JP6224490B2 - Glass substrate pretreatment method for forming an etching mask - Google Patents

Description

  The present invention relates to a glass substrate pretreatment method for forming an etching mask, which is applied to a glass substrate having a metal wiring and a nonconductive film made of an organic or inorganic material on the surface thereof, The present invention relates to a method of forming an etching mask on a glass substrate subjected to a treatment method, and a processing method by etching of a glass substrate provided with the etching mask formed by the method.

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

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

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

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

JP 2008-0776768 A JP 2010-072518 A

  However, in the methods described in Patent Documents 1 and 2, depending on the material of the glass constituting the glass substrate, it may take a long time to peel the etching mask formed using the resist composition from the surface of the glass substrate. There is a problem that a large amount of residue tends to remain on the surface of the glass substrate after the etching mask is peeled off. This problem is particularly remarkable when the polymer compound contained in the resist composition has a hydroxyl group or a carboxyl group.

  Moreover, a permanent film, which is a nonconductive film made of an organic or inorganic material, is often formed in advance on the surface of a glass substrate to be etched. However, when etching is performed after forming an etching mask using a resist composition on a glass substrate having a metal wiring and a permanent film on the surface, when the etching mask is peeled off, the glass substrate, the metal wiring, Due to the difference in surface state from the permanent film, there is a problem that an etching mask residue is partially generated on the glass substrate surface.

  In the present invention, when an etching mask is formed on a glass substrate provided with a metal wiring and a non-conductive film made of an organic or inorganic material on the surface, etching is performed and the etching mask is peeled off. Regardless of the type of surface material on the substrate, the glass substrate pretreatment method that enables the etching mask to be peeled off quickly without leaving any peeling residue on the entire surface of the glass substrate, and the pretreatment method are applied. Another object of the present invention is to provide a method for forming an etching mask on a glass substrate and a processing method by etching a glass substrate provided with the etching mask formed by the method.

  Prior to forming an etching mask on a glass substrate provided with a metal wiring and a non-conductive film made of an organic or inorganic material on the surface, the present inventors applied a predetermined lyophilic treatment to the glass substrate. And it discovered that the said subject can be solved by performing an alkali metal removal process and a hydrophobization process, and came to complete this invention.

A first aspect of the present invention is a pretreatment method for a glass substrate, which is performed before forming an etching mask on the surface of the glass substrate by a photolithography method using a resist composition,
The glass substrate has a metal wiring and a non-conductive coating made of an organic or inorganic material on the surface, a portion where the glass is exposed on the surface, a portion where the metal wiring is exposed, and a portion where the coating is exposed And contains sodium and / or potassium,
A lyophilic step for applying a lyophilic process for improving the wettability of the treatment liquid for removing the alkali metal to the exposed surface of the glass on the glass substrate,
After the lyophilic process, the surface of the glass substrate is brought into contact with the treatment solution for removing the alkali metal, and the alkali metal removal treatment is performed to reduce the amount of alkali metal on the surface layer of the glass substrate surface where the glass is exposed. Applying an alkali metal removal step;
After the alkali metal removal step, the surface of the glass substrate is subjected to a hydrophobizing treatment for hydrophobizing the surface of the glass substrate.
The treatment liquid for removing alkali metal is a treatment liquid containing an acid or a chelating agent,
The pretreatment method, wherein the total of the elemental component ratios of sodium and potassium in the surface layer from the surface to the depth of 10 μm is 13% by mass or less at the portion where the glass on the glass substrate subjected to the alkali metal removal treatment is exposed It is.

A second aspect of the present invention includes a coating film forming step of forming a coating film by applying a resist composition to the surface of the glass substrate treated by the pretreatment method according to the first aspect;
Exposing the coating film in a position-selective manner; and
A development step of developing an exposed coating film to form an etching mask.

In a third aspect of the present invention, etching is performed on a portion of the glass substrate provided with the etching mask formed by the etching mask forming method according to the second aspect, where the glass on the surface provided with the etching mask is exposed. Applying an etching process;
And a peeling step of peeling the etching mask from the surface of the glass substrate after the etching step.

  According to the present invention, when an etching mask is formed on a glass substrate having a metal wiring and a non-conductive film made of an organic or inorganic material on the surface, then etching processing and peeling of the etching mask are performed. Regardless of the type of surface material on the glass substrate, a pretreatment method for the glass substrate that enables the etching mask to be peeled off quickly with almost no peeling residue on the entire surface of the glass substrate, and the pretreatment method. It is possible to provide a method for forming an etching mask on a given glass substrate and a processing method by etching a glass substrate provided with the etching mask formed by the method.

  Hereinafter, regarding the present invention, a glass substrate to be processed, a resist composition used for forming an etching mask, a glass substrate pretreatment method, an etching mask forming method, and a glass substrate processing method will be described in this order. To do.

≪Glass substrate≫
In the pretreatment method of a glass substrate, a glass substrate provided with a metal wiring and a nonconductive film (hereinafter also referred to as a permanent film) made of an organic or inorganic material is used on the surface thereof. On the surface of the glass substrate, there are 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 a glass substrate will not be specifically limited if it is glass containing sodium and / or potassium. The material of the glass substrate is selected from conventionally known glasses in consideration of strength, product manufacturing cost, and the like.

As the glass substrate, a glass substrate having a Vickers hardness of 500 kgf / mm ² or more is preferable. Vickers hardness of the glass substrate 600 kgf / mm ² or more, more preferably, 650 kgf / mm ² or more is particularly preferable. The higher the Vickers hardness of the glass substrate, the better. However, the Vickers strength of the glass substrate that can be actually obtained is 2000 kgf / mm ² or less.

The type of 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 tempered glass substrate is obtained by ion exchange of sodium ions and potassium ions with respect 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. The degree of strengthening is not particularly limited as long as the strength after the treatment is improved compared to that before the ion exchange treatment, and the strength is not particularly limited. A layer is formed, and the strength of the glass substrate can be enhanced by, for example, 5 times or more.

  The Vickers hardness of the glass substrate can be measured according to 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 a thickness that is not broken by pressing of the indenter when measuring the hardness.

  As described above, the glass substrate includes a metal wiring and a permanent film that is a non-conductive film on the surface to be etched. For this reason, the etching with respect to the glass substrate which equips the surface with metal wiring and a permanent film is performed with respect to the part which glass exposes.

  An etched glass substrate is often used as a substrate for various devices with a metal wiring and a permanent film on the surface. However, when a large glass substrate that does not have metal wiring and permanent film on the surface is cut by etching and cut into a plurality of glass substrates of a predetermined size, the surface of each of the obtained small glass substrates is On the other hand, a complicated process for forming a metal wiring and a permanent film is required.

  On the other hand, if the metal wiring and the permanent film that should be provided on the small glass substrate are collectively formed on the surface of the large glass substrate before being cut, the small size obtained by cutting by etching. The glass substrate can be used as it is as a substrate for various apparatuses.

The method for forming the metal wiring on the surface of the glass substrate is not particularly limited. The metal wiring can be formed by a known method for forming a metal wiring on the surface of the glass substrate. Further, the material of the metal wiring is not particularly limited. Typical examples of metal wiring materials include transparent electrode materials such as ITO, SnO ₂ , and ZnO, reflective electrode materials such as AgPdCu, and Mo—Al—Mo laminates. Moreover, common metal wiring materials, such as copper, nickel, gold | metal | money, silver, chromium, aluminum, and these alloys, can also be used.

The permanent film formed on the surface of the glass substrate is a non-conductive film made of an organic or inorganic material. Here, that the permanent film is non-conductive 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, a spacer, a black matrix, and an insulating film. When the permanent film is an overcoat or a transparent spacer, the permanent film is required to have high transparency. In this case, it is preferable to form a permanent film using a photosensitive resin composition containing an alkali-soluble resin having a specific structure described later, a photopolymerizable compound, and a photopolymerization initiator. Formation of the permanent film using the photosensitive resin composition is performed according to a general photolithography method.

  Examples of the alkali-soluble resin contained in such a photosensitive resin composition include (a1) a unit derived from an unsaturated carboxylic acid and (a2) a unit derived from an alicyclic skeleton-containing unsaturated compound having no epoxy group. Can be used. (A1) A radiation-sensitive material that provides a cured film having excellent transparency by using an alkali-soluble resin containing (a2) units and (a2) units, and that suppresses excessive dissolution of exposed areas during development after exposure. It is easy to obtain a functional resin composition.

