JP2011227246A - Negative photosensitive resin composition, photosensitive dry film, and light receiving device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative photosensitive resin composition which can form a photosensitive resin layer having excellent developability, resolution and adhesiveness after patterning, a photosensitive dry film which has a photosensitive resin layer comprising the composition, and a light receiving device having a spacer that is obtained by curing the composition.SOLUTION: A negative photosensitive resin composition according to the present invention suitable to forming a spacer 13 for a light receiving device 1 comprises an alkali-soluble resin (A); a compound (B) which generates an acid or a radical by irradiation of active rays; a compound (C) crosslinkable by the acid or radical; an epoxy resin (D) expressed by a general formula (D-1); and a solvent (S). (In the formula, Rand Reach independently presents a methyl group or the like; Rthrough Reach independently presents a hydrogen atom or the like; "A" represents a di(ethyleneoxy)ethyl group or the like; and "n" is a natural number and its average is 1.2-5.)

Description

  The present invention relates to a negative photosensitive resin composition, a photosensitive dry film having a photosensitive resin layer made of the negative photosensitive resin composition, and a light-receiving device provided with a cured spacer of the negative photosensitive resin composition. About.

  In recent years, there has been a demand for a photosensitive dry film that can be bonded to a semiconductor wafer or the like, formed a pattern by exposure / development, and then crimped to a transparent substrate such as glass (see Patent Documents 1 and 2). When such a photosensitive dry film is used, the patterned photosensitive dry film has a function of a spacer between the semiconductor wafer and the transparent substrate.

  As the photosensitive resin layer of such a photosensitive dry film, in addition to being able to be patterned by a photolithography method, it is required that the shape can be maintained as a spacer. Further, since it is pressure-bonded to the transparent substrate after exposure / development, it is required to have excellent adhesion after patterning in addition to developability and resolution.

JP 2006-323089 A JP 2008-297540 A

  However, until now, no photosensitive resin composition capable of forming a photosensitive resin layer excellent in developability, resolution, and adhesion after patterning has been proposed.

  The present invention was made in view of such conventional circumstances, and is a negative photosensitive resin composition capable of forming a photosensitive resin layer excellent in developability, resolution, and adhesion after patterning, It is an object of the present invention to provide a photosensitive dry film having a photosensitive resin layer made of the negative photosensitive resin composition, and a light receiving device including a spacer obtained by curing the negative photosensitive resin composition.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, it has been found that the above problems can be solved by a negative photosensitive resin composition containing an epoxy resin having a specific structure, and the present invention has been completed. Specifically, the present invention provides the following.

The first aspect of the present invention is an alkali-soluble resin (A), a compound (B) that generates an acid or a radical upon irradiation with active rays, a compound (C) that can be cross-linked by an acid or a radical generated from the component (B). ), An epoxy resin (D) represented by the following general formula (D-1), and a negative photosensitive resin composition containing a solvent (S).
[In General Formula (D-1), R ^d1 and R ^d2 each independently represent a hydrogen atom or a methyl group, and R ^{d3 to} R ^d6 each independently represent a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom. . A is an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propyleneoxy) propyl group, a tri (propyleneoxy) propyl group, or a carbon number of 2 to 15 Represents an alkylene group. n is a natural number, and the average is 1.2-5. ]

  The second aspect of the present invention has a base film and a photosensitive resin layer formed on the surface of the base film, and the photosensitive resin layer is a negative photosensitive resin composition according to the present invention. A photosensitive dry film comprising:

  A third aspect of the present invention includes a support substrate on which a semiconductor element is mounted, a transparent substrate facing the support substrate, and a spacer provided between the support substrate and the transparent substrate. Is a light-receiving device that is a cured product of the negative photosensitive resin composition according to the present invention.

  According to the present invention, a negative photosensitive resin composition capable of forming a photosensitive resin layer excellent in developability, resolution, and adhesion after patterning, and a photosensitive resin comprising the negative photosensitive resin composition It is possible to provide a light receiving device including a photosensitive dry film having a layer and a spacer obtained by curing the negative photosensitive resin composition.

It is a figure which shows typical sectional drawing of a light-receiving device. 3 is a diagram showing a line and space pattern obtained in Example 1. FIG. It is a figure which shows the line and space pattern obtained by the comparative example 1.

≪Negative photosensitive resin composition≫
The negative photosensitive resin composition according to the present invention is crosslinkable with an alkali-soluble resin (A), a compound (B) that generates an acid or a radical upon irradiation with actinic radiation, and an acid or a radical generated from the component (B). Compound (C), an epoxy resin (D) having a specific structure, and a solvent (S).
This negative photosensitive resin composition has a chemical amplification type and a radical polymerization type, and the types of the components (A) to (C) are different in each case.
Hereinafter, each component contained in the negative photosensitive resin composition according to the present invention will be described in detail.

