsulfonium, (4-tert-butoxyphenyl)diphenylphosphonium, or a double (4-tert-butoxyphenyl)phenylhydrazine, ginseng (4-tert-butoxyphenyl)fluorene, (3-tert-butoxyphenyl)diphenylphosphonium, bis(3-tert -butoxyphenyl)phenylhydrazine, ginseng (3-tert-butoxyphenyl)anthracene, (3,4-ditert-butoxyphenyl)diphenylanthracene, bis(3,4- Ditert-butoxyphenyl)phenylindole, ginseng (3,4-ditert-butoxyphenyl)anthracene, diphenyl(4-thiophenoxyphenyl)anthracene, (4-tert -butoxycarbonylmethoxyphenyl)diphenylanthracene, ginseng (4-tert-butoxycarbonylmethoxyphenyl)anthracene, (4-tert-butoxyphenyl)bis(4-di Methylaminophenyl)anthracene, ginseng (4-dimethylaminophenyl)anthracene, 2-naphthyldiphenylanthracene, dimethyl-2-naphthyl anthracene, 4-hydroxyphenyldimethyl An anthracene cation such as fluorene, 4-methoxyphenyl dimethyl hydrazine, trimethyl hydrazine, 2-ketocyclohexylcyclohexylmethyl hydrazine, trinaphthyl fluorene or tribenzyl hydrazine, or diphenyl hydrazine , bis(4-tert-butylphenyl)fluorene, (4-tert-butoxyphenyl)phenylhydrazine, (4-methoxyl) A cation such as an aryl sulfonium cation such as phenyl)phenyl hydrazine.

Examples of the oxime sulfonate-based acid generator include [2-(propylsulfonyloxyimino)-2,3-dihydrothiophene-3-ylidene](o-methylphenyl)acetonitrile. --(p-toluenesulfonyloxyimino)-phenylacetonitrile, α-(phenylsulfonyloxyimino)-2,4-dichlorophenylacetonitrile, α-(phenylsulfonyloxy) Imino)-2,6-dichlorophenylacetonitrile, α-(2-chlorophenylsulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxy) Amino)-1-cyclopentenylacetonitrile and the like. Further, in addition to the above, a compound represented by the following formula (e-3) can be given.

In the formula (e-3), R ^e5 represents a monovalent, divalent or trivalent organic group, and R ^e6 represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic compound group, and r represents 1~ An integer of 6.

R ^e5 based group preferably an aromatic compound, such as an aromatic compound group include a phenyl group, a naphthyl group, etc. aromatic hydrocarbon group, or a furyl group, a thienyl group, etc. The heterocyclic group and the like. These may have a suitable substituent on the ring, and may have, for example, one or more halogen atoms, an alkyl group, an alkoxy group, a nitro group or the like. Further, 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. Further, r is preferably an integer of 1 to 3, and preferably 1 or 2.

As the acid generator of formula (e-3) represented by the, at r = 1, R ^e5 include such as phenyl, methylphenyl, methoxyphenyl, and in any one, and R ^e6 A compound that is a methyl group. More specifically, examples of the acid generator represented by the above formula (e-3) include α-(methylsulfonyloxyimino)-1-phenylacetonitrile and α-(methylsulfonate).醯oxyimino)-1-(p-methylphenyl)acetonitrile, and α-(methylsulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile.

When the acid generator represented by the formula (e-3) is r=2, an acid generator represented by the following formula may be mentioned.

The halogen-containing triazine compound may, for example, be 2,4-bis(trichloromethyl)-6-silveryl-1,3,5-triazine or 2,4-bis(trichloromethyl)-6. -[2-(2-furyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furyl)vinyl] -s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-ethyl-2-furyl)vinyl]-s-triazine, 2,4-bis (three Chloromethyl)-6-[2-(5-propyl-2-furyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3, 5-dimethoxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl)vinyl] -s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dipropoxyphenyl)vinyl]-s-triazine, 2,4-dual ( Trichloromethyl)-6-[2-(3-methoxy-5-ethoxyphenyl)vinyl]-s-triazine, 2,4-double (Trichloromethyl)-6-[2-(3-methoxy-5-propoxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6- [2-(3,4-Methylenedioxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-(3,4-methylenedioxy Phenyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloro Methyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrene Phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2-(4-methyl Oxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl) -1,3,5-triazine, 2-[2-(2-furyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2 -(5-methyl-2-furyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,5-dimethoxy Phenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]- 4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methylenedioxyphenyl)-4,6-bis(trichloromethyl)- 1,3,5-triazine, ginseng (1,3-dibromopropyl)-1,3,5-triazine a halogen-containing triazine compound such as (2,3-dibromopropyl)-1,3,5-triazine or the like: (2,3-dibromopropyl)isocyanate or the like ( E-4) A halogen-containing triazine compound represented.

In the formula (e-4), R ^e7 , R ^e8 and R ^e9 each independently represent a halogenated alkyl group having 1 to 6 carbon atoms.

Examples of the other acid generator include bis(p-toluenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, and 1-cyclohexylsulfonyl-1-( 1,1-dimethylethylsulfonyl)diazomethane, double (1,1-dimethylethylsulfonyl)diazomethane, bis(1-methylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, double (2, 4-dimethylphenylsulfonyl)diazomethane, bis(4-ethylphenylsulfonyl)diazomethane, bis(3-methylphenylsulfonyl)diazomethane, double (4 -Methoxyphenylsulfonyl)diazomethane, bis(4-fluorophenylsulfonyl)diazomethane, bis(4-chlorophenylsulfonyl)diazomethane, bis(4-tert- Butylsulfonyl diazomethane such as butylphenylsulfonyl)diazomethane; 2-methyl-2-(p-toluenesulfonyl)propiophenone, 2-(cyclohexylcarbonyl)-2-( P-toluenesulfonyl)propane, 2-methanesulfonyl-2-methyl-(p-methylthio)propiophenone, 2,4-dimethyl-2-(p-toluenesulfonyl)pentane a sulfonylcarbonyl alkane such as 3-ketone; 1-p-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-ethenyl-1-(1-methylethylsulfonyl) Diazo Alkane, 1-diazo-1-(p-toluenesulfonyl)-3,3-dimethyl-2-butanone, 1-diazo-1-phenylsulfonyl-3,3-dimethyl 2-butanone, 1-diazo-1-(p-toluenesulfonyl)-3-methyl-2-butanone, 2-diazo-2-(p-toluenesulfonyl)acetic acid cyclohexyl , 2-diazo-2-benzenesulfonyl acetic acid-tert-butyl, 2-diazo-2-methanesulfonyl acetic acid isopropyl, 2-diazo-2-benzenesulfonyl acetic acid cyclohexyl, 2-diazo-2-(p-toluenesulfonyl)acetic acid-tert-butyl and the like sulfonylcarbonyldiazomethane; p-toluenesulfonic acid-2-nitrobenzyl, p-toluenesulfonic acid- 2,6-dinitrobenzyl, p-trifluoromethylbenzenesulfonic acid-2,4-dinitrobenzyl and the like nitrobenzyl derivative; benzenetriol methanesulfonate, benzenetriol Phenyl sulfonate, benzenetriol P-tosylate, p-methoxybenzenesulfonate of benzenetriol, mesitylene sulfonate of benzenetriol, benzyl sulfonate of benzenetriol, methanesulfonic acid of alkyl gallic acid Ester, benzenesulfonate of gallic acid alkylate, p-toluenesulfonate of alkyl gallic acid, p-methoxybenzenesulfonate of alkyl gallic acid (alkyl group having 1 to 15 carbon atoms) An ester of a polyhydroxy compound such as a mesitylene group of a gallic acid alkyl group or a benzyl sulfonate of a gallic acid alkyl group, and an ester of an aliphatic or aromatic sulfonic acid.