  (A1) Unsaturated carboxylic acids that generate units include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; these dicarboxylic acids Anhydrous anhydride; and the like. Among these, (meth) acrylic acid and maleic anhydride are preferable in terms of copolymerization reactivity, alkali solubility of the resulting resin, availability, and the like. The alkali-soluble resin may contain a combination of two or more units (a1) derived from these unsaturated carboxylic acids.

(A2) As an alicyclic group containing unsaturated compound which does not have an epoxy group which gives a unit, the compound represented by following formula (a2-1)-(a2-7) is mentioned, for example. In these, since it is easy to obtain the photosensitive resin composition with favorable developability, the compounds represented by the following formulas (a2-3) to (a2-8) are preferable, and the following formula (a2-3) or The compound represented by (a2-4) is more preferable.

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 1 to 5 carbon atoms. Represents an alkyl group. R ¹⁰² is preferably a single bond or a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group or a hexamethylene group. R ¹⁰³ is preferably a methyl group or an ethyl group.

  The mass average molecular weight of the alkali-soluble resin (Mw: measured value by gel permeation chromatography (GPC) in terms of polystyrene. Same in this specification) is preferably 2000 to 200000, more preferably 2000 to 18000, and more preferably 3000 to 15000. Particularly preferred.

  The photopolymerizable compound contained in the photosensitive resin composition that gives the highly transparent permanent film is a photopolymerizable compound described later as a component of the second negative resist composition used for forming the etching mask. The same compound can be used. 5-60 mass% is preferable with respect to solid content of the photosensitive resin composition, and, as for content of a photopolymerizable compound, 10-50 mass% is more preferable.

  It does not specifically limit as a photoinitiator contained in the photosensitive resin composition which gives said highly transparent permanent film, A conventionally well-known photoinitiator 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-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime), 1,2-octanedione, 1- [4- (phenylthio)- , 2- (O-benzoyloxime)], 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4 -Ethyl dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1 -Phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxy Shim, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4- Diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene Peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl Benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin , Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloro Acetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butylto Chloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6 -Tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6 -Bis (trichloromethyl) -s-triazine, 2- [2- (furan 2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s -Triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl)- s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-butyl) Lomo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-Bromo-4-methoxy) styrylphenyl-s-triazine and the like. These photopolymerization initiators can be used alone or in combination of two or more.

  Among these, it is particularly preferable in terms of sensitivity to use an oxime-based photopolymerization initiator. Among oxime-based photopolymerization initiators, particularly preferred are ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyl). Oxime), and 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)].

  The content of the photopolymerization initiator in the photosensitive resin composition is preferably 0.1 to 50 parts by mass, and 0.5 to 10 parts by mass with respect to a total of 100 parts by mass of the solid content of the photosensitive resin composition. More preferred.

  The photosensitive resin composition that gives the highly transparent permanent film may contain an organic solvent as necessary. As the organic solvent, an organic solvent similar to the organic solvent described later can be used as a component of the positive resist composition used for forming the etching mask.

  Content of the organic solvent in the photosensitive resin composition is not specifically limited, It is the quantity in the range which can apply | coat the photosensitive resin composition to a board | substrate etc., and is suitably set according to a coating film thickness. The viscosity of the photosensitive resin composition is preferably 0.9 to 500 cp, more preferably 1 to 50 cp, and further preferably 1 to 30 cp. Moreover, 1-80 mass% is preferable and, as for the solid content density | concentration of the photosensitive resin composition, 5-50 mass% is more preferable.

≪Resist composition≫
Etching is performed when the glass substrate is processed by a method described later. For this reason, an etching mask is formed on the surface of the glass substrate prior to etching. This etching mask is formed by a photolithography method using a resist composition.

  The resist composition is not particularly limited as long as it is a resist composition conventionally used for forming an etching mask during etching. Among such resist compositions, a resist composition containing a polymer compound having a hydroxyl group or a carboxyl group is preferable. An etching mask formed using such a resist composition is advantageous in terms of the accuracy of etching because it has excellent adhesion to the substrate and is difficult to peel from the substrate during etching.

  On the other hand, an etching mask formed on the surface of a conventionally used glass substrate using a resist composition containing a polymer compound having a hydroxyl group or a carboxyl group leaves an etching mask residue after the etching process. It was difficult to peel off from the substrate surface in a short time. However, when a glass substrate pretreated by a method described later is used, the etching mask can be separated from the substrate surface in a short time without leaving a residue of the etching mask.

  Hereinafter, preferred specific examples of the resist composition will be described. The resist composition is not limited to the resist composition specifically described below.

<Positive resist composition>
The positive resist composition contains (A1) an alkali-soluble resin having a phenolic hydroxyl group and (B1) a quinonediazide group-containing compound.

[(A1) Alkali-soluble resin having phenolic hydroxyl group]
As an alkali-soluble resin having a phenolic hydroxyl group (hereinafter, also referred to as “component (A)”), for example, a polyhydroxystyrene resin can be used. The polyhydroxystyrene resin has at least a structural unit derived from hydroxystyrene.

  As used herein, “hydroxystyrene” refers to hydroxystyrene, and those obtained by substituting a hydrogen atom bonded to the α-position of hydroxystyrene with another substituent such as a halogen atom, an alkyl group, or a halogenated alkyl group, and derivatives thereof. The concept includes a hydroxystyrene derivative (monomer).

  In the “hydroxystyrene derivative”, at least a benzene ring and a hydroxyl group bonded thereto are maintained. For example, a hydrogen atom bonded to the α-position of hydroxystyrene is a halogen atom, an alkyl group having 1 to 5 carbon atoms, Those substituted with other substituents such as a halogenated alkyl group, and those having an alkyl group having 1 to 5 carbon atoms bonded to the benzene ring to which the hydroxyl group of hydroxystyrene is bonded, or benzene having this hydroxyl group bonded The ring further includes one having 1 to 2 hydroxyl groups bonded thereto (in this case, the total number of hydroxyl groups is 2 to 3).

  Examples of the halogen atom include a chlorine atom, a fluorine atom and a bromine atom, and a fluorine atom is preferable.

  The “α-position of hydroxystyrene” means a carbon atom to which a benzene ring is bonded, unless otherwise specified.

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

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

The alkyl group for R ^a1 preferably has 1 to 5 carbon atoms. Moreover, a linear or branched alkyl group is preferable, and a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc. Can be mentioned. Among these, a methyl group is preferable industrially.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

As the halogenated alkyl group, a part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms described above are substituted with a halogen atom. Among these, those in which all of the hydrogen atoms are substituted with fluorine atoms are preferable. Further, a linear or branched fluorinated alkyl group is preferable, and a trifluoromethyl group, a hexafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, and the like are more preferable, and a trifluoromethyl group (—CF ₃ ). Is most preferred.

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

^Examples of the alkyl group having 1 to 5 carbon atoms of R ^a2 include the same as those in the case of R ^a1 .

  q is an integer of 0-2. Among these, 0 or 1 is preferable, and 0 is particularly preferable industrially.

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

  p is an integer of 1 to 3, preferably 1. The substitution position of the hydroxyl group may be any of the ortho, meta and para positions when p is 1, but the para position is preferred because it is readily available and inexpensive. Furthermore, when p is 2 or 3, arbitrary substitution positions can be combined.

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

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

  It is preferable that the polyhydroxystyrene resin further has a structural unit derived from styrene. Here, the “structural unit derived from styrene” includes a structural unit obtained by cleaving an ethylenic double bond of styrene and a styrene derivative (not including hydroxystyrene).

  “Styrene derivatives” are those in which the hydrogen atom bonded to the α-position of styrene is substituted with other substituents such as a halogen atom, an alkyl group, a halogenated alkyl group, and the hydrogen atom of the phenyl group of styrene is carbon Including those substituted with a substituent such as an alkyl group having 1 to 5 atoms.