<Alkali-soluble resin (A)>
As the alkali-soluble resin, those conventionally used in chemically amplified and radical polymerization negative photosensitive resin compositions can be used without particular limitation. Specifically, an alkali-soluble resin (A1) having a phenolic hydroxyl group can be used in the case of a chemically amplified type, and an alkali-soluble resin having a structural unit derived from an unsaturated carboxylic acid in the case of a radical polymerization type. (A2) can be used.

(Alkali-soluble resin (A1) having phenolic hydroxyl group)
The alkali-soluble resin (A1) is not particularly limited, and examples thereof include polyhydroxystyrene resins, novolac resins, phenol-xylylene glycol condensation resins, cresol-xylylene glycol condensation resins, and phenol-dicyclopentadiene condensation resins. . Of these, polyhydroxystyrene resins and novolak resins are preferable, and polyhydroxystyrene resins are more preferable.

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

  The structural unit derived from hydroxystyrene is represented, for example, by the following general formula (A1-1).

In the general formula (A1-1), 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 represents 1 to 3 An integer is shown, and q is an integer of 0 to 2.

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

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

  The structural unit represented by the general formula (A1-1) may be used alone or in combination of two or more.

  In the polyhydroxystyrene resin, the proportion of structural units 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. It is more preferable that it is 80-100 mol%. Within this range, moderate alkali solubility can be obtained when a negative photosensitive resin composition is obtained.

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

The structural unit derived from styrene is represented by the following general formula (A2-1), for example. In general formula (A2-1), R ^a1 , R ^a2 and q have the same meanings as those in general formula (A1-1).

The R ^a1 and ^{R a2,} include those similar to respectively ^{R a1} and ^{R a2} in formula (A1-1).
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 o-position, the m-position, and the p-position when q is 1, and when q is 2, any substitution position can be combined.

  The structural unit represented by the general formula (A2-1) 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, and preferably 30 mol% or less with respect to all the structural units constituting the polyhydroxystyrene resin. Is more preferable, and it is further more preferable that it is 20 mol% or less. Within this range, when a negative photosensitive resin composition is obtained, moderate alkali solubility is obtained, and the balance with other structural units is also good.

  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. is there.

  The mass average molecular weight (polystyrene conversion standard by gel permeation chromatography, hereinafter the same in the present specification) of the polyhydroxystyrene resin is not particularly limited, but is preferably 1500 to 40000, more preferably 2000 to 8000.

  The novolak resin can be obtained by addition condensation of phenols and aldehydes in the presence of an acid catalyst.

Examples of the phenols include cresols such as phenol, o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3, Xylenols such as 4-xylenol and 3,5-xylenol; o-ethylphenol, m-ethylphenol, p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m- Alkylphenols such as butylphenol, p-butylphenol and p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; resorcinol, catechol, hydroquinone, ha Polyhydric phenols such as droquinone monomethyl ether, pyrogallol, 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 the 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. Can be mentioned. 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.

  Although the mass average molecular weight of the said novolak resin is not specifically limited, 1000-30000 are preferable and 3000-25000 are more preferable.

(Alkali-soluble resin (A2) having a structural unit derived from unsaturated carboxylic acid)
The alkali-soluble resin (A2) has at least a structural unit derived from an unsaturated carboxylic acid.
Examples of the unsaturated carboxylic acid include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid. Among these, (meth) acrylic acid is preferable. These unsaturated carboxylic acids may be used alone or in combination of two or more.
In the present specification, “(meth) acrylic acid” represents both methacrylic acid and acrylic acid. The same applies to “(meth) acrylate” and “(meth) acrylamide” described later.

  In the alkali-soluble resin (A2), the proportion of the structural unit derived from the unsaturated carboxylic acid is preferably 2 to 30 mol% with respect to all the structural units constituting the alkali-soluble resin (A2). More preferably, it is -20 mol%. Within this range, moderate alkali solubility can be obtained when a negative photosensitive resin composition is obtained.

The alkali-soluble resin (A2) preferably further has a structural unit derived from a polymerizable monomer other than the unsaturated carboxylic acid.
Examples of such polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, amyl (meth) acrylate, cyclohexyl (meth) acrylate, and dicyclopenta Nyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate , 2-methoxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, benzyl (meth) acrylate, methoxybenzyl (meth) (Meth) acrylic acid esters such as acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenyl (meth) acrylate; (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) Acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-tolyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl ( (Meth) acrylamide, N, N-methylethyl (meth) acrylamide, N, N-diphenyl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide, N-2-ace (Meth) acrylamides such as amidoethyl-N-acetyl (meth) acrylamide; hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, hydroxyethyl vinyl ether, benzyl vinyl ether, vinyl phenyl ether, vinyl tolyl Vinyl ethers such as ethers; Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate, vinyl naphthoate; styrene, N-vinylpyrrolidone, etc. And other vinyl compounds. These polymerizable monomers may be used alone or in combination of two or more.