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

The content of the component (E) is preferably 0.05 to 30 parts by mass, and preferably 0.1 to 10 parts by mass, per 100 parts by mass of the component (A). By setting the above range, the hardenability of the first negative photoresist composition becomes good.

[(C) polyvinyl alkyl ether]

The first negative photoresist composition may also contain a polyvinyl alkyl ether as a plasticizer (hereinafter also referred to as "(C) component"). By containing a polyvinyl alkyl ether as a plasticizer, the etching resistance of the first negative photoresist composition can be improved. As the polyvinyl alkyl ether, those exemplified in the positive resist composition can be used.

The content of the component (C) is preferably from 1 to 100 parts by mass based on 100 parts by mass of the component (A). By making the above range, the etching resistance of the first negative-type photoresist composition can be appropriately adjusted.

[(S) organic solvent]

The first negative-type photoresist composition also preferably contains an organic solvent for dilution (hereinafter also referred to as "(S) component"). As the organic solvent, those exemplified in the positive resistive grease composition can be used.

The content of the component (S) is not particularly limited, and is preferably such that the solid content of the first negative resist composition is 10 to 60% by mass, and preferably 20 to 50% by mass. .

[Other ingredients]

The first negative photoresist composition may contain an addition resin, a stabilizer, a colorant, a surfactant, an inorganic filler, a decane coupling agent, and the like, as needed.

The inorganic filler is not particularly limited, and inorganic fine particles such as barium sulfate and ceria are preferably used. By containing an inorganic filler, etching resistance, physical stress resistance, and thermal stress resistance can be made good.

As the decane coupling agent, a conventionally known decane coupling agent can be used, but it is preferably not contained. By not containing a decane coupling agent, it is possible to make the stability over time good.

<Second negative photoresist composition>

The second negative photoresist composition contains at least (F) an alkali-soluble resin having a carboxyl group, (G) a photopolymerizable compound, and (H) a photopolymerization initiator.

[(F) Alkali-soluble resin (A) having a carboxyl group]

A suitable example of the (F) alkali-soluble resin having a carboxyl group (hereinafter also referred to as "(F) component") is an acid-based acrylic resin. As the acid group-containing acrylic resin, a monomer such as an ethylenically unsaturated acid and an ester selected from (meth)acrylic acid, a vinyl aromatic compound, a guanamine-based unsaturated compound, or a polyolefin-based compound can be used. One or two or more copolymers obtained by copolymerization. Specifically, for example, ethylenic acid such as (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, or (anhydrous) maleic acid is not mentioned. A saturated acid is used as an essential component, and this is selected from, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate. Ester, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl methacrylate (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxy propyl (a) (meth)acrylic acid esters such as acrylate; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyl toluene, p-chlorostyrene; for example, (meth) acrylamide, acetamidine A guanamine-based unsaturated compound such as acetone acrylamide, N-methylol acrylamide or N-butoxymethyl acrylamide; for example, a polyolefin such as butadiene, isoprene or chloroprene Compounds and (meth)acrylonitrile, methyl isopropenyl ketone, vinyl acetate, VeoVa monomer (shell chemical), propionate ethyl ester, tert-butyl acid ethyl ester, etc. A copolymer obtained by copolymerizing one or more monomers of monomers.

Further, it is preferred that the resin obtained by reacting the acid group-containing acrylic resin with an alicyclic epoxy group-containing unsaturated compound is used as the alkali-soluble resin. In this case, the alicyclic epoxy group-containing unsaturated compound is preferably a compound having one ethylenically unsaturated group and an alicyclic epoxy group in one molecule. Specific examples thereof include compounds represented by the following formulas (f-1) to (f-15).

Here, R ¹¹ is a hydrogen atom or a methyl group. R ¹² is a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms. R ¹³ is a divalent hydrocarbon group having 1 to 10 carbon atoms. t is an integer from 0 to 10. R ¹² is preferably a linear or branched alkyl group such as methylene, ethyl, propyl, tetramethylene, ethylethyl, pentamethylene or hexamethylene. R ^{13 is} , for example, methylene, ethyl, propyl, tetramethylene, ethylethyl, pentamethylene, hexamethylene, phenylene, cyclohexyl, -CH ₂ - Ph-CH ₂ - (Ph is a stretching phenyl group) is preferred.

The reaction of the acid group-containing acrylic resin with the alicyclic epoxy group-containing unsaturated compound is, for example, after mixing an inert organic solvent solution containing an acid group-containing acrylic resin with an alicyclic epoxy group-containing unsaturated compound. It is carried out at about 20 to 120 ° C for about 1 to 5 hours. The inert organic solvent is not particularly limited, and examples thereof include alcohols, esters, aliphatic or aromatic hydrocarbons. The ratio of the acid group-containing acrylic resin to the alicyclic epoxy group-containing unsaturated compound can be changed depending on the type of the monomer to be used, but the number of unsaturated groups of the obtained resin is adjusted to a molecular weight of 1,000 per 1,000. It is preferably in the range of 0.2 to 4.0, preferably 0.7 to 3.5. By adjusting the number of the unsaturated groups in the obtained resin to such a range, it is possible to form an etching mask excellent in adhesion to a glass substrate, and it is easy to obtain a second excellent in curing property and storage stability. Negative photoresist composition.

The mass average molecular weight of the component (F) described above can be determined by measurement by gel permeation chromatography, and the value thereof is preferably from 1,000 to 100,000, preferably from 3,000 to 70,000, more preferably from 9000 to 5.00. 30000. The acid value of the component (F) is preferably from 20 to 200 mgKOH/g, more preferably from 30 to 150 mgKOH/g. Excellent development can be achieved by setting it to the lower limit or more. When the composition is at most the upper limit value, the chemical solution resistance is improved, and the pattern shape is also excellent.

[(G) Photopolymerizable Compound]

(G) The photopolymerizable compound (hereinafter also referred to as "(G) component") has a monofunctional compound and a polyfunctional compound.