  Examples of the halogen atom include a chlorine atom, a fluorine atom and a bromine atom, and a fluorine atom is preferable. The “α-position of styrene” means a carbon atom to which a benzene ring is bonded unless otherwise specified.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Examples of the compound having at least one phenolic hydroxyl group include polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,3,4,4′-tetrahydroxybenzophenone; tris (4-hydro Shikiphenyl) 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-dimethyl) Ruphenyl) -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, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4 -Hydroxyphenylmethane, bis (5-cyclohexyl-4-hydride) Xyl-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, and bis (5-cyclohexyl-4-hydroxy-2-methyl) Phenyl) -3,4-dihydroxyphenylmethane and other trisphenol type compounds;
Linear types such as 2,4-bis (3,5-dimethyl-4-hydroxybenzyl) -5-hydroxyphenol and 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4-methylphenol Trinuclear phenol 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-hydroxybenzyl) -4- Droxy-5-ethylphenyl] methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-diethyl-4-) Hydroxybenzyl) -4-hydroxy-5-ethylphenyl] methane, bis [2-hydroxy-3- (3,5-dimethyl-4-hydroxybenzyl) -5-methylphenyl] methane, bis [2-hydroxy-3 -(2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane, bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane, and bis [2, Linear tetranuclear phenolic compounds such as 5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane;
2,4-bis [2-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4-bis [4-hydroxy-3- (4-hydroxybenzyl) -5 -Methylbenzyl] -6-cyclohexylphenol and linear types such as 2,6-bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxybenzyl] -4-methylphenol Pentanuclear phenolic compounds;
Bis (2,3-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4′-hydroxyphenylmethane, 2- (2,3,4- Trihydroxyphenyl) -2- (2 ′, 3 ′, 4′-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ′, 4′-dihydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (4′-hydroxyphenyl) propane, 2- (3-fluoro-4-hydroxyphenyl) -2- (3′-fluoro-4′-hydroxyphenyl) propane, 2- ( 2,4-dihydroxyphenyl) -2- (4′-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4′-hydroxypheny) ) Propane, 2- (2,3,4-trihydroxyphenyl) -2- (4′-hydroxy-3 ′, 5′-dimethylphenyl) propane, and 4,4 ′-[1- [4- [1 Bisphenol type compounds such as-(4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol;
1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene and 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl] Polynuclear branched compounds such as -4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene;
And condensed phenol compounds such as 1,1-bis (4-hydroxyphenyl) cyclohexane. These compounds may be used alone or in combination of two or more.

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

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

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

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

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

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

[(S) Organic solvent]
The positive resist composition preferably contains an organic solvent for dilution (hereinafter also referred to as “(S) component”).

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

  Although content of (S) component is not specifically limited, Generally the quantity from which solid content concentration of a positive resist composition will be 10-60 mass% is preferable, and the quantity which will be 20-50 mass% is more preferable.

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

The inorganic filler is not particularly limited, but inorganic fine particles such as barium sulfate and silica are preferably used. By containing an inorganic filler, etching resistance, physical stress resistance, and thermal stress resistance can be improved.
A conventionally known silane coupling agent can be used as the silane coupling agent, but it is preferably not contained. By not containing a silane coupling agent, the temporal stability can be improved.

<First negative resist composition>
The first negative resist 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 phenolic hydroxyl group]
As the alkali-soluble resin having a phenolic hydroxyl group (hereinafter also referred to as “component (A)”), those exemplified in the positive resist composition can be used.

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

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

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

  The content of the component (D) is preferably 5 to 50 parts by mass and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the component (A). By setting it as said range, the sclerosis | hardenability and patterning characteristic of a 1st negative resist composition become favorable.

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

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

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

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

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

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

  Examples of the acid generator represented by the formula (e-1) include 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate and 4- (2-chloro-4-benzoylphenylthio). Phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoyl) Phenylthio) phenylbis (4-methylphenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4- (β-hydroxyethoxy) phenyl) sulfonium hexafluoroantimonate, 4 -(2- Til-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (3-methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4 -(2-Fluoro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate 4- (2,3,5,6-tetramethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,6-dichloro-4-benzoylsulfate Phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,6-dimethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2, 3-dimethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (3-Methyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-fluoro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) Nyl) sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,3,5,6-tetramethyl-4- Benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,6-dichloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2, 6-dimethyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,3-dimethyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium Oxafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoroantimonate 4- (2-chloro-4- (4-fluorobenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoroantimonate 4- (2-chloro-4-dodecanoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenylbis (4- Fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- ( 4-fluorobenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimony 4- (2-chloro-4-dodecanoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenylbis (4- Rolophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4- Fluorobenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-Chloro-4-dodecanoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonate Hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium perchlorate, 4- (2-chloro -4-benzoylphenylthio) phenyldiphenylsulfonium trifluoromethanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoyl) Phenylthio) phenylbis (4-fluorophenyl) sulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium -Chlorate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium trifluoromethanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium p-toluenesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium camphorsulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) ) Sulfonium nonafluorobutanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) ) Phenylbis (4-chlorophenyl) sulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium perchlorate, 4- (2-chloro-4-benzoylphenylthio) Phenylbis (4-chlorophenyl) sulfonium trifluoromethanesulfonate, diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotrispentafluoroethyl phosphate, diphenyl [4- (p-terphenylthio) phenyl] sulfonium hexafluoroantimonate, And diphenyl [4- (p-terphenylthio) phenyl] sulfonium trifluorotrispentafluoroethyl phosphate.

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

  Examples of the oxime sulfonate acid generator include [2- (propylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] (o-tolyl) acetonitrile, α- (p-toluenesulfonyloxyimino) -phenylacetonitrile. , Α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile and the like can be mentioned. In addition to the above, a compound represented by the following formula (e-3) can be given.

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

R ^e5 is particularly preferably an aromatic compound group. Examples of such an aromatic compound group include aromatic hydrocarbon groups such as a phenyl group and a naphthyl group, and heterocyclic rings such as a furyl group and a thienyl group. Groups and the like. These may have one or more suitable substituents such as a halogen atom, an alkyl group, an alkoxy group, and a nitro group on the ring. R ^e6 is particularly preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. R is preferably an integer of 1 to 3, and more preferably 1 or 2.

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

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

  Examples of halogen-containing triazine compounds include 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (2-furyl) ethenyl. ] -S-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [ 2- (5-ethyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-propyl-2-furyl) ethenyl] -s-triazine, 2 , 4-Bis (trichloromethyl) -6- [2- (3,5-dimethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-di Ethoxypheny ) Ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dipropoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6 -[2- (3-methoxy-5-ethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5-propoxyphenyl) ethenyl] -s -Triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- (3 4-methylenedioxyphenyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-triazine Loromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4- Bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-Methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (2-furyl) ethenyl] -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- [2- (5-methyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3 , 5-Zime Toxiphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (3,4-methylenedioxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, tris (1,3-dibromopropyl) -1 , 3,5-triazine, tris (2,3-dibromopropyl) -1,3,5-triazine and other halogen-containing triazine compounds, and tris (2,3-dibromopropyl) isocyanurate And halogen-containing triazine compounds represented by 4).