  In the alkali-soluble resin (A2), the proportion of the structural unit derived from the polymerizable monomer is preferably 70 to 98 mol% with respect to all the structural units constituting the alkali-soluble resin (A2). More preferably, it is 80-95 mol%. Within this range, when a negative photosensitive resin composition is obtained, moderate alkali solubility is obtained, and the balance with other structural units is also good.

<Compound (B) that generates acid or alkali upon irradiation with actinic radiation>
Compounds that generate acid or alkali upon irradiation with actinic rays are those that generate acids or radicals upon irradiation with actinic rays such as ultraviolet rays, far ultraviolet rays, KrF, ArF, etc., X-rays, electron beams, etc. For example, it can be used without any particular limitation. Specifically, in the case of the chemically amplified type, a compound that generates an acid upon irradiation with actinic rays (hereinafter referred to as “photoacid generator”) (B1) is used. Agent (B2) is used.

(Photoacid generator (B1))
As the photoacid generator (B1), a conventionally known compound can be used without particular limitation. For example, 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 (nitrobenzyl derivatives), iminosulfonates Examples include acid generators and disulfone acid generators.
Among these, a sulfonium salt-based acid generator, an oxime sulfonate-based acid generator, and a halogen-containing triazine compound are preferable from the viewpoint of excellent effects of the present invention. In particular, the crosslinker (C1) described later has good crosslinkability, while the reactivity with the epoxy resin (D) having a specific structure is low, and oxime sulfonate acid generation is possible because it can provide higher adhesion after patterning. Agents and halogen-containing triazine compounds are preferred.

  As a preferable sulfonium salt acid generator, specifically, for example, a compound represented by the following general formula (B1-1) can be used.

In the general formula (B1-1), R ^b1 and R ^b2 may each independently have a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group which may have a halogen atom, or a substituent. A good alkoxy group, R ^b3 represents a halogen atom or a p-phenylene group optionally having an alkyl group, R ^b4 represents a hydrogen atom, an oxygen atom or a hydrocarbon group optionally having a halogen atom, A benzoyl group which may have a substituent, or a polyphenyl group which may have a substituent, and X ⁻ represents a counter ion of an onium ion.

In the general formula (B1-1), X ⁻ is specifically SbF ₆ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , BF ₄ ⁻ , SbCl ₆ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , CH _3. SO ₃ ⁻ , FSO ₃ ⁻ , F ₂ PO ₂ ⁻ , p-toluenesulfonate, nonafluorobutanesulfonate, adamantanecarboxylate, tetraarylborate, fluorinated alkylfluorophosphate represented by the following general formula (B1-2) Anion etc. are mentioned.

  In the general formula (B1-2), Rf represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. m is the number and represents an integer of 1 to 5. The m Rf may be the same or different.

  Examples of the photoacid generator represented by the general formula (B1-1) include 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate and 4- (2-chloro-4-benzoyl). Phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro- 4-benzoylphenylthio) phenylbis (4-methylphenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4- (β-hydroxyethoxy) phenyl) sulfonium hexafluoroantimonate Nate 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (3-methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexanium Fluoroantimonate, 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- Benzoylphenylthio) 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 ( -Chlorophenyl) 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) Rufonium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoro Antimonate, 4- (2-chloro-4- (4-fluorobenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoro Antimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) pheny Rubis (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 hexafluoroantimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) pheny Bis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4 -(4-Fluorobenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimony 4- (2-chloro-4-dodecanoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenyl diphenate Rusulfonium 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- Benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) s Rufonium perchlorate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium trifluoromethanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluoro Phenyl) 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-benzoy) Phenylthio) 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.

  Other onium salt acid generators include, for example, triphenylsulfonium, (4-tert-butoxyphenyl) diphenylsulfonium, bis (4-tert-butoxyphenyl) for the cation moiety of the above general formula (B1-1). Phenylsulfonium, 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-thiof) Noxyphenyl) 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, tribenzylsulfonium, diphenyliodonium, bis 4-tert-butylphenyl) 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, compounds represented by general formula (B1-3) shown below can be given.

In the general formula (B1-3), R ^b5 represents a monovalent, divalent, or trivalent organic group, and R ^b6 represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic group. And r represents an integer of 1 to 6.
R ^b5 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. Further, particularly preferably an alkyl group having 1 to 6 carbon atoms as R ^b6, a methyl group, an ethyl group, a propyl group, a butyl group. R is preferably an integer of 1 to 3, and more preferably 1 or 2.