Examples of the monofunctional compound include (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, Propyloxymethyl (meth) decylamine, butoxymethoxymethyl (meth) decylamine, N-methylol (a) acrylamide, N-hydroxymethyl (meth) decylamine, (meth)acrylic acid, fumaric acid, maleic acid, anhydrous maleic acid, itaconic acid, anhydrous itaconic acid, citraconic acid , anhydrous citraconic acid, crotonic acid, 2-propenylamine-2-methylpropane sulfonic acid, tert-butyl acrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate , butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (A) Acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-(methyl) propylene oxy-2-hydroxypropyl Phthalate, glycerol mono(meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, epoxy propyl (meth) acrylate, 2 2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, a half (meth) acrylate of a decanoic acid derivative, or the like.

On the other hand, examples of the polyfunctional compound include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol II. (Meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(a) Acrylate, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate , pentaerythritol di(meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, two Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis(4-(meth) propylene decyloxy diethoxy phenyl) propane, 2,2- bis (4 -(A) propylene decyloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloxypropyl (meth) acrylate, ethylene glycol diepoxypropyl ether II ( Methyl) acrylate, diethylene glycol diepoxypropyl ether di(meth) acrylate, diepoxy propyl phthalate di(meth) acrylate, glycerol triacrylate, glycerol Polyepoxypropyl ether poly(meth) acrylate, urethane (meth) acrylate (ie, methyl phenyl diisocyanate), trimethyl hexamethylene diisocyanate and hexamethylene Reaction of diisocyanate with 2-hydroxyethyl (meth) acrylate, methylene bis(meth) decylamine, (meth) acrylamide, methylene ether, polyvalent alcohol and N-hydroxymethyl ( A) a polyfunctional monomer such as a condensate of acrylamide or triacrylformal. Further, a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol type epoxy resin, and a bisphenol type epoxy resin An epoxy group (meth) acrylate obtained by reacting a bifunctional or higher epoxy resin such as a resin with (meth)acrylic acid can also be used as the polyfunctional compound.

The component (G) described above may be used singly or in combination of two or more. Among the above components (G), a polyfunctional compound is preferred. When the second negative-type photoresist composition contains a polyfunctional compound as the component (G), an etching mask excellent in flexibility can be formed, and a second negative-type photoresist composition excellent in curability can be easily prepared.

(G) component relative to 100 parts by mass of (F) component The content is preferably 30 to 250 parts by mass, more preferably 40 to 200 parts by mass, and more preferably 50 to 160 parts by mass. By making the above range, the hydrofluoric acid resistance of the etching mask formed using the second negative-type photoresist composition can be improved. Further, by setting the upper limit value or lower, the development characteristics are improved.

[(H) Photopolymerization initiator]

The (H) photopolymerization initiator (hereinafter also referred to as "(H) component)" is not particularly limited, and examples thereof include 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl group. 1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4- Isopropyl phenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2 -dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)one, 2-methyl-1-[4-(methylthio)phenyl ]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, ethyl ketone-1-[ 9-Ethyl-6-(2-methylbenzylindenyl)-9H-indazol-3-yl]-1-(o-ethylindenyl), 2,4,6-trimethylbenzylidene Diphenylphosphine oxide, 4-benzylindolyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl, 4-dimethyl Ethyl benzoic acid ethyl, 4-dimethylamino benzoic acid butyl, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isopentyl benzoin Acid, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-benzene -1,2-propanedione-2-(o-ethoxycarbonyl)anthracene, o-benzylmercaptobenzoic acid methyl, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2 ,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methyl Thiophene, 2-isopropylthioxanthene, 2-ethylhydrazine, octamethylguanidine, 1,2-benzopyrene, 2,3-diphenylanthracene, azobisisobutyronitrile, Benzoyl peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-di ( M-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-double Diethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, Benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethyl Acetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p- Tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, pentyl -4-dimethylamino benzoate, 9-phenyl acridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane Alkane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-parade(trichloromethyl)-s-triazine, 2-methyl-4 ,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s- Triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino)- 2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4 ,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4- Ethoxystyryl-4,6-bis(trichloromethyl)-s- Triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3- Bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2, 4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo 4-methoxy)styrylphenyl-s-triazine and the like. These photopolymerization initiators can be used singly or in combination of two or more.

The content of the component (H) and the content of the component (G) may be appropriately adjusted, and it is preferably 1 to 25 parts by mass, more preferably 2 to 15 parts by mass, based on 100 parts by mass of the alkali-soluble resin (F). 5 to 15 parts by mass is more preferred. By setting the above range, it is possible to obtain sufficient heat resistance and chemical resistance, and it is possible to improve the coating film forming ability and to suppress photohardening failure.

[(S) organic solvent]

The second negative-type photoresist composition also preferably contains an organic solvent for dilution (hereinafter also referred to as "(S) component"). As the organic solvent system, those exemplified in the positive resist composition can be used.

The content of the component (S) is not particularly limited, and the solid content of the second negative-type photoresist composition is preferably from 10 to 60% by mass, and preferably from 20 to 50% by mass.

[Other ingredients]

The second negative photoresist composition may further contain an addition resin, a stabilizer, a colorant, a surfactant, an inorganic filler, and a decane coupling agent as needed. Wait.

The inorganic filler is not particularly limited, and inorganic fine particles such as barium sulfate and ceria are preferably used. By containing an inorganic filler, etching resistance, physical stress resistance, and thermal stress resistance can be made good.

As the decane coupling agent, a conventionally known decane coupling agent can be used, but it is preferably not contained. By not containing a decane coupling agent, it is possible to make the stability over time good.

Pre-treatment method≫

The glass substrate pretreatment method includes an amine treatment step of subjecting the surface of the glass substrate to an amine treatment using a treatment liquid containing an amine having no functional group capable of chemically bonding to the surface of the glass substrate.

In addition, the pretreatment method may further include a lyophilization step and a alkali metal removal step; the lyophilization step is performed by lyophilizing the surface of the glass substrate, and the lyophilization treatment is performed to enhance the glass exposure on the glass substrate. a portion of the liquid wettability; the alkali metal removal step is performed by an alkali metal removal treatment between the lyophilization step and the amine treatment step, and the alkali metal removal treatment is performed to remove the surface of the glass substrate from the alkali metal The liquid contacts, and reduces the amount of alkali metal in the surface layer of the exposed portion of the glass substrate surface.

Hereinafter, the lyophilization step, the alkali metal removal step, and the amine treatment step will be described in order.

<Hydrophilization step>

The lyophilization step applies a lyophilic treatment to the surface of the glass substrate, and the lyophilization treatment enhances the liquid wettability of the treatment liquid for alkali metal removal with respect to the exposed portion of the glass on the glass substrate. The treatment liquid for alkali metal removal uses a treatment liquid containing an acid or a chelating agent. The treatment liquid for removing an alkali metal is a solution of an aqueous solution of an acid or a chelate agent, a highly polar organic solvent of an acid or a chelate agent, or a liquid organic acid or a liquid from the viewpoint of uniformity of the treatment liquid. Chelating agents are preferred. From the viewpoint of ease of preparation and parity, it is preferred that the treatment liquid be an aqueous solution of an acid, a liquid organic acid, an aqueous solution of a chelating agent, and a liquid chelating agent.

