KR101666231B1 - Negative photosensitive resin composition, photosensitive dry film, and light receiving device - Google Patents

Abstract

[식 중, R^d1 및 R^d2 는 각각 독립적으로 메틸기 등을 나타내고, R^d3 ∼ R^d6 은 각각 독립적으로 수소 원자 등을 나타낸다. A 는 디(에틸렌옥시)에틸기 등을 나타낸다. n 은 자연수이며, 그 평균은 1.2 ∼ 5 이다] assignment
A negative photosensitive resin composition capable of forming a photosensitive resin layer excellent in developability, resolution and adhesiveness after patterning, a photosensitive dry film having a photosensitive resin layer composed of the composition, and a light receiving element having a cured spacer Device.
Solution
The negative-working photosensitive resin composition of the present invention, which is preferable for forming the spacer 13 of the light receiving device 1, comprises an alkali-soluble resin (A), a compound (B) which generates an acid or a radical by irradiation of an active ray, (C) crosslinkable by a radical, an epoxy resin (D) represented by the general formula (D-1), and a solvent (S).

^Wherein R ^d1 and R ^d2 Each independently represent a methyl group or the like, R ^d3 ~ R ^d6 Each independently represent a hydrogen atom or the like. A represents a di (ethyleneoxy) ethyl group or the like. n is a natural number, the average being 1.2 to 5]

Description

TECHNICAL FIELD [0001] The present invention relates to a negative photosensitive resin composition, a photosensitive dry film, and a light receiving device.

The present invention relates to a negative photosensitive resin composition, a photosensitive dry film having a photosensitive resin layer composed of the negative photosensitive resin composition, and a light receiving device comprising the spacer in which the negative photosensitive resin composition is cured.

2. Description of the Related Art Recently, there is a demand for a photosensitive dry film which can be adhered to a transparent substrate such as glass after bonding to a semiconductor wafer or the like, forming a pattern by exposure or development (see Patent Documents 1 and 2). When such a photosensitive dry film is used, the photosensitive dry film after patterning has a spacer action between the semiconductor wafer and the transparent substrate.

The photosensitive resin layer of such a photosensitive dry film is required to be capable of being patterned by a photolithography method and capable of maintaining its shape as a spacer. In addition, in order to adhere to a transparent substrate after exposure and development, it is required to have excellent developability and resolution as well as excellent adhesiveness after patterning.

Japanese Laid-Open Patent Publication No. 2006-323089 Japanese Patent Application Laid-Open No. 2008-297540

However, a photosensitive resin composition capable of forming a photosensitive resin layer having excellent developability, resolution, and adhesion after patterning has not been proposed so far.

SUMMARY OF THE INVENTION The present invention has been made in view of such conventional circumstances, and it is an object of the present invention to provide a negative photosensitive resin composition capable of forming a photosensitive resin layer having excellent developability, resolution and adhesiveness after patterning, a photosensitive resin composition comprising the negative photosensitive resin composition It is an object of the present invention to provide a light-receiving device having a photosensitive dry film having a layer and a spacer in which the negative photosensitive resin composition is cured.

The present inventors have conducted intensive studies in order 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 accomplished. Specifically, the present invention provides the following.

A first aspect of the present invention is a method for producing a resin composition which comprises an alkali-soluble resin (A), a compound (B) that generates an acid or a radical by irradiation of an actinic ray, an acid or a radical- , An epoxy resin (D) represented by the following general formula (D-1), and a solvent (S).

[Chemical Formula 1]

[In the general formula (D-1), R ^d1 and R ^d2 Each independently represent a hydrogen atom or a methyl group, R ^d3 ~ R ^d6 Each independently represent a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom. A is an alkylene group having 2 to 15 carbon atoms, such as an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propylenoxy) . n is a natural number, the average being 1.2 to 5]

A second aspect of the present invention is a photosensitive dry film comprising a base film and a photosensitive resin layer formed on the surface of the base film, wherein the photosensitive resin layer is composed of the negative photosensitive resin composition related to the present invention.

A third aspect of the present invention is a semiconductor device comprising a support substrate on which a semiconductor element is mounted, a transparent substrate facing the support substrate, and a spacer formed between the support substrate and the transparent substrate, Which is a cured product of the photosensitive resin composition.