As the photoacid generator represented by the general formula (B1-3), when r = 1, R ^b5 is any one of a phenyl group, a methylphenyl group, and a methoxyphenyl group, and R ^Examples include compounds in which ^b6 is a methyl group. More specifically, as the photoacid generator represented by the general formula (B1-3), α- (methylsulfonyloxyimino) -1-phenylacetonitrile, α- (methylsulfonyloxyimino) -1- ( p-methylphenyl) acetonitrile and α- (methylsulfonyloxyimino) -1- (p-methoxyphenyl) acetonitrile.

  The photoacid generator represented by the general formula (B1-3) is a photoacid generator represented by the following formulas (B1-3-1) to (B1-3-8) when r = 2. Agents.

  Examples of halogen-containing triazine compounds include 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (2-furyl) ethenyl. ] -S-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [ 2- (5-ethyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-propyl-2-furyl) ethenyl] -s-triazine, 2 , 4-Bis (trichloromethyl) -6- [2- (3,5-dimethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-di Ethoxypheny ) Ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dipropoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6 -[2- (3-methoxy-5-ethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5-propoxyphenyl) ethenyl] -s -Triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- (3 4-methylenedioxyphenyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-triazine Loromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4- Bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-Methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (2-furyl) ethenyl] -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- [2- (5-methyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3 , 5-Zime Toxiphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (3,4-methylenedioxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, tris (1,3-dibromopropyl) -1 , 3,5-triazine, halogen-containing triazine compounds such as tris (2,3-dibromopropyl) -1,3,5-triazine, and the following general formulas such as tris (2,3-dibromopropyl) isocyanurate ( And halogen-containing triazine compounds represented by B1-4).

In the general formula (B1-4), R ^b7 , R ^b8 , and R ^b9 each independently represent a halogenated alkyl group having 1 to 6 carbon atoms.

Other photoacid generators include bis (p-toluenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1- (1,1-dimethylethylsulfonyl) diazomethane, bis (1 , 1-dimethylethylsulfonyl) diazomethane, bis (1-methylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (4-ethylphenylsulfonyl) diazomethane, bis ( 3-methylphenylsulfonyl) diazomethane, bis (4-methoxyphenylsulfonyl) diazomethane, bis (4-fluorophenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazo Bissulfonyldiazomethanes such as tan, bis (4-tert-butylphenylsulfonyl) diazomethane; 2-methyl-2- (p-toluenesulfonyl) propiophenone, 2- (cyclohexylcarbonyl) -2- (p-toluenesulfonyl) ) Sulfonylsulfonyl alkanes such as propane, 2-methanesulfonyl-2-methyl- (p-methylthio) propiophenone, 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one; -Toluenesulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-methylsulfonyl-4-phenyl-2-butanone, 1-cyclohexylsulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-cyclohexylsulfonyl-3,3 -Dimethyl 2-butanone, 1-diazo-1- (1,1-dimethylethylsulfonyl) -3,3-dimethyl-2-butanone, 1-acetyl-1- (1-methylethylsulfonyl) diazomethane, 1-diazo- 1- (p-toluenesulfonyl) -3,3-dimethyl-2-butanone, 1-diazo-1-benzenesulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1- (p-toluenesulfonyl) -3-methyl-2-butanone, 2-diazo-2- (p-toluenesulfonyl) acetate cyclohexyl, 2-diazo-2-benzenesulfonylacetate-tert-butyl, 2-diazo-2-methanesulfonylacetate isopropyl, 2 -Diazo-2-benzenesulfonylacetate cyclohexyl, 2-diazo-2- (p-toluenesulfonyl) acetate-tert-butyl Sulfonylcarbonyldiazomethanes such as p-toluenesulfonic acid-2-nitrobenzyl, p-toluenesulfonic acid-2,6-dinitrobenzyl, p-trifluoromethylbenzenesulfonic acid-2,4-dinitrobenzyl, etc. Derivatives: pyrogallol methane sulfonate, pyrogallol benzene sulfonate, pyrogallol p-toluene sulfonate, pyrogallol p-methoxybenzene sulfonate, pyrogallol mesitylene sulfonate, pyrogallol benzyl sulfonate, gallic acid Alkyl methanesulfonate ester, alkyl gallate benzenesulfonate ester, alkyl gallate p-toluenesulfonate ester, alkyl gallate (alkyl group charcoal) The number of which is 1 to 15), such as p-methoxybenzene sulfonate ester, alkyl gallate mesitylene sulfonate ester, alkyl gallate benzyl sulfonate ester, and the like, and ester of aliphatic or aromatic sulfonic acid And the like.
These photoacid generators may be used alone or in combination of two or more.