式（ｅ−４）中、Ｒ^ｅ７、Ｒ^ｅ８、Ｒ^ｅ９はそれぞれ独立に炭素原子数１〜６のハロゲン化アルキル基を示す。

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

  Other acid generators include bis (p-toluenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1- (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1- Dimethylethylsulfonyl) diazomethane, bis (1-methylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (4-ethylphenylsulfonyl) diazomethane, bis (3-methyl Phenylsulfonyl) diazomethane, bis (4-methoxyphenylsulfonyl) diazomethane, bis (4-fluorophenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane, Bissulfonyldiazomethanes such as bis (4-tert-butylphenylsulfonyl) diazomethane; 2-methyl-2- (p-toluenesulfonyl) propiophenone, 2- (cyclohexylcarbonyl) -2- (p-toluenesulfonyl) propane Sulfonylcarbonylalkanes such as 2-methanesulfonyl-2-methyl- (p-methylthio) propiophenone and 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one; 1-p-toluene Sulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-methylsulfonyl-4-phenyl-2-butanone, 1-cyclohexylsulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-cyclohexylsulfonyl-3,3-dimethyl -2- Thanone, 1-diazo-1- (1,1-dimethylethylsulfonyl) -3,3-dimethyl-2-butanone, 1-acetyl-1- (1-methylethylsulfonyl) diazomethane, 1-diazo-1- ( p-toluenesulfonyl) -3,3-dimethyl-2-butanone, 1-diazo-1-benzenesulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1- (p-toluenesulfonyl) -3- Methyl-2-butanone, 2-diazo-2- (p-toluenesulfonyl) acetate cyclohexyl, 2-diazo-2-benzenesulfonylacetate-tert-butyl, 2-diazo-2-methanesulfonylacetate isopropyl, 2-diazo- 2-benzenesulfonyl acetate cyclohexyl, 2-diazo-2- (p-toluenesulfonyl) acetate-tert-butyl Phenylcarbonyldiazomethanes; nitrobenzyl derivatives such as p-toluenesulfonic acid-2-nitrobenzyl, p-toluenesulfonic acid-2,6-dinitrobenzyl, p-trifluoromethylbenzenesulfonic acid-2,4-dinitrobenzyl Methanesulfonate of pyrogallol, benzenesulfonate of pyrogallol, p-toluenesulfonate of pyrogallol, p-methoxybenzenesulfonate of pyrogallol, mesitylene sulfonate of pyrogallol, benzyl sulfonate of pyrogallol, gallic acid Alkyl methanesulfonate ester, alkyl gallate benzenesulfonate ester, alkyl gallate p-toluenesulfonate ester, alkyl gallate (number of carbon atoms in the alkyl group) 1 to 15) esters of polyhydroxy compounds such as p-methoxybenzenesulfonic acid ester, alkyl gallate mesitylene sulfonic acid ester, alkyl gallic acid benzyl sulfonic acid ester and aliphatic or aromatic sulfonic acid; Etc.

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

  The content of the component (E) is preferably 0.05 to 30 parts by mass and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A). By setting it as the above range, the curability of the first negative resist composition is improved.

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

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

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

The content of the component (S) is not particularly limited, but in general, the amount of the solid content concentration of the first negative resist composition is preferably 10 to 60% by mass, and more preferably 20 to 50% by mass. preferable.
[Other ingredients]
The first negative resist composition may optionally contain an additional resin, a stabilizer, a colorant, a surfactant, an inorganic filler, a silane coupling agent, and the like.

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

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

<Second negative resist composition>
The second negative resist 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 carboxyl group]
(F) Preferable examples of the alkali-soluble resin having a carboxyl group (hereinafter also referred to as “component (F)”) include acid group-containing acrylic resins. As the acid group-containing acrylic resin, one or two kinds selected from monomers such as ethylenically unsaturated acid and (meth) acrylic acid esters, vinyl aromatic compounds, amide unsaturated compounds, polyolefin compounds, etc. A copolymer obtained by copolymerizing the above can be used. Specifically, for example, an ethylenically unsaturated acid such as (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, and (anhydrous) maleic acid is an essential component. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, hydroxyethyl (Meth) acrylates, esters of (meth) acrylic acid such as hydroxypropyl (meth) acrylate; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene; Diacetone Amyl unsaturated compounds such as chloramide, N-methylol acrylamide, N-butoxymethyl acrylamide; polyolefin compounds such as butadiene, isoprene, chloroprene, and (meth) acrylonitrile, methyl isopropenyl ketone, vinyl acetate, veova monomer (shell chemical products) ), A copolymer obtained by copolymerizing one or more monomers selected from other monomers such as vinyl propionate and vinyl pivalate.

  A resin obtained by reacting the above acid group-containing acrylic resin with an alicyclic epoxy group-containing unsaturated compound is also preferable 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 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 of 0-10. R ¹² is preferably a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. Examples of R ¹³ include a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexylene group, —CH ₂ —Ph—CH ₂ — (Ph is A phenylene group).

  The reaction between an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound is, for example, mixing an inert organic solvent solution of an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound. And about 20 to 120 ° C. for about 1 to 5 hours. Examples of the inert organic solvent include, but are not limited to, alcohols, esters, aliphatic or aromatic hydrocarbons. The ratio between the acid group-containing acrylic resin and the alicyclic epoxy group-containing unsaturated compound can be changed depending on the type of monomer used, but the number of unsaturated groups the resulting resin has per 1000 molecular weights. It may be adjusted to a range of 0.2 to 4.0, preferably 0.7 to 3.5. By adjusting the number of unsaturated groups of the obtained resin to such a range, an etching mask having excellent adhesion to a glass substrate can be formed, and a second negative resist composition having excellent curability and storage stability. Easy to get things.

  The mass average molecular weight of the component (F) described above can be determined by measurement by gel permeation chromatography, and the value is preferably 1000 to 100,000, more preferably 3000 to 70000, and still more preferably 9000. ~ 30,000. The acid value of such component (F) is preferably 20 to 200 mgKOH / g, and more preferably 30 to 150 mgKOH / g. Excellent developability is achieved by setting the lower limit value or more. By setting it to the upper limit value or less, the chemical resistance becomes good and the pattern shape is also excellent.

[(G) Photopolymerizable compound]
(G) Photopolymerizable compounds (hereinafter also referred to as “component (G)”) include monofunctional compounds and polyfunctional compounds.

  Monofunctional compounds include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- ( (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) ) Acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative.

  On the other hand, as polyfunctional compounds, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxy) Ethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly ( ) Acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene Examples thereof include polyfunctional monomers such as ethers, polyhydric alcohols and N-methylol (meth) acrylamide condensates, and triacryl formal. Also, bifunctional or higher functional epoxy resins such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, and biphenol type epoxy resin (meta ) Epoxy (meth) acrylate obtained by reacting with acrylic acid can also be used as a polyfunctional compound.

  The (G) component demonstrated above can be used individually or in combination of 2 or more types. In said (G) component, a polyfunctional compound is preferable. When the second negative resist composition contains a polyfunctional compound as the component (G), an etching mask having excellent flexibility can be formed, and a second negative resist composition having excellent curability can be easily prepared.

  The content of the component (G) is preferably 30 to 250 parts by mass, more preferably 40 to 200 parts by mass, and even more preferably 50 to 160 parts by mass with respect to 100 parts by mass of the component (F). By setting it as said range, the hydrofluoric acid tolerance of the etching mask formed using a 2nd negative resist composition can be improved. Further, when the upper limit value is set, the development characteristics are improved.

[(H) Photopolymerization initiator]
(H) The photopolymerization initiator (hereinafter also referred to as “component (H)”) is not particularly limited, and examples thereof include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl Propan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethyl) Aminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- -(4-morpholinophenyl) -butan-1-one, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime) 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethyl Butyl aminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione- 2- (o-ethoxycarbonyl) oxime, o-benzoylbenzoic acid Chill, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthio Xanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzo Imidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chloro Lobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin Ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p -Tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-ter -Butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis -(9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bi (Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4) -Dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxy Styryl) -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) styryl And phenyl-s-triazine. These photopolymerization initiators can be used alone or in combination of two or more.
The content of the component (H) may be appropriately adjusted according to the content of the component (G), but is preferably 1 to 25 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (F). -15 mass parts is more preferable, and 5-15 mass parts is further more preferable. By setting it as said range, sufficient heat resistance and chemical-resistance can be acquired, a coating-film formation ability can be improved, and photocuring failure can be suppressed.

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

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

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

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

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

≪Pre-processing method≫
The pretreatment method of the glass substrate is
A lyophilic step for improving the wettability of the treatment liquid for removing alkali metal on the surface of the glass substrate, where the glass on the glass substrate is exposed, and
After the lyophilic process, the surface of the glass substrate is brought into contact with the treatment solution for removing the alkali metal, and the alkali metal removal treatment is performed to reduce the amount of alkali metal on the surface layer of the glass substrate surface where the glass is exposed. Applying an alkali metal removal step;
And a hydrophobizing step of performing a hydrophobizing treatment for hydrophobizing the surface of the glass substrate on the surface of the glass substrate after the alkali metal removing step. Hereinafter, the lyophilic step, the alkali metal removing step, and the hydrophobizing step will be described in order.

<Liquidification process>
In the lyophilic process, a lyophilic process is performed on the surface of the glass substrate to improve the wettability of the alkali metal removing process liquid on the exposed portion of the glass on the glass substrate. As the treatment liquid for removing the alkali metal, a treatment liquid containing an acid or a chelating agent is used. As the treatment liquid for removing alkali metals, from the viewpoint of the uniformity of the treatment liquid, an aqueous solution of an acid or a chelating agent, a solution of a highly polar organic solvent of an acid or a chelating agent, a liquid organic acid, and a liquid chelating agent are available. preferable. Among these treatment liquids, an acid aqueous solution, a liquid organic acid, a chelating agent aqueous solution, and a liquid chelating agent are preferable because they are easy to prepare and inexpensive.