INDUSTRIAL APPLICABILITY According to the present invention, there can be provided a negative photosensitive resin composition capable of forming a photosensitive resin layer having excellent developability, resolution and adhesion after patterning, a photosensitive dry film having a photosensitive resin layer composed of the negative photosensitive resin composition, It is possible to provide a light-receiving device in which the negative-type photosensitive resin composition has a cured spacer.

1 is a diagram showing a schematic sectional view of a light receiving device.
2 is a view showing the line and space pattern obtained in Example 1. Fig.
Fig. 3 is a diagram showing the line and space pattern obtained in Comparative Example 1. Fig.

≪ Negative-type photosensitive resin composition &

The negative-type photosensitive resin composition according to the present invention is a negative-type photosensitive resin composition comprising an alkali-soluble resin (A), a compound (B) that generates an acid or a radical by irradiation of an actinic ray, an acid or a radical (C), an epoxy resin (D) having a specific structure, and a solvent (S).

The negative-type photosensitive resin composition may be of a chemically amplified type or 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-type 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 or radical polymerization type negative photosensitive resin compositions can be used without particular limitation. Specifically, in the case of a chemically amplified type, an alkali-soluble resin (A1) having a phenolic hydroxyl group can be used, and in the case of a radical polymerization type, an alkali-soluble resin (A2) having a constituent unit derived from an unsaturated carboxylic acid can be used .

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

Examples of the alkali-soluble resin (A1) include, but are not limited to, polyhydroxystyrene resins, novolak resins, phenol-xylylene glycol condensation resins, cresol-xylylene glycol condensation resins, phenol-dicyclopentadiene condensation resins, . Of these, a polyhydroxystyrene resin and a novolac resin are preferable, and a polyhydroxystyrene resin is more preferable.

The polyhydroxystyrene-based resin has at least a constitutional unit derived from hydroxystyrene.

Here, "hydroxystyrene" means a hydrostyrene derivative in which hydrogen atoms bonded to the α-position of hydroxystyrene and hydroxystyrene are substituted with other substituents such as a halogen atom, an alkyl group and a halogenated alkyl group, and a derivative of the hydroxystyrene derivative (monomer) .

The term "hydroxystyrene derivative" means a compound in which at least a benzene ring and a hydroxyl group bonded thereto are retained. For example, when the hydrogen atom bonded to the α-position of the hydroxystyrene is a halogen atom, an alkyl group having 1 to 5 carbon atoms, , One in which an alkyl group having 1 to 5 carbon atoms is further bonded to the benzene ring to which the hydroxyl group of the hydroxystyrene is bonded and a benzene ring in which the hydroxyl group is bonded are further bonded with 1 to 2 hydroxyl groups (In this case, the total number of hydroxyl groups is 2 to 3), 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 " position of hydroxystyrene " refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.

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

(2)

In the general formula (A1-1), R ^a1 R ^a2 represents an alkyl group having 1 to 5 carbon atoms; p represents an integer of 1 to 3; q represents an integer of 0 to 2;

The alkyl group of R ^a1 preferably has 1 to 5 carbon atoms. The alkyl group is preferably a linear or branched alkyl group, more preferably 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, And the like. Among them, 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 hydrogen atoms of the above-described alkyl group having 1 to 5 carbon atoms is substituted with a halogen atom. Among them, it is preferable that all the hydrogen atoms are substituted with fluorine atoms. The fluorinated alkyl group is preferably a linear or branched fluorinated alkyl group, more preferably a trifluoromethyl group, a hexafluoroethyl group, a heptafluoropropyl group or a nonafluorobutyl group, and more preferably a trifluoromethyl group (-CF ₃ ) is most preferable.

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

The alkyl group having 1 to 5 carbon atoms for R ^{a2 includes} the same groups as those for R ^a1 .

and q is an integer of 0 to 2. Of these, 0 or 1 is preferable, and an industrial aspect is particularly preferably 0.

The substitution position of R ^a2 may be any of o-position, m-position and p-position when q is 1, and arbitrary substitution positions may be combined when q is 2.

p is an integer of 1 to 3, preferably 1.

The substitution position of the hydroxyl group may be any of o-position, m-position and p-position when p is 1, but it is preferably p-position because it is readily available and inexpensive. 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 two or more kinds may be used in combination.

The proportion of the structural unit derived from hydroxystyrene in the polyhydroxystyrene-based resin is preferably 60 to 100 mol%, more preferably 70 to 100 mol% based on the total structural units constituting the polyhydroxystyrene-based resin, , And more preferably 80 to 100 mol%. Within this range, suitable alkali solubility can be obtained when the negative type photosensitive resin composition is used.