  The content of the photoacid generator (B1) 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 alkali-soluble resin (A1). Within this range, the curability of the negative photosensitive resin composition is improved.

(Radical polymerization initiator (B2))
As the radical polymerization initiator (B2), a conventionally known compound can be used without particular limitation.
Specifically, thioxanthone derivatives such as 2,4-diethylthioxanthone, isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone; benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone, N , N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl Aromatic ketones such as -1- [4- (methylthio) phenyl] -2-morpholino-propanone-1; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone 2,3-benzua Traquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, 2,3 -Quinones such as dimethyl anthraquinone; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin; benzyl derivatives such as benzyl dimethyl ketal; 2- (o- Chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenyl Imidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-tria 2,4,5-triarylimidazole dimers such as reel imidazole dimer; acridine derivatives such as 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane; ethanone, 1- [9 Examples include oxime esters such as -ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); N-phenylglycine; and coumarin compounds.
These radical polymerization initiators may be used alone or in combination of two or more.

  The content of the radical polymerization initiator (B2) is preferably 0.05 to 30 parts by mass and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A2). Within this range, the curability of the negative photosensitive resin composition is improved.

<Compound capable of crosslinking by acid or radical (C)>
The compound that can be cross-linked by an acid or a radical is not particularly limited as long as it can be cross-linked with another compound by the acid or radical generated from the component (B) or between the compounds. be able to. Specifically, the crosslinking agent (C1) is used in the case of the chemical amplification type, and the polymerizable monomer (C2) is used in the case of the radical polymerization type.

(Crosslinking agent (C1))
The crosslinking agent (C1) is crosslinked with the alkali-soluble resin (A1) by the action of the acid generated from the photoacid generator (B1).
Such a crosslinking agent is not particularly limited, and for example, a compound having at least two alkyl etherified amino groups in the molecule can be used. This compound includes nitrogen-containing alkyl ethers of some or all of the active methylol groups such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, (poly) methylolated urea, etc. Compounds. Examples of the alkyl group include a methyl group, an ethyl group, a butyl group, or a mixture thereof, and may contain an oligomer component that is partially self-condensed. Specific examples include hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycoluril, and tetrabutoxymethylated glycoluril.
These cross-linking agents may be used alone or in combination of two or more.

  It is preferable that it is 5-50 mass parts with respect to 100 mass parts of alkali-soluble resin (A1), and, as for content of a crosslinking agent (C1), it is more preferable that it is 10-30 mass parts. Within this range, the curability and patterning characteristics of the negative photosensitive resin composition are improved.

(Polymerizable monomer (C2))
The polymerizable monomers (C2) are cross-linked with each other by the action of radicals generated from the radical polymerization initiator (B2) to be polymerized.
Such polymerizable monomers include monofunctional monomers and polyfunctional monomers.
Monofunctional monomers 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-methylpropane sulfonic acid, tert-butylacrylamide sulfonic 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 ( And (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers may be used alone or in combination of two or more.

  On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene 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 tetra (meth) acrylate, dipentaerythritol Pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meta) ) Acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) 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 Sterol (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate Reaction product, methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, polyfunctional monomers such as a condensate of polyhydric alcohol and N-methylol (meth) acrylamide, and triacryl formal. These polyfunctional monomers may be used alone or in combination of two or more.

  The content of the polymerizable monomer (C2) is preferably 10 to 100 parts by mass and more preferably 30 to 80 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A2). Within this range, the curability and patterning characteristics of the negative photosensitive resin composition are improved.

<Epoxy resin with specific structure (D)>
The epoxy resin having a specific structure is represented by the following general formula (D-1). By adding such an epoxy resin to a negative photosensitive resin composition, a photosensitive resin layer having excellent developability, resolution, and adhesiveness after patterning when a negative photosensitive resin composition is obtained. Can be formed.

In the general formula (D-1), R ^d1 and R ^d2 each independently represent a hydrogen atom or a methyl group. R ^{d3 to} R ^d6 each independently represent a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom, and among them, a hydrogen atom is preferable. A is an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propyleneoxy) propyl group, a tri (propyleneoxy) propyl group, or a carbon number of 2 to 15 Represents an alkylene group. n is a natural number, and the average is 1.2-5.

Specific examples of the epoxy resin represented by the general formula (D-1) include resins represented by the following formulas (D-1-1) to (D-1-14).
These compounds may be used alone or in combination of two or more.