When the treatment liquid for alkali metal removal is an aqueous solution of an acid, an aqueous solution of a liquid organic acid, a chelating agent, and a highly polar treatment liquid such as a liquid chelating agent, the glass on the glass substrate is exposed. Partial application of UV cleaning such as UV/ozone cleaning, or plasma treatment such as O ₂ plasma treatment, can improve the wettability of the treatment liquid for alkali metal removal on the exposed portion of the glass on the glass substrate.

Whether the wettability of the exposed portion of the treatment liquid for alkali metal removal on the exposed portion of the glass substrate is improved by comparing the contact angle of the treatment liquid for removing alkali metal before and after the lyophilization treatment to the exposed portion of the glass on the glass substrate confirm. When the contact angle after the lyophilization treatment is lower than the contact angle before the lyophilization treatment, it is judged that the lyophilization treatment has been favorably performed.

When the treatment liquid for removing alkali metal is a highly polar treatment liquid, it is not a contact angle of the alkali metal removal liquid before and after the lyophilization treatment, but By comparing the contact angle of water before and after the lyophilization treatment, it can also be judged whether or not the lyophilization treatment is well performed.

The treatment liquid for removing an alkali metal is exposed to the glass on the glass substrate by lyophilization treatment using an aqueous solution of an acid, a liquid organic acid, an aqueous solution of a chelating agent, or a liquid chelating agent. Part of the water contact angle is preferably as low as 30 or less, preferably as low as 20 or less, and as low as less than 10 or less.

As the solvent contained in the treatment liquid, a low polarity organic solvent can also be selected. When a low polarity treatment liquid having a low polarity organic solvent as a main body is used, the exposed portion of the glass on the glass substrate can be improved by treating the exposed portion of the glass on the glass substrate by using a known deuteration agent which is a water repellent agent of various materials. The wettability of the low polarity treatment liquid to the glass.

<alkali metal removal step>

After the lyophilization step, the glass substrate is subjected to an alkali metal removal treatment by contacting the surface of the glass substrate with the treatment liquid for removing the alkali metal, thereby reducing the exposed portion of the surface glass of the glass substrate. The amount of alkali metal in the surface layer.

As described earlier, in the alkali metal removing step, a treatment liquid for removing an alkali metal containing an acid or a chelating agent is used. When the treatment liquid for removing an alkali metal contains a solvent for dissolving an acid or a chelate compound, the solvent may be water, an organic solvent having no acidic group, or an organic solvent having no acidic group. Aqueous solution. As a treatment liquid for alkali metal removal, an aqueous solution or acid of an acid or a chelate compound is used from the viewpoint of uniformity of the treatment liquid. A solution of a highly polar organic solvent of a chelate agent, or a liquid organic acid or a liquid chelate compound is preferred. Among these treatment liquids, an aqueous acid solution, a liquid organic acid, an aqueous solution of a chelating agent, and a liquid chelating agent are preferred from the viewpoint of easy preparation and parity.

The chelate agent in the treatment liquid for removing an alkali metal containing a chelate agent is not particularly limited, and can be suitably selected from known chelate compounds. The chelate agent is usually used as a solution of water or an organic solvent, for example, a chelating agent which is liquid at room temperature as in the case of ethyl acetoacetate, diacetone alcohol, and ethyl acetate, without dissolving. In the case of water or an organic solvent, it can be used as a treatment liquid for alkali metal removal. The treatment liquid for removing an alkali metal composed of a chelating agent which is liquid in the vicinity of room temperature is extremely useful on a surface which hardly corrodes the metal wiring.

As described previously, when the chelate is solid near room temperature, the chelate is used as a solution of water or an organic solvent. Examples of the chelate compound which is solid at around room temperature include benzenetriol or catechol. As the organic solvent for dissolving the chelating agent, for example, an alcohol solvent or a glycol solvent can be used. Specific examples of the organic solvent that dissolves the chelating agent include methanol, ethanol, and the like.

From the viewpoint of the effect of reducing the sodium and potassium, the treatment liquid for removing the alkali metal is selected from the group consisting of inorganic acids and organic acids from the viewpoint of easiness of disposal or purification of the treatment liquid after the surface of the glass substrate is treated. The treatment liquid composed of the acidic compound and water is preferred.

As the inorganic acid and the organic acid, Brinell is usually used. Examples of the inorganic acid include hydrochloric acid, hydrogen bromide, sulfuric acid, and nitrate. Acid, phosphoric acid, hypochlorous acid, perchloric acid, sulfurous acid, persulfuric acid, nitrous acid, phosphorous acid, hypophosphorous acid, and phosphonic acid. Among these, hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid are preferred. Examples of the organic acid include acetic acid, formic acid, propionic acid, butyric acid, lactic acid, oxalic acid, fumaric acid, maleic acid, citric acid, succinic acid, tartaric acid, benzoic acid, methanesulfonic acid, and ethanesulfonic acid. Benzenesulfonic acid, and p-toluenesulfonic acid.

The concentration of the acidic compound in the treatment liquid is not particularly limited, and is preferably 50% by mass or less, more preferably 10% by mass or less, and preferably 5 for the treatment liquid for removing an alkali metal composed of an acidic compound and water. The mass % or less is particularly preferable, and the mass ratio is preferably 3% by mass or less.

The treatment liquid for removing an alkali metal selected from the group consisting of an acidic compound selected from a mineral acid and an organic acid and water may further contain a salt of an acidic compound contained in the treatment liquid for the purpose of buffering. The salt of the acidic compound is preferably an alkali metal salt, preferably a sodium salt or a potassium salt. The pH of the treatment liquid for buffering alkali metal removal is preferably 3 or more and less than 7, and preferably 4 or more and 6 or less.

The treatment of the glass substrate using the treatment liquid for removing the alkali metal is performed on a glass substrate in which the total ratio of the elemental components of sodium and potassium in the surface layer from the surface to the depth of 10 μm is more than 13% by mass. In the chemically strengthened glass substrate which is preferably a glass substrate, the total ratio of the elemental ratios of sodium and potassium in the surface layer from the surface to the depth of 10 μm is generally more than 13% by mass.

Further, the treatment for treating the liquid glass substrate for alkali metal removal is carried out until the exposed portion of the glass on the glass substrate is The total amount of the elemental ratios of sodium and potassium in the surface layer up to the depth of 10 μm is 13% by mass or less. Thereby, in the portion where the glass on the glass substrate is exposed, it is easy to peel off the etching mask formed by using the photoresist composition with almost no residue remaining.

In addition, if the alkali metal removal treatment is applied to the glass substrate without performing the lyophilization treatment, the treatment liquid for removing the alkali metal is less likely to be in contact with the surface of the glass substrate, and it is difficult to expose the glass present on the glass substrate. The alkali metal on part of the surface layer is removed to the desired extent.