The polyhydroxystyrene-based resin preferably has a structural unit derived from styrene.

Here, the "constitutional unit derived from styrene" is meant to include a constitutional unit formed by cleavage of an ethylenic double bond of styrene and a styrene derivative (but not hydroxystyrene).

The "styrene derivative" is a compound in which a hydrogen atom bonded to the α-position of styrene is substituted with another substituent such as a halogen atom, an alkyl group, or a halogenated alkyl group, and a hydrogen atom of a phenyl group of styrene is substituted with a substituent such as an alkyl group having 1 to 5 carbon atoms 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 " position of styrene " refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.

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

(3)

R ^a1 and R ^a2 roneun, R ^a1 and R ^a2 in the formula (A1-1) Respectively.

and q is an integer of 0 to 2. Of these, 0 or 1 is preferable, and an industrial aspect is particularly preferably 0.

The substitution position of R ^a2 may be any of o-position, m-position and p-position when q is 1, and arbitrary substitution positions may be combined when q is 2.

The structural unit represented by the general formula (A2-1) may be used alone, or two or more kinds may be used in combination.

The proportion of the styrene-derived constituent units in the polyhydroxystyrene-based resin is preferably not more than 40 mol%, more preferably not more than 30 mol% with respect to all the constituent units constituting the polyhydroxystyrene-based resin, More preferably 20 mol% or less. Within this range, suitable alkali solubility can be obtained when the negative photosensitive resin composition is used, and the balance with other constituent units is also good.

The polyhydroxystyrene-based resin may have a constitutional unit derived from hydroxystyrene or a constitutional unit derived from styrene. More preferably, the polyhydroxystyrene-based resin is a polymer comprising only a constituent unit derived from hydroxystyrene, or a copolymer comprising a constituent unit derived from hydroxystyrene and a constituent unit derived from styrene.

The mass average molecular weight (based on polystyrene conversion by gel permeation chromatography) of the polyhydroxystyrene-based resin is not particularly limited, but is preferably 1500 to 40000, more preferably 2000 to 8000 desirable.

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

Examples of the phenol include cresols such as phenol, o-cresol, m-cresol and p-cresol; Such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5- Ylenol; butylphenol, p-butylphenol, p-methylphenol, p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, alkylphenols such as tert-butylphenol; Trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; Polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and fluoroglycinol; Alkyl-substituted phenols such as alkyl resorcin, alkyl catechol and alkyl hydroquinone (all alkyl groups having 1 to 4 carbon atoms); ? -naphthol,? -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 mixing ratio of the two.

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

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 para-toluenesulfonic acid; And metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more.

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

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

(Alkali-soluble resin (A2) having a constituent unit derived from an unsaturated carboxylic acid)

The alkali-soluble resin (A2) has at least a constitutional unit derived from an unsaturated carboxylic acid.

Examples of the unsaturated carboxylic acid include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; And dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid. Among them, (meth) acrylic acid is preferable. These unsaturated carboxylic acids may be used alone or in combination of two or more.

In the present specification, the term "(meth) acrylic acid" refers to both methacrylic acid and acrylic acid. The same applies to "(meth) acrylate" and "(meth) acrylamide" to be described later.

The proportion of the constituent unit derived from the unsaturated carboxylic acid in the alkali-soluble resin (A2) is preferably from 2 to 30 mol%, more preferably from 5 to 20 mol% based on the total constituent units constituting the alkali-soluble resin (A2) % Is more preferable. Within this range, suitable alkali solubility can be obtained when the negative type photosensitive resin composition is used.

The alkali-soluble resin (A2) preferably further comprises a constituent unit derived from a polymerizable monomer other than the unsaturated carboxylic acid.

Examples of the polymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, amyl (meth) acrylate, cyclohexyl (Meth) acrylate, dicyclopentanyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2,2-dimethylhydroxypropyl Acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol mono (meth) acrylate, (Meth) acrylates such as benzyl (meth) acrylate, methoxybenzyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate and phenyl (meth) acrylate; (Meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (Meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl- (Meth) acrylamides such as amide; Vinyl ethers such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, hydroxyethyl vinyl ether, benzyl vinyl ether, vinyl phenyl ether and vinyl tolyl ether Ryu; Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethylacetate, vinyl methoxyacetate, vinyl phenylacetate, vinyl benzoate, vinyl salicylate, and vinyl naphthoate; And other vinyl compounds such as styrene and N-vinylpyrrolidone. These polymerizable monomers may be used alone or in combination of two or more.