  The content of the component (D) is preferably 1 to 40 parts by mass and more preferably 5 to 35 parts by mass with respect to 100 parts by mass of the component (A). Within this range, when a negative photosensitive resin composition is obtained, a photosensitive resin layer excellent in developability, resolution, and adhesiveness after patterning can be formed.

<Solvent (S)>
As the solvent (S), conventionally known solvents for negative photosensitive resin compositions can be used without particular limitation.
Specifically, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like Propylene glycol monoalkyl 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 propylene 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; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate Other esters such as ru, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene, xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; N-dimethylformamide, Examples include amides such as N-methylacetamide, N, N-dimethylacetamide, and N-methylpyrrolidone; lactones such as γ-butyrolacun.
These solvents may be used alone or in combination of two or more.

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

<Other ingredients>
The negative photosensitive resin composition according to the present invention may contain an additional resin, a stabilizer, a colorant, a surfactant and the like as desired.

≪Photosensitive dry film≫
The photosensitive dry film according to the present invention has a base film and a photosensitive resin layer formed on the surface of the base film, and the photosensitive resin layer is a negative photosensitive resin composition according to the present invention. It consists of things.

  As a base film, what has a light transmittance is preferable. Specific examples include a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyethylene (PE) film, and the like, and a polyethylene terephthalate (PET) film is preferable in terms of excellent balance between light transmittance and breaking strength.

  When forming the photosensitive resin layer on the base film, using an applicator, bar coater, wire bar coater, roll coater, curtain flow coater, etc., the dry film thickness will be 5 to 100 μm on the base film. The negative photosensitive resin composition according to the present invention is applied to and dried.

  The photosensitive dry film according to the present invention may further have a protective film on the photosensitive resin layer. Examples of the protective film include a polyethylene terephthalate (PET) film, a polypropylene (PP) film, and a polyethylene (PE) film.

≪Light receiving device≫
A light receiving device according to the present invention includes a support substrate on which a semiconductor element is mounted, a transparent substrate facing the support substrate, and a spacer provided between the support substrate and the transparent substrate. Is a cured product of the negative photosensitive resin composition according to the present invention.

  A schematic cross-sectional view of the light receiving device is shown in FIG. As shown in FIG. 1, the light receiving device 1 includes a support substrate 10, a light receiving unit 11 made of a semiconductor element mounted on the support substrate 10, a transparent substrate 12 facing the support substrate 10, a support substrate 10 and a transparent substrate. And a spacer 13 provided between the substrate 12 and the substrate 12.

For example, the light receiving device 1 can be manufactured as follows.
First, a photosensitive dry film is bonded onto the support substrate 10 so that the light receiving unit 11 and the photosensitive resin layer are in contact with each other. Next, the photosensitive resin layer is irradiated with active rays such as ultraviolet rays on a portion to be a spacer, and the photosensitive resin layer is heated at 40 to 200 ° C. as necessary. Next, the base film of the photosensitive dry film is peeled off, and the uncured portion is dissolved and removed with a developer such as an aqueous solution of tetramethylammonium hydroxide (TMAH), thereby forming the spacer 13. Thereafter, the light receiving device 1 can be obtained by placing the transparent substrate 12 on the spacer 13 and performing thermocompression bonding. The conditions for thermocompression bonding are, for example, 100 to 200 ° C. and 0.05 to 100 MPa.

  In the above example, the photosensitive resin layer is formed on the light receiving unit 11 by attaching a photosensitive dry film, but the present invention is not limited to this. For example, the photosensitive resin layer may be formed on the light receiving unit 11 by applying the above-described negative photosensitive resin composition on the light receiving unit 11 and drying it. As a coating method, spin coating is preferable in terms of high film thickness uniformity. By increasing the film thickness uniformity, the adhesion surfaces of the spacers 13 and the transparent substrate 12 are aligned after patterning, and the adhesion is improved.

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

<Examples 1-11, Comparative Examples 1-4>
According to the formulation shown in Table 1 (unit is part by mass), an alkali-soluble resin, a photoacid generator, a crosslinking agent, an epoxy resin, and a solvent are mixed, and the negative types of Examples 1 to 7 and Comparative Examples 1 and 2 A photosensitive resin composition was prepared.
Moreover, according to the prescription (a unit is a mass part) of Table 2, alkali-soluble resin, a radical polymerization initiator, a polymerizable monomer, an epoxy resin, and a solvent are mixed, and Examples 8-11 and Comparative Examples 3 and 4 are mixed. A negative photosensitive resin composition was prepared.
Details of each component in Tables 1 and 2 are as follows.