From the viewpoint of peeling off the etching mask from the surface of the substrate in a short time, the ratio of the elemental composition of sodium and potassium in the surface layer from the surface to the depth of 10 μm in the portion exposed by the glass on the glass substrate after the alkali metal removal treatment The total amount is preferably 10% by mass or less, more preferably 8% by mass or less, and particularly preferably 3% by mass or less.

In the portion exposed to the glass on the glass substrate after the alkali metal removal treatment, the ratio of the potassium element component of the surface layer from the surface to the depth of 10 μm is preferably 10% by mass or less, more preferably 8.5% by mass or less. 3 mass% or less is particularly preferable.

In the portion where the glass on the glass substrate is exposed after the alkali metal removal treatment, the ratio of the sodium element component of the surface layer from the surface to the depth of 10 μm is preferably 3% by mass or less, more preferably 2% by mass or less. 0.5% by mass or less is particularly preferred.

The ratio of the elemental composition of sodium and potassium in the surface layer from the surface to the depth of 10 μm in the exposed portion of the glass on the glass substrate is The measurement can be performed using the XPS method (X-ray photoelectron spectroscopy).

The treatment of the glass substrate using the treatment liquid for removing the alkali metal may be carried out on a glass substrate having a total content ratio of elemental components of sodium and potassium from the surface to a depth of 10 μm of 13% by mass or less. In this case, even if the alkali metal removal treatment is not performed, the etching mask can be easily peeled off in the exposed portion of the glass on the surface of the glass substrate, but the etching can be more quickly performed by performing the alkali metal removal treatment. The cover is peeled off.

The method of removing the alkali metal is not particularly limited as long as the elemental ratio of potassium and sodium in the surface layer of the glass substrate can be reduced to a desired level. In this treatment, the surface of the glass substrate is brought into contact with the treatment liquid, and potassium and sodium are eluted into the treatment liquid for alkali metal removal. The method of bringing the treatment liquid for removing the alkali metal into contact with the surface of the glass substrate, for example, a method of immersing the glass substrate in the treatment liquid and then washing the surface of the substrate, and floating the surface of the glass substrate with the treatment liquid A method of washing the surface of the substrate, a method of spraying the surface of the glass substrate with water, and then washing the surface of the substrate, or a method of allowing the treatment liquid to flow down the surface of the glass substrate and then washing the surface of the substrate.

The time during which the surface of the glass substrate is in contact with the treatment liquid is preferably 45 seconds or longer, more preferably 1 minute or more, and particularly preferably 2 minutes or more. Further, the contact time is preferably 10 minutes or less. Even if the surface of the glass substrate is brought into contact with the treatment liquid for more than 10 minutes, no significant defects are caused, but an additional excellent effect is not obtained in the improvement of the peeling property of the etching mask. Further, depending on the type or pH of the treatment liquid, the treatment liquid is brought into contact with the glass substrate more than At 10 minutes, there is concern about corrosion metal wiring.

<Amine treatment step>

If necessary, after performing the above-described lyophilization step and alkali metal removal step, the surface of the glass substrate is subjected to an amine treatment. The amine treatment is carried out using a treatment liquid containing an amine which does not have a functional group capable of chemically bonding to the surface of the glass substrate.

Here, the functional group capable of chemically bonding to the surface of the glass substrate means a functional group capable of forming a covalent bond by reacting with a ruthenium atom or a hydroxyl group of various metal atoms bonded to the surface of the glass substrate. Examples of such a functional group include an alkoxy group bonded to an atom such as ruthenium, aluminum or titanium, a halogen atom, a cyano group, a trimethyl decylamino group contained in a decane or the like, and the like. . The functional groups capable of chemically bonding to the surface of the glass substrate are not limited to the functional groups specifically exemplified herein.

By applying an amine treatment to the surface of the glass substrate, the adhesion of the etching mask to the glass substrate can be maintained, and the peeling property of the etching mask in the portion where the permanent film of the surface of the glass substrate is exposed and the portion where the metal wiring is exposed can be maintained. . Further, by the amine treatment, it is easy to suppress the area on the side of the glass substrate on the opening of the etching mask formed on the glass substrate to be larger than the area of the opening on the surface of the etching mask.

The amine contained in the treatment liquid used for the amine treatment may be a primary amine, a secondary amine, or a tertiary amine. Specific examples of the amine contained in the treatment liquid used for the amine treatment include n-propylamine, n-butylamine, n-hexylamine, n-octylamine, and N,N-dimethyl group. Amine, N, N-diethyl Amine, N,N-di-n-propylamine, N,N-di-n-butylamine, trimethylamine, triethylamine, tri-n-propylamine, tri-n-butyl Alkylamine such as amine; methanolamine, ethanolamine, n-propanolamine, n-butanolamine, N-methylmethanolamine, N-ethylmethanolamine, N-ethylethanolamine, Nn-propylethanolamine, Nn -butylethanolamine, N-methyl-n-propanolamine, N-ethyl-n-propanolamine, Nn-propyl-n-propanolamine, Nn-butyl-n-propanolamine, N -Methyl-n-butanolamine, N-ethyl-n-butanolamine, Nn-propyl-n-butanolamine, Nn-butyl-n-butanolamine, N,N-dimethyl Methanolamine, N,N-diethylmethanolamine, N,N-di-n-propylmethanolamine, N,N-di-n-butylmethanolamine, N,N-dimethylethanolamine, N, N-diethylethanolamine, N,N-di-n-propylethanolamine, N,N-di-n-butylethanolamine, N,N-dimethyl-n-propanolamine, N,N-di Ethyl-n-propanolamine, N,N-di-n-propyl-n-propanolamine, N,N-di-n-butyl-n-propanolamine, N,N-dimethyl -n-butanolamine, N,N-diethyl-n-butanolamine, N,N-di-n-propyl-n-butanolamine, N,N-di-n-butyl-n -butanolamine, N-methyldimethanolamine, N-ethyldimethanolamine, Nn-propyldimethanolamine, Nn- Dimethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-propyldiethanolamine, Nn-butyldiethanolamine, N-methyldi-n-propanolamine, N-ethyldi -n-propanolamine, Nn-propyl di-n-propanolamine, Nn-butyldi-n-propanolamine, N-methyldi-n-butanolamine, N-ethyldi-n -butanolamine, Nn-propylbis-n-butanolamine, Nn-butyldi-n-butanolamine, N-(aminomethyl)methanolamine, N-(aminomethyl)ethanolamine, N-(Aminomethyl)-n-propanolamine, N-(aminomethyl)-n-butanolamine, N-(2-aminoethyl)methanolamine, N-(2-amino group Ethyl)ethanolamine, N-(2-aminoethyl)-n-propanolamine, N-(2-aminoethyl)-n-butanolamine, N-(3-amino-n-propyl Methanol Amine, N-(3-amino-n-propyl)ethanolamine, N-(3-amino-n-propyl)-n-propanolamine, N-(3-amino-n-propyl) -n-butanolamine, N-(4-amino-n-butyl)methanolamine, N-(4-amino-n-butyl)ethanolamine, N-(4-amino-n-butyl Alkanolamines such as -n-propanolamine, N-(4-amino-n-butyl)-n-butanolamine, triethanolamine, tri-n-propanolamine; aniline, N-methylaniline , N-ethylaniline, N,N-dimethylaniline, N,N-diethylaniline, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, etc. a metal amine; tetramethylethylenediamine such as tetramethylethylenediamine, tetraethylethylenediamine, tetra-n-propylethylenediamine, tetra-n-butylethylenediamine; methylaminomethyl Amine, 2-methylaminoethylamine, 3-methylamino-n-propylamine, 4-methylamino-n-butylamine, ethylaminomethylamine, 2-ethyl Aminoethylamine, 3-ethylamino-n-propylamine, 4-ethylamino-n-butylamine, n-propylaminomethylamine, 2-n-propylamino Ethylamine, 3-n-propylamino-n-propylamine, 4-n-propylamino-n-propylamine, n-butylaminomethylamine, 2-n-butyl Aminoethylamine, 3-n-butylamino-n-propylamine, 4-n-butylamine An alkylaminoalkylamine such as -n-butylamine; a polyamine such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine; pyridine, pyrrole a cyclic amine such as piperazine, pyrrolidine, piperidine, pyridyl, morpholine, methylmorpholine, dioxodicyclooctane, diazepaneheptanone or dinonicycloundecene.