When the treatment solution for removing alkali metal is a highly polar treatment solution such as an acid aqueous solution, a liquid organic acid, a chelating agent aqueous solution, or a liquid chelating agent, the glass on the glass substrate is exposed. By performing UV cleaning such as UV / ozone cleaning or plasma processing such as O ₂ plasma processing on the part, the glass on the glass substrate of the alkali metal removal processing liquid is exposed. The wettability can be improved.

  Whether or not the wettability of the processing liquid for removing alkali metal to the exposed part of the glass on the glass substrate has been improved depends on whether or not the processing liquid for removing alkali metal on the glass substrate before and after the lyophilic treatment. This can be confirmed by comparing the contact angle with the exposed part of the glass. If the contact angle after the lyophilic process is lower than the contact angle before the lyophilic process, it is determined that the lyophilic process has been performed satisfactorily.

  When the treatment liquid for alkali metal removal is a highly polar treatment liquid, the contact angle of the water before and after the lyophilic treatment is compared with the contact angle of the alkali metal removal liquid before and after the lyophilic treatment. It can be determined whether the process has been performed satisfactorily.

  When an aqueous acid solution, a liquid organic acid, an aqueous solution of a chelating agent, or a liquid chelating agent is used as the treatment liquid for removing alkali metal, water for the portion of the glass substrate on which the glass is exposed by lyophilic treatment The contact angle is preferably lowered to 30 ° or less, more preferably 20 ° or less, and further preferably 10 ° or less.

  As the solvent contained in the treatment liquid, a low-polar organic solvent can also be selected. In the case of using a low-polar treatment liquid mainly composed of a low-polar organic solvent, the glass on the glass substrate is exposed using a known silylating agent used as a water repellent for various materials. By treating the portion, the wettability of the low-polarity treatment liquid to the glass can be improved.

<Alkali metal removal step>
Subsequent to the lyophilic step, the surface of the glass substrate is brought into contact with the treatment solution for removing the alkali metal to remove the alkali metal in the surface layer where the glass on the surface of the glass substrate is exposed. The treatment is performed on the glass substrate.

  As described above, in the alkali metal removal step, a treatment liquid for removing an alkali metal containing an acid or a chelating agent is used. When the treatment solution for removing the alkali metal contains a solvent for dissolving the acid or chelating agent, the solvent does not have an acidic group even if it is water or an organic solvent having no acidic group. An aqueous solution of an organic solvent may be used. As the treatment liquid for removing alkali metals, from the viewpoint of the uniformity of the treatment liquid, an aqueous solution of an acid or a chelating agent, a solution of a highly polar organic solvent of an acid or a chelating agent, a liquid organic acid, and a liquid chelating agent preferable. Among these treatment liquids, an acid aqueous solution, a liquid organic acid, a chelating agent aqueous solution, and a liquid chelating agent are preferable because they are easy to prepare and inexpensive.

  The chelating agent in the treatment liquid for removing an alkali metal containing a chelating agent is not particularly limited, and can be appropriately selected from known chelating agents. The chelating agent is usually used as a solution of water or an organic solvent. For example, a chelating agent that is liquid near room temperature such as acetylacetone, diacetone alcohol, and ethyl acetoacetate is dissolved in water or an organic solvent. Without any problem, it can be used as it is as a treatment liquid for removing alkali metals. A treatment solution for removing an alkali metal comprising a chelating agent that is liquid at around room temperature is useful in that it hardly corrodes metal wiring.

  As described above, when the chelating agent is solid at room temperature, the chelating agent is used as a solution of water or an organic solvent. Examples of chelating agents that are solid around room temperature include pyrogallol and 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 for dissolving the chelating agent include methanol and ethanol.

  Among the above-mentioned treatment solutions for removing alkali metals, inorganic acids and organics are used from the viewpoint of the effect of reducing sodium and potassium and the ease of disposal and purification of the treatment solution after treating the surface of the glass substrate. A treatment liquid comprising an acidic compound selected from acids and water is preferred.

  As the inorganic acid and organic acid, a Bronsted acid is usually used. Examples of inorganic acids include hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, hypochlorous acid, perchloric acid, sulfurous acid, persulfuric acid, nitrous acid, phosphorous acid, hypophosphorous acid, and phosphinic acid Is mentioned. Among these, hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid are preferable. Organic acids 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, ethanesulfonic acid, benzenesulfonic acid, and p -Toluenesulfonic acid.

  The concentration of the acidic compound in the treatment liquid is not particularly limited with respect to the treatment liquid for removing alkali metal consisting of an acidic compound and water, but is preferably 50% by mass or less, more preferably 10% by mass or less, and more preferably 5% by mass or less. Is particularly preferable and 3% by mass or less is most preferable.

  About the processing liquid for alkali metal removal containing the acidic compound selected from an inorganic acid and an organic acid, and water, the processing liquid contains the salt of the acidic compound further contained in a processing liquid for the purpose of buffering. Also good. As a salt of an acidic compound, an alkali metal salt is preferable, and a sodium salt or a potassium salt is preferable. About the buffered processing solution for alkali metal removal, the pH is preferably 3 or more and less than 7, and more preferably 4 or more and 6 or less.

  The treatment of the glass substrate using the treatment liquid for removing the alkali metal may be performed on the glass substrate in which the total amount of elemental component ratios of sodium and potassium in the surface layer from the surface to a depth of 10 μm is more than 13% by mass. Many. This is because, in a chemically strengthened glass substrate which is a preferred glass substrate, the total amount of elemental component ratios of sodium and potassium in the surface layer from the surface to a depth of 10 μm is generally more than 13% by mass.

  And the process of the glass substrate using the process liquid for alkali metal removal is the total amount of the element component ratio of sodium and potassium of the surface layer from the surface to the depth of 10 micrometers in the part where the glass on the glass substrate is exposed. It is performed so that it may become 13 mass% or less. By doing so, the etching mask formed using the resist composition can be quickly peeled off in the portion where the glass on the glass substrate is exposed, leaving almost no residue.

  In addition, when performing an alkali metal removal process with respect to a glass substrate, without performing the above-mentioned lyophilic process, the alkali metal which exists in the surface layer of the part which the glass on a glass substrate exposes is removed to a desired extent. Is difficult.

  After the alkali metal removal treatment, in the portion where the glass on the glass substrate is exposed, the sum of the elemental component ratios of sodium and potassium on the surface layer from the surface to a depth of 10 μm is less than the etching mask from the substrate surface in a shorter time. 10 mass% or less is preferable at the point which can be made to peel, 8 mass% or less is more preferable, and 3 mass% or less is especially preferable.

  The element component ratio of potassium in the surface layer from the surface to a depth of 10 μm in the exposed portion of the glass on the glass substrate after the alkali metal removal treatment is preferably 10% by mass or less, and 8.5% by mass or less. More preferred is 3% by mass or less.

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

  The elemental component ratio of sodium and potassium in the surface layer from the surface to a depth of 10 μm in the portion where the glass on the glass substrate is exposed can be measured 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 performed on the glass substrate in which the total ratio of elemental components of sodium and potassium in the surface layer from the surface to a depth of 10 μm is 13% by mass or less. . In this case, the etching mask is peeled off well in the portion where the glass on the surface of the glass substrate is exposed without performing the alkali metal removal treatment, but the etching mask can be peeled off more quickly by performing the alkali metal removal treatment. it can.

  The method of alkali metal removal treatment is not particularly limited as long as the elemental content ratio of potassium and sodium on the surface layer of the glass substrate can be reduced to a desired level. In the said process, the surface of a glass substrate is made to contact a process liquid and potassium and sodium are eluted in the process liquid for alkali metal removal. As a method of bringing the treatment liquid for removing the alkali metal into contact with the surface of the glass substrate, a method of rinsing the surface of the substrate after immersing the glass substrate in the treatment liquid, or the above treatment liquid was deposited on the surface of the glass substrate. A method of washing the surface of the substrate with water later, a method of washing the surface of the substrate after spraying the treatment liquid on the surface of the glass substrate, a method of washing the surface of the substrate with the treatment liquid flowing down on the surface of the glass substrate, etc. Is mentioned.