Alkali-soluble resin A: polyhydroxystyrene (mass average molecular weight 2500)
Alkali-soluble resin B: copolymer of hydroxystyrene / styrene = 80/20 (molar ratio) (mass average molecular weight 2500)
Alkali-soluble resin C: cresol novolak resin obtained by mixing m-cresol and p-cresol at m-cresol / p-cresol = 60/40 (mass ratio), adding formalin and subjecting to addition condensation by a conventional method ( (Mass average molecular weight 20000)
Alkali-soluble resin D: copolymer of 2-methoxyethyl acrylate / n-butyl acrylate / dicyclopentanyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate = 4/4/65/20/7 (molar ratio) (mass ratio) (Average molecular weight 20000)
Alkali-soluble resin E: 2-methoxyethyl acrylate / n-butyl acrylate / dicyclopentanyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate / N-vinyl pyrrolidone = 4/4/66/16/9/1 (molar ratio) ) Copolymer (mass average molecular weight 20000)

Photoacid generator A: [2- (propylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] (o-tolyl) acetonitrile (manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE PAG103)
Photoacid generator B: diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotrispentafluoroethyl phosphate (manufactured by San Apro, CPI-210S)
Photoacid generator C: 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate (manufactured by ADEKA, Adekaoptomer SP-172)
Photoacid generator D: α, α-bis (butylsulfonyloxyimino) -m-phenylenediacetonitrile (compound represented by the above formula (B1-3-3). Based on the description in JP-A-9-208554 Synthesized.)
Photoacid generator E: α- (methylsulfonyloxyimino) -1- (p-methoxyphenyl) acetonitrile (synthesized based on the description in JP-A-9-95479)
Radical polymerization initiator A: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (manufactured by Ciba Specialty Chemicals, CGI242)

Crosslinking agent A: 2,4,6-tris [bis (methoxymethyl) amino] -1,3,5-triazine (manufactured by Sanwa Chemical Co., Ltd., Mw-100LM)
Crosslinking agent B: 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., Mw-270)
Polymerizable monomer A: dipentaerythritol tetraacrylate (DPHA)
Polymerizable monomer B: trimethylolpropane tri (meth) acrylate (manufactured by Toa Gosei Co., Ltd., Aronix M309)
Polymerizable monomer C: polyethylene glycol diacrylate (manufactured by Toa Gosei Co., Ltd., Aronix M240)

Epoxy resin A: Resin in which n = 1.6 (average value) in the above formula (D-1-1) (DIC Corporation, EXA4850-150)
Epoxy resin B: Resin in which n = 1.2 (average value) in the above formula (D-1-1) (DIC Corporation, EXA4850-1000)
Epoxy resin C: bifunctional bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd., jER828)
Solvent A: Propylene glycol monomethyl ether acetate

<Development evaluation>
The negative photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 4 were coated on an 8-inch silicon wafer with a spin coater and dried at 120 ° C. for 5 minutes to form a photosensitive resin layer having a thickness of 50 μm. Obtained. Subsequently, this photosensitive resin layer was irradiated with ghi rays through a mask at an irradiation amount of 250 mJ / cm ² . Next, after heating on a hot plate at 115 ° C. for 5 minutes, uncured portions were dissolved and removed by paddle development (60 seconds × 2) using a 2.38 mass% tetramethylammonium hydroxide aqueous solution, and the line width was 40 μm. A line and space pattern including a space pattern was formed. Then, the developability of the photosensitive resin layer was evaluated with a circle having no residue in the space portion and a circle having a residue. The results are shown in Tables 1 and 2.

<Evaluation of adhesiveness>
The negative photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 4 were coated on an 8-inch silicon wafer with a spin coater and dried at 120 ° C. for 5 minutes to form a photosensitive resin layer having a thickness of 50 μm. Obtained. Next, this photosensitive resin layer was irradiated with ghi rays at an irradiation amount of 250 mJ / cm ² and heated on a hot plate at 115 ° C. for 5 minutes. Next, a glass substrate having a thickness of 0.7 mm was thermocompression bonded on the heated photosensitive resin layer under the conditions of 100 ° C. and 0.1 MPa. Then, the adhesiveness of the photosensitive resin layer was evaluated by making the case where the glass substrate adheres as ◯ and the case where the glass substrate is not attached as x. The results are shown in Tables 1 and 2.

<Evaluation of resolution>
The negative photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 4 were coated on an 8-inch silicon wafer with a spin coater and dried at 120 ° C. for 5 minutes to form a photosensitive resin layer having a thickness of 50 μm. Obtained. Subsequently, this photosensitive resin layer was irradiated with ghi rays through a mask at an irradiation amount of 250 mJ / cm ² . Next, after heating on a hot plate at 115 ° C. for 5 minutes, uncured portions were dissolved and removed by paddle development (60 seconds × 2) using a 2.38 mass% tetramethylammonium hydroxide aqueous solution, and line-and-space. A pattern was formed. Then, the limit resolution was obtained by changing the mask dimension. The results are shown in Tables 1 and 2.