Since the peeling property of the etching mask becomes good, the amine is preferably a primary amine among the above specific examples.

Further, the amine contained in the treatment liquid is preferably an amine which is solid at room temperature. Here, the room temperature means the normal temperature (5 to 35 ° C) prescribed by JIS Z 8703. When a solid amine at room temperature is used, the treatment liquid is applied to the glass. After the substrate, a solid amine adheres to the surface of the glass substrate. Therefore, the viscosity of the surface of the glass substrate after the amine treatment is suppressed. If the viscosity of the glass substrate after the amine treatment is suppressed, it is easier to operate the glass substrate in the step after the amine treatment.

From the viewpoint of easily obtaining the desired effect obtained by the amine treatment, and from the viewpoint of easily suppressing the viscosity after the amine treatment, it is preferred to use 2, 2, 6 which can be N-substituted by an alkyl group having 1 to 20 carbon atoms. 6-Tetramethylpiperidin-4-ylamine. The alkyl group substituted for the nitrogen atom may be a linear alkyl group or a branched alkyl group. The number of carbon atoms of the alkyl group replacing the nitrogen atom is preferably from 1 to 12, more preferably from 1 to 6. As the amine, 2,2,6,6-tetramethylpiperidin-4-yl which can be N-substituted by an alkyl group having 1 to 20 carbon atoms, and 2,2,6,6-tetramethyl Preferably, the piperidin-4-yl group and the N-methyl-2,2,6,6-tetramethylpiperidin-4-yl group are preferred.

The molecular weight of the amine having 2,2,6,6-tetramethylpiperidin-4-yl group which may be N-substituted with an alkyl group having 1 to 6 carbon atoms is not particularly limited, and it is easy to suppress the glass after the amine treatment. The viewpoint of the surface stickiness of the substrate is preferably 200 to 5,000, and preferably 1500 to 5,000.

A suitable example of the amine having 2,2,6,6-tetramethylpiperidin-4-yl group which may be N-substituted with an alkyl group having 1 to 6 carbon atoms is exemplified by the following structures. Further, the n-number described in the lower right of the parentheses in the following structural formula represents the number of repetitions of the structural unit in the parentheses. The number of repeating units is not particularly limited, but it is preferred that the molecular weight is within the above range.

When a liquid amine is used at the temperature of the amine treatment, the liquid amine can be directly used as a treatment liquid. Typically, the treatment liquid is preferably diluted with an organic solvent. In particular, when the amine is solid at room temperature, the amine is used in a state of being diluted in an organic solvent. In this case, the concentration of the amine in the treatment liquid is not particularly limited, but is preferably 0.01 to 90% by mass, more preferably 0.05 to 50% by mass, and particularly preferably 0.08 to 25% by mass.

When the treatment liquid is a solution containing an amine, the solvent is not particularly limited as long as it does not inhibit the object of the present invention, and an aqueous solution of water, an organic solvent or an organic solvent can be used. From the viewpoint that the surface of the glass substrate is easily wetted by the treatment liquid, the solvent is preferably an organic solvent. Examples of the organic solvent include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether and propylene glycol single Propylene glycol monoalkyl ether such as ethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether; propylene glycol dioxane such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether or propylene glycol dibutyl ether a propylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; Kesai Susu, butyl 赛苏苏, etc. Sai Su; butyl Carbitol such as alcohol; methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, etc.; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate Aliphatic carboxylic acid esters such as ester, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate; 3-methoxypropane Other esters such as methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; toluene, An aromatic hydrocarbon such as hydrazine; a ketone such as 2-heptanone, 3-heptanone, 4-heptanone or cyclohexanone; N-dimethylformamide, N-methylacetamide, N,N- Examples include decylamines such as dimethylacetamide and N-methylpyrrolidone; and lactones such as γ-butyrolactone. These organic solvents may be used singly or in combination of two or more.

The amine treatment adheres the amine to the surface of the glass substrate by applying a treatment liquid containing an amine and removing the solvent in the treatment liquid as necessary. The method of applying the treatment liquid on the glass substrate is not particularly limited, and examples thereof include a contact transfer type coating apparatus such as a roll coater, a reverse coater, and a bar coater, or a spin coater or a shower. A method of a non-contact type coating apparatus such as a curtain coater, a slit coater, or a spray coater, or a method of immersing a glass substrate in a treatment liquid.

On the glass substrate subjected to the amine treatment by the above method, an etching mask is formed by a method or the like described later.

How to form a etch mask

An etching mask is formed using the photoresist composition on the glass substrate subjected to the pretreatment by the aforementioned method.

Specifically, it comprises a coating film forming step of forming a coating film by coating a photoresist composition on a surface of a glass substrate which has been subjected to pretreatment by the above method, and selectively exposing and coating the film. An etch mask is formed by the exposure step of the film and the method of developing the exposed coating film to form an etch mask.

Hereinafter, the coating film forming step, the exposing step, and the developing step will be described in order.

<Coating film forming step>

The coating film forming step uses a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, or a spin coater, a curtain coater, a slit coater, or the like. In the non-contact type coating apparatus, the photoresist composition is applied onto a glass substrate to form a coating film. The formed coating film may also be heated (prebaked) as necessary.

The film thickness of the formed coating film is not particularly limited, but is, for example, about 20 to 200 μm. The heating conditions at the time of prebaking are not particularly limited, and are, for example, about 70 to 150 ° C for 2 to 60 minutes. Further, the coating and prebaking of the photoresist composition may be carried out a plurality of times until a coating film having a desired film thickness can be formed.