The proportion of the constituent unit derived from the polymerizable monomer in the alkali-soluble resin (A2) is preferably 70 to 98 mol%, more preferably 80 to 95 mol% with respect to the total constituent units constituting the alkali-soluble resin (A2) Mol% is more preferable. Within this range, suitable alkali solubility can be obtained when the negative photosensitive resin composition is used, and the balance with other constituent units is also good.

≪ Compound (B) that generates an acid or an alkali by irradiation of an active ray >

Examples of the compound capable of generating an acid or an alkali by irradiation of an actinic ray include compounds capable of generating an acid or a radical by irradiation with active rays such as excimer laser light such as ultraviolet light, deep ultraviolet light, KrF, ArF, X- Can be used without. Specifically, in the case of a chemically amplified type, a compound (hereinafter referred to as a "photo acid generator") (B1) which generates an acid by irradiation of an active ray is used, and in the case of a radical polymerization type, a radical polymerization initiator .

(Photo acid generator (B1))

As the photo acid generator (B1), conventionally known compounds may 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 Benzyl derivatives), iminosulfonate calculation generators, and disulfone-based acid generators.

Of these, sulfonium salt-based acid generators, oxime sulfonate-based acid generators, and halogen-containing triazine compounds are preferable from the viewpoint of excellent effects of the present invention. Particularly, since the crosslinking property with the crosslinking agent (C1) to be described later is good, the reactivity with the epoxy resin (D) of a specific structure is low, and since higher adhesiveness can be given after patterning, the oximesulfonate- Halogen-containing triazine compounds are preferred.

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

[Chemical Formula 4]

In the general formula (B1-1), R ^b1 and R ^b2 Each independently represents a hydrocarbon group which may have a hydrogen atom, a halogen atom, an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent, and R ^b3 Represents a halogen atom or a p-phenylene group which may have an alkyl group, R ^b4 Represents a hydrocarbon group which may have a hydrogen atom, an oxygen atom or 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 above formula (B1-1), X ^- specifically, as _{^{is, 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 alkyl Fluorophosphoric acid anion and the like.

[Chemical Formula 5]

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

Examples of the photo acid generator represented by the general formula (B1-1) include 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2- Benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-methylphenyl) sulfonium hexafluoroantimonate, 4- 4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4 (2-methyl- (2-fluoro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- Phenyl) sulfonium hexafluoroantimo 4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,3,5,6-tetramethyl-4-benzoyl (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,6-dichloro-4-benzoylphenylthio) phenylbis (2,3-dimethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,3- (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-fluoro-4-benzoylphenylthio) phenylbis ) Sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoyl Phenylthiophenyl) sulfonium hexafluoroantimonate, 4- (2,3,5,6-tetramethyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium (2,6-dimethyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,6- Benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,3-dimethyl- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- 4- (2-chloro-4- (4-fluorobenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- - methoxybenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoro (2-chloro-4-dodecanoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenylbis (4-methylbenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-fluorobenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- ) Phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenylbis 4- (2-chloro-4-acetylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- Phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroaniline 4- (4-fluorobenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenylbis Phenyldiphenylsulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4- Benzoylphenylthio) phenyldiphenylsulfonium trifluoromethanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium perchlorate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluorophosphate, 4- Phonium tetraflu (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium perchlorate, 4- ) Sulfonium trifluoromethanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium p- toluenesulfonate, 4- 4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium nonafluorobutanesulfonate, 4 (4-fluorophenyl) sulfonium camphorsulfonate, 4- - (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium 4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium perchlorate, 4- (2-chloro-4- ) Sulfonium triple Phenyl] sulfonium hexafluoroantimonate, diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotris pentafluoroethylphosphite, diphenyl [4- (p- terphenylthio) phenyl] sulfonium hexafluoroantimo Diphenyl [4- (p-terphenylthio) phenyl] sulfonium trifluorotris pentafluoroethyl phosphite, and the like.