  The time for contacting the surface of the glass substrate and the treatment liquid is preferably 45 seconds or more, more preferably 1 minute or more, and particularly preferably 2 minutes or more. The contact time is preferably 10 minutes or less. Even if the surface of the glass substrate and the treatment liquid are brought into contact with each other for more than 10 minutes, no significant problem occurs, but a particularly excellent effect is not obtained with respect to improvement of the peelability of the etching mask. Depending on the type and pH of the treatment liquid, when the treatment liquid and the glass substrate are contacted for a long time exceeding 10 minutes, the metal wiring may be corroded.

<Hydrophobicization process>
After the alkali metal removal step, the surface of the glass substrate is subjected to a hydrophobizing treatment for hydrophobizing the surface of the glass substrate. By applying a hydrophobic treatment to the surface of the glass substrate, while maintaining the adhesion of the etching mask to the glass substrate, the portion where the permanent film on the surface of the glass substrate is exposed, and the portion where the metal wiring is exposed, The peelability of the etching mask can be improved.

  The hydrophobizing treatment is usually performed by bringing a hydrophobizing agent into contact with the surface of the glass substrate. The hydrophobizing agent can be selected without particular limitation from hydrophobizing agents conventionally used for hydrophobizing various materials. Preferred hydrophobizing agents include various silane coupling agents, N, N-dialkylaminosilane compounds, acyclic disilazane compounds, and cyclic silazane compounds that are used for hydrophobizing applications.

  Examples of N, N-dialkylaminosilane compounds include N, N-dimethylaminotrimethylsilane, N, N-dimethylaminodimethylsilane, N, N-dimethylaminomonomethylsilane, N, N-diethylaminotrimethylsilane, and t-butyl. Aminotrimethylsilane, allylaminotrimethylsilane, trimethylsilylacetamide, N, N-dimethylaminodimethylvinylsilane, N, N-dimethylaminodimethylpropylsilane, N, N-dimethylaminodimethyloctylsilane, N, N-dimethylaminodimethyl Examples include phenylethylsilane, N, N-dimethylaminodimethylphenylsilane, N, N-dimethylaminodimethyl-t-butylsilane, N, N-dimethylaminotriethylsilane, and trimethylsilanamine.

  Examples of acyclic disilazane compounds include hexamethyldisilazane, N-methylhexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,3-dimethyldisilazane, 1,3-di-n. -Octyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,1,3,3, -tetramethyldisilazane, tris (dimethylsilyl) amine, tris (trimethylsilyl) amine, -Ethyl-1,1,3,3,3-pentamethyldisilazane, 1-vinyl-1,1,3,3,3-pentamethyldisilazane, 1-propyl-1,1, -3,3 3-pentamethyldisilazane, 1-phenylethyl-1,1,3,3,3-pentamethyldisilazane, 1-tert-butyl-1,1,3,3,3-pentamethyldisilazane, 1- Feni 1,1,3,3,3 pentamethyl disilazane, and 1,1,1-trimethyl-3,3,3-triethyl-disilazane and the like.

  Examples of cyclic silazane compounds include 2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane, 2,2,6,6-tetramethyl-2,6-disila-1- Cyclic disilazane compounds such as azacyclohexane; cyclic trisilazane compounds such as 2,2,4,4,6,6-hexamethylcyclotrisilazane and 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane A cyclic tetrasilazane compound such as 2,2,4,4,6,6,8,8-octamethylcyclotetrasilazane;

  When the hydrophobizing agent is a solid or a liquid having a high viscosity, the hydrophobizing agent may be diluted with an organic solvent having no reactivity with the hydrophobizing agent.

  Examples of the method for bringing the hydrophobizing agent into contact with the glass substrate include a method of immersing the glass substrate in a liquid hydrophobizing agent, a method of depositing a liquid hydrophobizing agent on the surface of the glass substrate, and a surface of the glass substrate. And a method of spraying a liquid hydrophobizing agent, a method of bringing the hydrophobizing agent vapor into contact with the surface of the glass substrate, a method of causing the liquid hydrophobizing agent to flow down on the surface of the glass substrate, and the like.

  When the hydrophobizing agent is brought into contact with the glass substrate, the hydrophobizing agent or the glass substrate may be heated for the purpose of promoting the reaction between the hydrophobizing agent and the surface of the glass substrate. The heating temperature in this case is typically about 30 to 150 ° C. Although the time which makes a glass substrate and a hydrophobizing agent contact is not specifically limited, Typically, it is 1 to 30 minutes, and 1 to 10 minutes are preferable.

  The hydrophobization treatment is preferably performed so that the contact angle of water with the surface of the permanent film on the glass substrate is 30 ° or more. When an etching mask is provided on a glass substrate that has been subjected to hydrophobic treatment in this manner, etching is performed quickly without leaving a residue on the glass substrate where the permanent film is exposed and where the metal wiring is exposed. Easy to peel off the mask.

  After performing the hydrophobizing treatment, the surface of the glass substrate is rinsed and dried as necessary to obtain a pretreated substrate.

<< Method of forming etching mask >>
An etching mask is formed using a resist composition on the glass substrate pretreated by the above-described method.
Specifically, a coating film forming step of forming a coating film by applying a resist composition on the surface of the glass substrate pretreated by the above-described method,
Exposing the coating film in a position-selective manner; and
The etching mask is formed by a method including a developing step of developing the exposed coating film to form an etching mask.
Hereinafter, the coating film forming step, the exposure step, and the development step will be described in order.

<Coating film formation process>
In the coating film forming process, for example, the resist described above on the glass substrate using a contact transfer type coating apparatus such as a roll coater, reverse coater, bar coater, or a non-contact type coating apparatus such as a spinner, curtain flow coater, or slit coater. The composition is applied to form a coating film. The formed coating film may be heated (pre-baked) as necessary.

  Although the film thickness of the coating film formed is not specifically limited, For example, it is about 20-200 micrometers. Although the heating conditions in the case of prebaking are not specifically limited, For example, it is about 2 to 60 minutes at 70-150 degreeC. In addition, you may repeat application | coating and prebaking of a resist composition in multiple times so that the coating film of a desired film thickness can be formed.

  When the resist composition can be used as a dry film, a dry film of the resist composition can be attached to the surface of the glass substrate to form a coating film. The dry film of the resist composition can be formed by applying the resist composition on the release film and then drying the resist composition as necessary.

<Exposure process>
In the exposure step, the coating film is selectively exposed by irradiating active energy rays such as ultraviolet rays through the light shielding pattern. For the exposure, a light source that emits ultraviolet rays such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used. The energy dose to be irradiated varies depending on the composition of the resist composition, but is preferably about 30 to 3000 mJ / cm ² , for example. In the exposure, the coating film may be heated (PEB) as necessary. Although the heating conditions in that case are not specifically limited, For example, it is about 3 to 20 minutes at 80-150 degreeC.

<Development process>
In the development step, the coating film exposed in the position selective manner in the exposure step is developed using a developer to obtain an etching mask. The development method is not particularly limited, and an immersion method, a spray method, a shower method, a paddle method, or the like can be used. The developer is appropriately selected according to the type of resist composition. Examples of the developer include 0.25 to 3% by mass of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, organic amine, tetramethylammonium hydroxide, triethanolamine, N-methylpyrrolidone, dimethyl sulfoxide and the like. The development time is not particularly limited, but is, for example, about 1 to 120 minutes. The developer may be heated to about 25 to 40 ° C. After development, the etching mask may be heated (post-baked). Although heating conditions are not specifically limited, For example, it is about 2-120 minutes at 70-300 degreeC.

  Further, when the resist composition is a positive type, after the development, the etching mask may be subjected to after-cure that is heated while being irradiated with active energy rays such as ultraviolet rays. In after-cure, the quinonediazide group-containing compound contained in the resist composition forms an intermediate (indenketene) by active energy rays, which is combined with an alkali-soluble resin having a phenolic hydroxyl group or a quinonediazide group-containing compound to form a polymer. To do.

  In addition, when the etching process mentioned later is given with respect to both the front and back surfaces of a glass substrate, after performing the above-mentioned pre-processing with respect to the back and front surfaces of a glass substrate, an etching mask is formed with respect to the back and front surfaces of a glass substrate. The In this case, the glass substrate may be provided with metal wiring and a permanent film on at least one side.