<Evaluation of remaining film ratio>
The negative photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 4 were coated on an 8-inch silicon wafer with a spin coater and dried at 120 ° C. for 5 minutes to form a photosensitive resin layer having a thickness of 50 μm. Obtained. Next, this photosensitive resin layer was irradiated with ghi rays at an irradiation amount of 250 mJ / cm ² and heated on a hot plate at 115 ° C. for 5 minutes. Furthermore, it heated at 180 degreeC for 2 hours using the clean oven. And the ratio (%) with respect to the original film thickness of the film thickness after a heating was calculated | required, and the remaining film rate was evaluated. The results are shown in Tables 1 and 2.

  As can be seen from Table 1, in the case of a chemically amplified negative photosensitive resin composition, an example using a negative photosensitive resin composition containing an epoxy resin represented by the above general formula (D-1). In Nos. 1 to 7, the photosensitive resin layer was excellent in developability, resolution, adhesion after patterning, and remaining film ratio. On the other hand, in Comparative Example 1 using a negative photosensitive resin composition containing an epoxy resin different from the epoxy resin represented by the general formula (D-1), the developability is poor and the negative type does not contain an epoxy resin. In Comparative Example 2 using the photosensitive resin composition, the adhesiveness was poor.

In the above <development evaluation>, the line and space pattern obtained in Example 1 is shown in FIG. 2, and the line and space pattern obtained in Comparative Example 1 is shown in FIG. In the figure, the whitest part is the space part. As can be seen from FIGS. 2 and 3, in Example 1, there is no residue in the space portion, whereas in Comparative Example 1, there are many residues.
Thus, the difference in developability appears because the normal epoxy resin used in Comparative Example 1 reacts with the crosslinking agent during heating of the photosensitive resin layer and tends to remain as a residue, whereas Examples 1 to 7 It is presumed that the epoxy resin represented by the general formula (D-1) used in 1) has low reactivity with the cross-linking agent and hardly remains as a residue.

Further, as can be seen from Table 2, in the case of a radical polymerization type negative photosensitive resin composition, a negative photosensitive resin composition containing an epoxy resin represented by the above general formula (D-1) was used. In Examples 8-11, it was excellent in all of the developability of a photosensitive resin layer, resolution, the adhesiveness after patterning, and the remaining film rate. On the other hand, in Comparative Examples 3 and 4 using a negative photosensitive resin composition containing an epoxy resin different from the epoxy resin represented by the general formula (D-1), developability and resolution were poor.
Among these, the difference in developability appears because the normal epoxy resin used in Comparative Examples 3 and 4 reacts with the carboxy group of the alkali-soluble resin during heating of the photosensitive resin layer, and tends to remain as a residue, It is estimated that the epoxy resin represented by the general formula (D-1) used in Examples 8 to 11 has a low reactivity with a carboxy group and hardly remains as a residue.

  DESCRIPTION OF SYMBOLS 1 Light receiving device, 10 Support substrate, 11 Light-receiving part, 12 Transparent substrate, 13 Spacer

Claims (5)

Alkali-soluble resin (A), compound (B) that generates acid or radical upon irradiation with actinic radiation, compound (C) that can be cross-linked by acid or radical generated from component (B), and the following general formula (D-1) A negative photosensitive resin composition containing an epoxy resin (D) represented by the formula (A) and a solvent (S).
[In General Formula (D-1), R ^d1 and R ^d2 each independently represent a hydrogen atom or a methyl group, and R ^{d3 to} R ^d6 each independently represent a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom. . A is an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propyleneoxy) propyl group, a tri (propyleneoxy) propyl group, or a carbon number of 2 to 15 Represents an alkylene group. n is a natural number, and the average is 1.2-5. ]   The negative photosensitive resin composition according to claim 1, wherein the content of the component (D) is 5 to 40 parts by mass with respect to 100 parts by mass of the component (A).   The negative photosensitive resin according to claim 1 or 2, wherein the component (A) is an alkali-soluble resin (A1) having a phenolic hydroxyl group or an alkali-soluble resin (A2) having a structural unit derived from an unsaturated carboxylic acid. Composition.   A negative photosensitive resin composition according to any one of claims 1 to 3, further comprising a base film and a photosensitive resin layer formed on a surface of the base film. A photosensitive dry film comprising: A support substrate on which a semiconductor element is mounted;
A transparent substrate facing the support substrate;
A spacer provided between the support substrate and the transparent substrate;
A light receiving device, wherein the spacer is a cured product of the negative photosensitive resin composition according to claim 1.