As other onium salt-based acid generators, the cation unit of the above-mentioned general formula (B1-1) is, for example, triphenylsulfonium, (4-tert-butoxyphenyl) diphenylsulfonium, Butoxyphenyl) phenylsulfonium, bis (3-tert-butoxyphenyl) phenylsulfonium, tris (4-tert-butoxyphenyl) (3,4-ditert-butoxyphenyl) phenylsulfonium, tris (3-tert-butoxyphenyl) (4-tert-butoxycarbonylmethyloxyphenyl) diphenylsulfonium, tris (4-tert-butoxyphenyl) sulfonium, diphenyl Butoxycarbonylmethyloxyphenyl) sulfonium, (4-tert-butoxyphenyl) bis (4-dimethylaminophenyl) sulfonium, tris (4-dimethylaminophenyl) sulfonium, 2-naphthyldiphenylsulfonium, Dimethyl-2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethyl (4-tert-butylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, and the like can be used. 4-tert-butoxyphenyl) phenyliodonium, and (4-methoxyphenyl) phenyliodonium, and other aryl iodonium cation.

Examples of the oxime sulfonate-based acid generators include [2- (propylsulfonyloxyimino) -2,3-dihydrothiophen-3-ylidene] (o-tolyl) acetonitrile, (Benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile,? - (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, 2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, and? - (ethylsulfonyloxyimino) -1-cyclopentenyl acetonitrile.

In addition to the above, a compound represented by the following general formula (B1-3) may be mentioned.

[Chemical Formula 6]

In the general formula (B1-3), R ^b5 R ^b6 represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic compound 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 phenyl group and naphthyl group, and heterocyclic groups such as furyl group and thienyl group. They may have one or more suitable substituents on the ring, for example, a halogen atom, an alkyl group, an alkoxy group, a nitro group and the like. R ^b6 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. Also, r is preferably an integer of 1 to 3, more preferably 1 or 2.

The photo acid generating agent represented by the above formula (B1-3) is, when r = 1 il, R ^b5 Is a phenyl group, a methylphenyl group or a methoxyphenyl group, and R ^b6 is a methyl group. More specifically, examples of the photo acid generator represented by the general formula (B1-3) include α- (methylsulfonyloxyimino) -1-phenylacetonitrile, α- (methylsulfonyloxyimino) -1- p-methylphenyl) acetonitrile and? - (methylsulfonyloxyimino) -1- (p-methoxyphenyl) acetonitrile.

Examples of the photo acid generator represented by the general formula (B1-3) include photo acid generators represented by the following formulas (B1-3-1) to (B1-3-8) when r = 2.

(7)

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- (Trichloromethyl) -6- [2- (5-ethyl-2-furyl) ethenyl] -s-triazine, 2,4-bis -Tetrahydro] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5- dimethoxyphenyl) ethenyl] (Trichloromethyl) -6- [2- (3,5-diethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (3-methoxy-5-ethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- -triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5-propoxyphenyl) ethenyl] L-methylethyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl] - (trichloromethyl) -6- (3,4-methylenedioxyphenyl) -s-triazine, 2,4-bis-trichloromethyl-6- 4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- Trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis- 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4 (Trichloromethyl) -1,3,5-triazine, 2- [2- (2-furyl) ethenyl] -4,6-bis (trichloromethyl) Triazine, 2- 2- (5-methyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) - dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4- dimethoxyphenyl) ethenyl] Bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-methylenedioxyphenyl) -4,6- (Trichloromethyl) -1,3,5-triazine, tris (1,3-dibromopropyl) -1,3,5-triazine, tris (2,3-dibromopropyl) -1 , Halogen-containing triazine compounds such as 3,5-triazine, and halogen-containing triazine compounds represented by the following general formula (B1-4) such as tris (2,3-dibromopropyl) .

[Chemical Formula 8]

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.