When the photoresist composition can be used as a dry film, a dry film of the photoresist composition is applied to the surface of the glass substrate to form a coating film. The dry film system of the photoresist composition can be formed by applying a photoresist composition onto the release film and drying the photoresist composition as necessary.

<Exposure step>

The exposure step is to selectively expose the coating film by irradiating an active energy ray such as ultraviolet rays through a light-shielding pattern. The exposure system can use a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, or the like to emit ultraviolet light. The amount of the energy ray to be irradiated differs depending on the composition of the photoresist composition, but is preferably, for example, about 30 to 3,000 mJ/cm ² . During the exposure, the coating film may be heated (PEB) as necessary. The heating conditions at this time are not particularly limited, and are, for example, about 3 to 20 minutes at 80 to 150 °C.

<Exposure step>

The developing step is to obtain an etching mask by developing a region-selectively exposed coating film in an exposure step using a developing solution. The development method is not particularly limited, and a dipping method, a spray method, a shower method, a liquid-filling method, or the like can be used. The imaging liquid is suitably selected depending on the type of the photoresist composition. The developing solution may, for example, be a 0.25 to 3% by mass aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an organic amine, tetramethylammonium hydroxide, triethanolamine, N-methylpyrrolidone or dimethyl hydrazine. Wait. The development time is not particularly limited, and is, for example, about 1 to 120 minutes. Also, the imaging liquid system can be heated to a temperature of 25 to 40 °C. After the development, the etching mask can also be heated (post-baking). The heating conditions are not particularly limited, and are, for example, about 2 to 120 minutes at 70 to 300 °C.

Further, when the photoresist composition is a positive type, after the development, the etching mask may be irradiated with an active energy ray such as ultraviolet rays and heated at the same time. After cure. The post-hardening system causes the quinonediazide-containing compound contained in the photoresist composition to form an intermediate (indene ketene) by an active energy ray, and this is combined with an alkali-soluble resin having a phenolic hydroxyl group or The compound containing a quinonediazide group is bonded to polymerize.

Further, in the case where the etching process described later is performed on both the front and back surfaces of the glass substrate, after performing the above-described pretreatment on both the front and back surfaces of the glass substrate, an etching mask is formed on both surfaces of the front and back of the glass substrate. In this case, the glass substrate may have a metal wiring and a permanent film on at least one surface.

Processing method of glass substrate

The glass substrate having the etching mask formed by the above method is processed by etching.

Specifically, the etching step of etching the portion of the glass substrate having the etching mask on the surface of the etching mask is performed; after the etching step, the etching mask is peeled off from the surface of the glass substrate The method of the stripping step is to process the glass substrate.

Hereinafter, the etching step and the peeling step will be described in order.

<etching step>

Examples of the processing of the glass substrate formed by the etching include forming a dot or a linear recess on the surface of the substrate, forming a through hole through the substrate in the thickness direction, and cutting the substrate. As the etching method, wet etching which is generally performed by immersion in an etching liquid can be mentioned. As the etching solution, for example, hydrogen Fluoric acid alone, mixed acid of hydrofluoric acid and ammonium fluoride, hydrofluoric acid and other acids (hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc.). The etching treatment time is not particularly limited, and is, for example, about 10 to 60 minutes. Also, the etching solution can be heated to a temperature of 25 to 60 ° C.

<Peeling step>

After the etching step, the etching mask is peeled off from the surface of the glass substrate in the stripping step. The method of peeling the etching mask from the surface of the glass substrate is not particularly limited, and the peeling of the etching mask is typically performed using a peeling liquid.

The peeling liquid is not particularly limited as long as it can be peeled off from the surface of the glass substrate, and can be suitably selected from the peeling liquid used in the past for peeling off the film formed using the photoresist composition.

Examples of the stripping liquid include a stripping solution such as an organic solvent, or a nitrogen-containing basic organic compound such as an organic amine or a quaternary ammonium hydroxide, or an ammonia or a basic alkali metal compound. An alkaline stripping solution of an inorganic basic compound. Examples of the organic amines include monoethanolamine, diethanolamine, and triethanolamine. Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide and the like. Examples of the basic alkali metal compound include sodium hydroxide, potassium hydroxide, sodium carbonate, and the like. The solvent contained in the alkaline stripping solution can be appropriately selected from water, an organic solvent, and an aqueous solution of an organic solvent. Among the above-mentioned peeling liquids, a peeling liquid containing a basic compound and an organic solvent which is easy to peel off the etching mask is preferable.

When the alkaline stripper contains water as a solvent, the alkaline stripper may contain a rust preventive. As the rust preventive agent, those known in the past can be suitably used.

When the peeling liquid is an alkaline stripping liquid, it is preferable that the basic compound contained in the stripping liquid has less damage to the metal wiring due to the nitrogen-containing basic organic compound. Further, when the solvent in the stripping solution contains an organic solvent, the solvent composed only of the organic solvent has less damage to the metal wiring, so that it is preferably composed of only an organic solvent, and the solvent is composed only of an organic solvent. It is preferred to include an aprotic polar organic solvent. The solvent in the stripping liquid may be combined with two or more kinds of aprotic polar organic solvents. Examples of the aprotic polar organic solvent which may be contained in the stripping solution include N-methyl-2-pyrrolidone, N,N-dimethylformamide, γ-butyrolactone, and N. N-dimethylacetamide, dimethyl hydrazine, dimethyl urea, and dimethyl imidazolidinone. When the stripping solution contains a solvent composed only of an organic solvent containing an aprotic polar organic solvent, the content of the aprotic polar organic solvent in the solvent is preferably 70% by mass or more, and more preferably 80% by mass or more. It is particularly good at 90% by mass or more.

The peeling method of the etching mask formed by the peeling liquid is not specifically limited. Examples of the method of peeling off the etching mask by the stripping liquid include a liquid-filling method, a dipping method, a liquid-filling method, and a spray method. The condition when the etching mask is peeled off by the peeling liquid is not particularly limited. The stripping solution can also be used after heating to 25~60 °C.

[Examples]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by the examples.

[Examples 1 to 6 and Comparative Examples 1 to 6]

In Examples 1 to 6 and Comparative Examples 1 to 6, the following GL1 was used for the glass substrate. Further, the total ratio of the elemental components of sodium to potassium is the total of the ratio of the elemental components of sodium to potassium in the surface layer from the surface to the depth of 10 μm.

<GL1>

Type: chemically strengthened glass substrate

Total ratio of elemental composition of sodium to potassium: 20% by mass

Vickers hardness: 570kgf/mm ²

Thickness: 0.55mm

The GL1 described above is a pattern having a metal wiring composed of a Mo-Al-Mo laminate, and a transparent permanent film formed using the following permanent film material.