≪Glass substrate processing method≫
Etching is performed on the glass substrate provided with the etching mask formed by the above-described method.
Specifically, etching is performed on a portion of the glass substrate provided with the etching mask, where the glass on the surface provided with the etching mask is exposed, and
After the etching step, the glass substrate is processed by a method including a peeling step of peeling the etching mask from the surface of the glass substrate.
Hereinafter, the etching process and the peeling process will be described in order.

<Etching process>
Examples of processing of a glass substrate by etching include formation of a dot-like or linear recess on the substrate surface, formation of a through-hole penetrating the substrate in the thickness direction, cutting of the substrate, and the like. Examples of the etching method include wet etching that is generally performed and is immersed in an etching solution. Examples of the etchant include hydrofluoric acid alone, hydrofluoric acid and ammonium fluoride, mixed acid of hydrofluoric acid and other acids (hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc.), and the like. The etching processing time is not particularly limited, but is, for example, about 10 to 60 minutes. In addition, you may heat an etching liquid to about 25-60 degreeC.

<Peeling process>
After the etching process, the etching mask is peeled off from the surface of the glass substrate in the peeling process. A method for peeling the etching mask from the surface of the glass substrate is not particularly limited, but typically, the etching mask is peeled off using a peeling solution.

  The stripping solution is not particularly limited as long as the etching mask can be stripped from the surface of the glass substrate. From the stripping solution conventionally used for stripping a film formed using a resist composition. It is selected appropriately.

Examples of stripping solutions include organic solvent-based stripping solutions, nitrogen-containing basic organic compounds such as organic amines and quaternary ammonium hydroxides, or inorganic basic compounds such as ammonia and basic alkali metal compounds. Basic stripping solution containing Examples of organic amines include monoethanolamine, diethanolamine, triethanolamine and the like. Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide. Examples of the basic alkali metal compound include sodium hydroxide, potassium hydroxide, sodium carbonate and the like. The solvent contained in the basic stripping solution is appropriately selected from water, an organic solvent, and an organic solvent aqueous solution. Among the above stripping solutions, stripping solutions containing a basic compound and an organic solvent that can easily strip the etching mask are preferable.
When the basic stripping solution contains water as a solvent, the basic stripping solution may contain a rust inhibitor. A conventionally well-known thing can be used suitably as a rust preventive agent.

  When the stripping solution is a basic stripping solution, the basic compound contained in the stripping solution is preferably a nitrogen-containing basic organic compound because damage to metal wiring is small. Further, when the solvent in the stripping solution contains an organic solvent, since the damage to the metal wiring is small, it is preferable that the solvent consists only of the organic solvent, and the solvent consisting only of the organic solvent contains the aprotic polar organic solvent. Is more preferable. The solvent in the stripping solution may contain a combination of two or more aprotic polar organic solvents. Examples of the aprotic polar organic solvent that may be contained in the stripper include N-methyl-2-pyrrolidone, N, N-dimethylformamide, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, dimethylurea And dimethylimidazolidinone and the like. 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, more preferably 80% by mass or more. Preferably, 90 mass% or more is particularly preferable.

  The method for removing the etching mask with the remover is not particularly limited. Examples of the method for peeling the etching mask with a peeling solution include a liquid piling method, a dipping method, a paddle method, and a spray method. Conditions for peeling off the etching mask with the peeling liquid are not particularly limited. The stripping solution may be used after being heated to 25 to 60 ° C.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

[Examples 1 to 10 and Comparative Examples 1 to 4]
In Examples 1 to 8, Example 10, and Comparative Examples 1 to 4, the following GL1 was used as a glass substrate. The total of the elemental component ratios of sodium and potassium is the total of the elemental component ratios of sodium and potassium in the surface layer from the surface to a depth of 10 μm.
<GL1>
Type: Chemically strengthened glass substrate Total element component ratio of sodium and potassium: 20% by mass
Vickers hardness: 570 kgf / mm ²
Thickness: 0.55mm

In Example 9, the following GL2 was used as the glass substrate.
<GL2>
Type: Total elemental component ratio of soda lime glass sodium and potassium: 7% by mass
Thickness: 0.55mm

Said GL1 and GL2 were provided with the pattern of the metal wiring which consists of a Mo-Al-Mo laminated body, and the transparent permanent film formed using the following permanent film materials.
<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 (numerical values are mass% of each unit in the resin) and OXE-01 (manufactured by BASF) 0.5 parts by mass, 7 parts by mass of dipentaerythritol hexaacrylate, 0.5 parts by mass of BYK-310 (manufactured by BYK Japan), 15 parts by mass of propylene glycol monomethyl ether acetate, and 35 parts by mass of diethylene glycol monomethyl ether Were mixed into a uniform solution to prepare a permanent film material.

  A lyophilic treatment was performed on the glass substrate of the type described in Table 1 under the conditions described in Table 1. The contact angle of water was measured for a portion where the glass on the glass substrate subjected to the lyophilic treatment was exposed. The measurement results of the water contact angle are shown in Table 1.

The lyophilic conditions in Table 1 are as follows.
Condition A: UV treatment (wavelength: 257 nm, 154 nm, energy: 1000 mJ / cm ² )
Condition B: UV treatment (wavelength: 257 nm, 154 nm, energy: 500 mJ / cm ² )
Condition C: O ₂ plasma treatment (treatment time: 15 seconds)
Condition D: O ₂ plasma treatment (treatment time: 30 seconds)

  Subsequently, the alkali metal removal treatment liquid was brought into contact with the glass substrate to reduce the amount of alkali metal in the surface layer where the glass on the glass substrate was exposed. Specifically, the glass substrate was immersed in a treatment liquid for removing alkali metals of the type shown in Table 2 for 1 minute at room temperature (23 ° C.) to perform alkali metal removal treatment. After immersion, the surface of the glass substrate was rinsed with ion exchange water. After rinsing, the glass substrate is dried, and the elemental component ratio of potassium and sodium in the surface layer from the surface to a depth of 10 μm in the exposed portion of the glass on the glass substrate is XPS (X-ray photoelectron spectroscopy) Measured with The total of the measured elemental component ratios of potassium and sodium is shown in Table 2.

The types of treatment liquids for removing alkali metals in Table 2 are as follows.
Treatment liquid 1: Citric acid aqueous solution with a concentration of 1% by mass 2: sulfuric acid aqueous solution with a concentration of 1% by mass 3: Acetylacetone treatment solution 4: An aqueous pyrogallol solution with a concentration of 1% by mass

Subsequently, the glass substrate was subjected to a hydrophobic treatment under the conditions described in Table 3. After the hydrophobic treatment, the glass substrate was dried. For the glass substrate before the hydrophobic treatment and the glass substrate after the hydrophobic treatment, the water contact angle of the portion where the glass on the glass substrate is exposed and the water contact angle of the portion where the permanent film is exposed Was measured. The measurement results of the contact angle are shown in Table 3. The hydrophobization conditions in Table 3 are as follows.
Condition I: A 70 ° C. sealed oven was placed in a hexamethyldisilazane atmosphere, and the glass substrate was allowed to stand in the oven for 7 minutes.
Condition II: N-phenyl-3-aminopropyltrimethoxysilane was applied to a glass substrate, then baked on a hot plate at 130 ° C. for 1 minute, and rinsed with acetone.

According to the following method, the etching resistance of the etching mask formed on the glass substrate pretreated by the above-described method or an untreated glass substrate (Comparative Example 1) was evaluated.
First, a resist composition was applied on a glass substrate to form a coating film having a thickness of 70 μm. The formed coating film was subjected to position selective exposure and developed to form an etching mask having holes with a hole diameter of 2 mm.

[Resist composition]
80 parts by mass of resin, 30 parts by mass of fine particles of barium sulfate, 10 parts by mass of a crosslinking agent, 0.5 parts by mass of an acid generator, and 10 parts by mass of a plasticizer are added in an organic solvent so that the solid content concentration becomes 50% by mass The composition 1 was obtained by mixing uniformly.
As the resin, a cresol novolak resin obtained by condensing m-cresol and p-cresol with formalin at m-cresol / p-cresol = 60/40 (mass ratio) was used. The mass average molecular weight of the cresol novolak resin was 5000.
As the cross-linking agent, 2,4,6-tris [bis (methoxymethyl) amino] -1,3,5-triazine was used.
As the acid generator, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine was used.
As the plasticizer, polyvinyl methyl ether (mass average molecular weight: 100,000) was used.
As the organic solvent, propylene glycol monomethyl ether acetate was used.

After the formation of the etching mask, an etching process is performed by shaking the glass substrate for 90 minutes using an etching solution (composition: hydrofluoric acid / sulfuric acid / water = 15/15/70 (mass ratio)) at 55 ° C. A through hole was formed in the substrate.
After the etching process, the etching mask and the through hole were observed. As a result, in any of the examples and comparative examples, no peeling of the etching mask and side etching were observed on the glass substrate, and the etching resistance of the etching mask was good.

  After the etching process of the glass substrate, the etching mask peeling time, the amount of residue after the etching mask peeling, and the wiring damage due to the peeling liquid at the time of peeling the etching mask were evaluated according to the following methods. These evaluation results are shown in Table 4.

[Peeling time]
A glass substrate provided with an etching mask after etching is immersed in a stripping solution (tetramethylammonium hydroxide / dimethylsulfoxide / propylene glycol = 2/90/8 (mass%)) heated to 60 ° C. The etching mask was peeled off. The time from the start of immersion until the time when the etching mask was peeled off from the surface of the glass substrate was measured. The time for completion of peeling was judged visually.

[Amount of residue after etching mask removal]
In the peeling time evaluation, on the glass substrate from which the etching mask was peeled off, the etching mask for each of the portion where the glass is exposed, the portion where the permanent film is exposed, and the portion where the metal wiring is exposed The presence or absence of residue was visually observed. When a residue was not confirmed by visual observation, the surface of the glass substrate was observed at a magnification of 100 using an optical microscope. Based on visual observation and microscopic observation of the glass substrate, the degree of etching mask residue of each example and comparative example was evaluated according to the following criteria.
A: No etching mask residue was observed on the substrate surface.
○: A slight amount of etching mask residue was observed on the substrate surface during microscopic observation.
X: A large amount of etching mask residue was observed on the substrate surface during microscopic observation or visual observation.

[Wiring damage due to stripping solution]
According to the following method, the degree of damage of the metal wiring when the etching mask was peeled off from the surface of the glass substrate using a peeling solution was evaluated.
Specifically, from the change in the sheet resistance value of the metal wiring portion on the surface of the glass substrate before and after the treatment with the stripping solution in the evaluation of the stripping time, the amount of decrease in the thickness of the metal wiring after processing (nm) ) Was measured. From the measured decrease in film thickness, the degree of wiring damage due to the stripping solution was evaluated according to the following criteria.
○: 5 nm or less.
X: Over 5 nm.

From Tables 1 to 4, as in Examples 1 to 10, the metal wiring and the glass substrate provided with a permanent film on its surface,
A lyophilic treatment for improving the wettability of the treatment liquid for removing alkali metal to the exposed portion of the glass on the glass substrate;
-Alkali metal removal treatment for the exposed part of the glass on the glass substrate;
・ After applying the hydrophobic treatment to the surface of the glass substrate,
When forming an etching mask using a resist composition on the surface of the glass substrate, and then performing etching processing and peeling of the etching mask, a portion of the glass substrate where the glass is exposed, a portion where the metal wiring is exposed, and It can be seen that in any portion where the permanent film is exposed, the etching mask is peeled off rapidly with almost no residue left.

  From Comparative Example 1, an etching mask was formed on the surface of the glass substrate using a resist composition without performing pretreatment on the glass substrate having a metal wiring and a permanent film on the surface, and then an etching process. When the etching mask is peeled off, a large amount of peeling residue is generated in any portion where the glass is exposed, where the metal wiring is exposed, and where the permanent film is exposed. It turns out that it takes time.

From Comparative Example 2, a glass substrate having a metal wiring and a permanent film on its surface is not subjected to lyophilic treatment, and after alkali metal removal treatment and hydrophobization treatment are performed on the surface of the glass substrate. When an etching mask is formed using a resist composition, and then etching and peeling of the etching mask are performed, a large amount of peeling residue is generated between the portion where the glass is exposed and the portion where the permanent film is exposed. It can be seen that it takes a long time to peel off.
Further, from Comparative Example 3, a glass substrate provided with a metal wiring and a permanent film on its surface is subjected to a lyophilic treatment and a hydrophobization treatment, but without performing an alkali metal removal treatment on the surface of the glass substrate. When an etching mask is formed using a resist composition, and then etching and peeling of the etching mask are performed, a large amount of peeling residue is generated at a portion where the glass is exposed, and it may take a long time to remove the etching mask. I understand.

From Comparative Example 2, when the alkali metal removal treatment is performed without performing the lyophilic treatment, the total of the elemental component ratios of sodium and potassium in the surface layer from the surface of the portion where the glass on the glass substrate is exposed to a depth of 10 μm is calculated. It can be seen that it is difficult to reduce to a desired level.
Moreover, from the comparative examples 2 and 3, when the total of the elemental component ratios of sodium and potassium in the surface layer from the surface of the portion where the glass on the glass substrate is exposed to a depth of 10 μm exceeds 13% by mass, It can be seen that a large amount of peeling residue is generated in the portion where the glass is exposed.
Furthermore, from the comparison between Comparative Example 2 and Comparative Example 3, the lyophilic treatment seems to enhance the effect of improving the peelability of the etching mask on the permanent film by the hydrophobic treatment. For this reason, in Comparative Example 2 in which the etching mask was formed on the hydrophobicized glass substrate without performing the lyophilic process, it is considered that a large amount of peeling residue was generated even at the portion where the permanent film was exposed.

  From Comparative Example 4, a glass substrate having a metal wiring and a permanent film on its surface is subjected to a lyophilic treatment and an alkali metal removal treatment, and a resist composition is formed on the surface of the glass substrate without applying a hydrophobic treatment. When an etching mask is formed using an object, and then etching processing and peeling of the etching mask are performed, a large amount of peeling residue is generated between the portion where the permanent film is exposed and the portion where the metal wiring is exposed, It can be seen that peeling takes a long time.

Claims (7)

A pretreatment method for a glass substrate, which is performed before forming an etching mask on the surface of the glass substrate by a photolithography method using a resist composition,
The glass substrate includes a metal wiring and a non-conductive coating made of an organic or inorganic material on the surface, a portion where the glass is exposed on the surface, a portion where the metal wiring is exposed, and the coating is exposed. Part is present and contains sodium and / or potassium,
A lyophilic process for improving the wettability of the alkali metal removal treatment liquid to the exposed surface of the glass substrate on the surface of the glass substrate, and
After the lyophilic step, the surface of the glass substrate and the treatment liquid for removing the alkali metal are brought into contact with each other to reduce the amount of alkali metal in the surface layer where the glass on the surface of the glass substrate is exposed. An alkali metal removal step for performing a metal removal treatment;
After the alkali metal removing step, subjecting the surface of the glass substrate to a hydrophobizing treatment for hydrophobizing the surface of the glass substrate,
The treatment liquid for removing the alkali metal is a treatment liquid containing an acid or a chelating agent,
The total of the elemental component ratios 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 subjected to the alkali metal removal treatment is 13% by mass or less. Processing method.   The pretreatment method according to claim 1, wherein the treatment liquid for removing the alkali metal is selected from the group consisting of an acid aqueous solution, a liquid organic acid, a chelating agent aqueous solution, and a liquid chelating agent.   The pretreatment method according to claim 2, wherein a contact angle of water is reduced to 30 ° or less in a portion where the glass on the glass substrate is exposed by the lyophilic treatment.   The pretreatment method according to claim 1, wherein a contact angle of water in the coating on the glass substrate is increased to 30 ° or more by the hydrophobic treatment. The pretreatment method according to claim 1, wherein the glass substrate is a glass substrate having a Vickers hardness of 500 kgf / mm ² or more. A coating film forming step of forming a coating film by applying a resist composition to the surface of the glass substrate treated by the pretreatment method according to any one of claims 1 to 5,
Exposing the coating film in a position-selective manner; and
A development step of developing the exposed coating film to form an etching mask. An etching step of performing etching on a portion of the glass substrate provided with the etching mask formed by the etching mask forming method according to claim 6 where the glass on the surface provided with the etching mask is exposed;
A peeling method of peeling the etching mask from the surface of the glass substrate after the etching step.