<permanent film material>

15 parts by mass of an alkali-soluble resin composed of the following units I/II/III/IV=14/11/40/35 (the numerical value is the mass% of each unit in the resin), and OXE-01 (manufactured by BASF Corporation) 0.5 parts by mass, 7 parts by mass of dipentaerythritol hexaacrylate, 0.5 parts by mass of BYK-310 (manufactured by BicChemy Japan Co., Ltd.), 15 parts by mass of propylene glycol monomethyl ether acetate, and diethylene glycol monomethyl ether 35 The mass fraction is made into a homogeneous solution and prepared into a permanent film material.

In the examples and comparative examples, the following amines were used as the amine in the treatment liquid for the amine treatment. The types of the amines used in the respective examples and comparative examples and the concentrations of the amines in the treatment liquid are shown in Table 1. The solvent used for the dilution of the treatment liquid was propylene glycol monomethyl ether acetate.

A1: Amines of the following structure

A2: monoethanolamine

A3: 3-aminopropylmethyldimethoxydecane

A4: hexamethyldioxane

In each of the examples and comparative examples, the amine treatment liquid was spin-coated on a glass substrate. In Examples 1 to 5 and Comparative Examples 1 to 6, spin coating was performed under conditions of 1000 rpm and 30 seconds, and in Example 6, it was 3000 rpm. Spin coating was carried out under conditions of 30 seconds. In the case of using an amine treatment liquid containing a solvent, the solvent was removed by baking at 110 ° C for 120 seconds. The glass substrate was subjected to an amine treatment by the above method.

Next, an etching mask was formed on the glass substrate pretreated by the above method in accordance with the following method. First, a photoresist composition was applied onto a glass substrate to form a coating film having a film thickness of 70 μm. The formed coating film was exposed to the exposure amount shown in Table 1 through a mask for forming a hole having a diameter of 300 μm, and then developed to form an etching mask having a hole.

[Photoresist composition]

80 parts by mass of the resin, 10 parts by mass of the crosslinking agent, 0.5 part by mass of the acid generator, and 10 parts by mass of the plasticizer were uniformly mixed in an organic solvent to obtain a solid content concentration of 50% by mass, and then the composition 1 was obtained.

The resin is a cresol novolac resin obtained by condensing m-cresol with p-cresol at a m-cresol/p-cresol=60/40 (mass ratio) by a formaldehyde solution. The cresol novolac resin has a mass average molecular weight of 5,000.

As the crosslinking agent, 2,4,6-gin[bis(methoxymethyl)amino]-1,3,5-triazine was used.

The acid generator is 2,4-bis(trichloromethyl)-6-mallowyl-1,3,5-triazine.

The plasticizer used was polyvinyl methyl ether (mass average molecular weight: 100,000).

The organic solvent is propylene glycol monomethyl ether acetate.

[Graph shape evaluation]

For the direction of the surface of the glass substrate, the formed etching mask is observed from the vertical above using a microscope, and the opening diameter (top diameter) of the hole on the surface opposite to the surface of the glass substrate which is in contact with the etching mask is measured, and the glass is measured. The diameter of the hole on the surface of the substrate (bottom diameter). The case where the value of the bottom diameter-top diameter was 30 μm or less was judged as ○, and the case where the value of the bottom diameter-top diameter exceeded 30 μm was judged as ×.

[Peeling time evaluation]

After the etching mask was formed, an etching solution of 55 ° C (composition: hydrofluoric acid / sulfuric acid / water = 15 / 15 / 70 (mass ratio)) was used, and the glass substrate was etched by etching for 90 minutes on the glass substrate. A through hole is formed.

The glass substrate on which the through-holes were formed was immersed in a peeling liquid (ST-120, manufactured by Tokyo Ohka Kogyo Co., Ltd.) heated to 60 ° C, and the etching mask was peeled off from the glass substrate. The time from the start of the immersion to the peeling of the etch mask from the surface of the glass substrate was measured. The time at which the peeling was completed was judged visually. The case where the time until the end of the peeling was less than 10 minutes was judged as ○, and the case where the time was 10 minutes or more was judged as ×.

In the examples 1 to 6, it is understood that a treatment liquid containing an amine having no functional group capable of chemically bonding to the surface of the glass substrate is applied to the glass substrate having the metal wiring and the non-conductive coating on the surface thereof. The amine treatment can form an etching mask having an opening portion having a small difference between the top area and the bottom area, and the exposed portion of the glass, the portion where the metal wiring is exposed, and the portion where the non-conductive film is exposed can be formed. Both can quickly peel off the etch mask.

On the other hand, in Comparative Examples 1 to 6, it was found that the treatment of the glass substrate was carried out by using an amine having a functional group capable of chemically bonding to the surface of the glass substrate, resulting in formation of a top surface and a bottom portion. The etching mask of the opening portion having a large difference in area requires a long time to peel off the etching mask.

Claims (8)

A pretreatment method for a glass substrate, which is a method for performing a treatment before forming an etch mask on a surface of a glass substrate by photolithography using a photoresist composition, which comprises an amine treatment step; The surface of the glass substrate is treated with an amine formed by a treatment liquid, and the treatment liquid contains an amine having no functional group capable of chemically bonding with the surface of the glass substrate; the glass substrate has metal wiring on the surface, A non-conductive film made of an organic or inorganic material has a portion where the glass is exposed, a portion where the metal wiring is exposed, and a portion where the film is exposed, and contains sodium and/or potassium. The method of claim 1, wherein the aforementioned amine contained in the treatment liquid used in the aforementioned amine treatment is an amine which is solid at room temperature. The method of claim 1, comprising a lyophilization step and an alkali metal removal step; the lyophilization step is performed by lyophilizing the surface of the glass substrate, and the lyophilization treatment is performed on the glass substrate a liquid wettability of the exposed portion of the glass; the alkali metal removing step is performed by an alkali metal removal treatment between the lyophilization step and the amine treatment step, and the alkali metal removal treatment is performed on the surface of the glass substrate and the alkali The treatment liquid for metal removal is contacted to reduce the amount of alkali metal in the surface layer of the exposed portion of the glass substrate. The method of claim 3, wherein the alkali metal removal is performed The treatment liquid used is selected from the group consisting of an aqueous acid solution, a liquid organic acid, an aqueous solution of a chelating agent, and a liquid chelate compound. The method of claim 1, wherein the water contact angle in the exposed portion of the glass on the glass substrate is reduced to 30 or less by the lyophilization treatment. The method of claim 1, wherein the glass substrate is a glass substrate having a Vickers hardness of 500 kgf/mm ² or more. A method for forming an etching mask, comprising: a coating film forming step of forming a coating film by coating a photoresist composition on a surface of the glass substrate processed by a processing method before the request item 1; An exposure step of selectively exposing the coating film; developing the exposed coating film to form an etching step of the etching mask. A method for processing a glass substrate, comprising: exposing a glass having a surface of the etching mask to a glass substrate having an etching mask formed by the method of forming an etching mask of claim 7; An etching step of partially etching; after the etching step, a peeling step of peeling the etching mask from the surface of the glass substrate.