Examples of other photoacid generators include bis (p-toluenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1- (1,1- Bis (1-methylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2-ethylsulfonyl) diazomethane, bis , 4-dimethylphenylsulfonyl) diazomethane, bis (4-ethylphenylsulfonyl) diazomethane, bis (3-methylphenylsulfonyl) diazomethane, bis , Bis (4-fluorophenylsulfonyl) diazomethane such as bis (4-fluorophenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane, bis Ryu; Methyl-2- (p-toluenesulfonyl) propiophenone, 2- (cyclohexylcarbonyl) -2- (p- toluenesulfonyl) propane, 2- Methylthio) propiophenone, and 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one; 1-cyclohexylcarbonyldiazomethane, 1-diazo-1-methylsulfonyl-4-phenyl-2-butanone, 1-cyclohexylsulfonyl-1-cyclohexylcarbamyl Diazo-1-cyclohexylsulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1- (1,1-dimethylethylsulfonyl) Dimethyl-2-butanone, 1-acetyl-1- (1-methylethylsulfonyl) diazomethane, 1-diazo-1- (p- toluenesulfonyl) -3,3- , 1-diazo-1-benzenesulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1- (p- toluenesulfonyl) 2-diazo-2-benzenesulfonylacetic acid isopropyl, 2-diazo-2-methanesulfonyl acetoacetate, Sulfonylcarbonyldiazomethanes such as cyclohexyl 2-benzenesulfonylacetate and -tert-butyl 2-diazo-2- (p-toluenesulfonyl) acetic acid; nitrobenzyl derivatives of p-toluenesulfonic acid-2-nitrobenzyl, p-toluenesulfonic acid-2,6-dinitrobenzyl, p-trifluoromethylbenzenesulfonic acid-2,4-dinitrobenzyl and the like; Methanesulfonic acid esters of pyrogallol, benzenesulfonic acid esters of pyrogallol, p-toluenesulfonic acid esters of pyrogallol, p-methoxybenzenesulfonic acid esters of pyrogallol, mesylenesulfonic acid esters of pyrogallol, benzylsulfonic acid esters of pyrogallol, Methanesulfonic acid ester of alkyl, methanesulfonic acid ester of alkylsulfate, p-toluenesulfonic acid ester of alkylsulfuric acid, p-methoxybenzenesulfonic acid ester of alkyl (having alkyl group of 1 to 15 carbon atoms) ester, , Benzylsulfonic acid esters of alkyl allyl, and esters of aliphatic or aromatic sulfonic acids.

These photo acid 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, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the alkali-soluble resin (A1). Within this range, the curability of the negative-working photosensitive resin composition is improved.

(Radical polymerization initiator (B2))

As the radical polymerization initiator (B2), conventionally known compounds may be used without particular limitation.

Specific examples thereof include thioxanthone derivatives such as 2,4-diethylthioxanthone, isopropylthioxanthone, 2-chlorothioxanthone, and 2,4-dimethylthioxanthone; Benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy- Phenanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) -1 or the like; Diethylanthraquinone, 2,3-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-di 2-methyl anthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl 1,4-naphthoquinone, 2,3-dimethyl anthraquinone Quinones; Benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; Benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin; Benzyl derivatives such as benzyl dimethyl ketal; 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o- (O-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- , 2,4,5-triarylimidazole dimer such as 5-diphenylimidazole dimer and 2,4,5-triarylimidazole dimer; Acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9'-acridinyl) heptane; Oxime esters such as ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime); N-phenylglycine; Coumarin-based compounds, and the like.

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, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the alkali-soluble resin (A2). Within this range, the curability of the negative-working photosensitive resin composition is improved.

≪ Compound (C) capable of crosslinking by an acid or a radical &

The compound capable of being crosslinked by an acid or a radical is not particularly limited as long as it is crosslinkable with another compound or an acid or radical generated from the above component (B) or between the compounds. Specifically, the crosslinking agent (C1) is used in the case of a chemically amplified type, and the polymerizable monomer (C2) is used in the case of a 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 photo acid 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. Examples of the compound include an alkyl etherified product of a part or all of active methylol groups such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Nitrogen compounds. Examples of the alkyl group include a methyl group, an ethyl group, a butyl group, and mixtures thereof, and may contain an oligomer component that is partially self-condensed. Specific examples thereof include hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril and the like.

These crosslinking agents may be used alone or in combination of two or more.

The content of the crosslinking agent (C1) is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, per 100 parts by mass of the alkali-soluble resin (A1). Within this range, the curability and patterning characteristics of the negative-working photosensitive resin composition are improved.

(Polymerizable monomer (C2))

The polymerizable monomer (C2) cross-links with each other due to the action of the radicals generated from the radical polymerization initiator (B2) to polymerize.

Such polymerizable monomers include monofunctional monomers and polyfunctional monomers.

Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, (Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl 2-phenoxy-2-hydroxypropyl (meth) (Meth) acrylate, glycidyl (meth) acrylate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (Meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate and half . These monofunctional monomers may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di Acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylol (meth) acrylate, (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, Pentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxy diethoxyphenyl) (Meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, 2-hydroxypropyl Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) (Meth) acrylate (i.e., tolylene diisocyanate), a reaction product of trimethylhexamethylene diisocyanate and hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylene bis (meth) acrylamide, It can be given a mid-methylene ether, polyhydric alcohol and N- methylol (meth) such as the condensation product of a polyfunctional acrylamide monomer, or triacrylate formal and the like. These multifunctional 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, more preferably 30 to 80 parts by mass, per 100 parts by mass of the alkali-soluble resin (A2). Within this range, the curability and patterning characteristics of the negative-working photosensitive resin composition are improved.

≪ Epoxy resin of 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 the negative-type photosensitive resin composition, a photosensitive resin layer having excellent developability, resolution, and adhesion after patterning can be formed by using a negative-working photosensitive resin composition.

[Chemical Formula 9]

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 alkylene group having 2 to 15 carbon atoms, such as an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propylenoxy) . n is a natural number and its average is 1.2 to 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.

[Chemical formula 10]

(11)

The content of the component (D) is preferably 1 to 40 parts by mass, more preferably 5 to 35 parts by mass, per 100 parts by mass of the component (A). Within this range, a photosensitive resin layer having excellent developability, resolution, and adhesion after patterning can be formed by using a negative-working photosensitive resin composition.

≪ Solvent (S) >

As the solvent (S), those known as solvents for the conventional negative-type photosensitive resin composition can be used without particular limitation.

Specific examples thereof include 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; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether and propylene glycol dibutyl ether; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate; Cellosolve such as ethyl cellosolve and butyl cellosolve; Carbitols such as butyl carbitol; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate; Aliphatic carboxylic acid esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate and isobutyl propionate Ryu; Other esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate and ethyl pyruvate; Aromatic hydrocarbons such as toluene and xylene; 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; and lactones such as? -butyrolactone.

These solvents may be used alone, or two or more solvents may be used in combination.

The content of the component (S) is not particularly limited, but is generally preferably such that the solid concentration of the negative-working photosensitive resin composition is 10 to 60 mass%, more preferably 20 to 50 mass%.

≪ Other components >

The negative-working photosensitive resin composition according to the present invention may contain an additive resin, a stabilizer, a colorant, a surfactant, etc., 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 composed of the negative photosensitive resin composition related to the present invention.

As the base film, it is preferable that it has light transmittance. Specifically, a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyethylene (PE) film and the like can be mentioned. A polyethylene terephthalate (PET) film is preferable because of excellent balance between light transmittance and breaking strength Do.

When a photosensitive resin layer is formed on a base film, a dry film thickness of 5 to 100 mu m is formed on the base film by using an applicator, a bar coater, a wire bar coater, a roll coater, a curtain flow coater, The negative photosensitive resin composition is applied 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 formed between the support substrate and the transparent substrate, wherein the spacer is a negative photosensitive And is a cured product of the resin composition.

A schematic sectional view of the light receiving device is shown in Fig. 1, the light receiving device 1 includes a light receiving portion 11 formed of a semiconductor element mounted on a support substrate 10 and a support substrate 10, a transparent substrate (not shown) facing the support substrate 10 12, and a spacer 13 formed between the support substrate 10 and the transparent substrate 12.

This light receiving device 1 can be manufactured, for example, as follows.

First, a photosensitive dry film is pasted on the support substrate 10 so that the light receiving portion 11 and the photosensitive resin layer are in contact with each other. Subsequently, a portion of the photosensitive resin layer which becomes a spacer is irradiated with active rays such as ultraviolet rays, and the photosensitive resin layer is heated at 40 to 200 DEG C as necessary. Then, the base film of the photosensitive dry film is peeled off, and the uncured portions are dissolved and removed by a developer such as tetramethylammonium hydroxide (TMAH) aqueous solution to form the spacer 13. Thereafter, the transparent substrate 12 is placed on the spacer 13 and heat-pressed, whereby the light receiving device 1 can be obtained. The conditions of hot pressing are, for example, 100 to 200 DEG C and 0.05 to 100 MPa.

In the above example, the photosensitive resin layer is formed on the light receiving portion 11 by attaching the photosensitive dry film, but the present invention is not limited thereto. For example, a photosensitive resin layer may be formed on the light-receiving portion 11 by applying the negative-type photosensitive resin composition on the light-receiving portion 11 and drying the negative-type photosensitive resin composition. As the application method, spin coating is preferable because the film thickness uniformity is enhanced. As the uniformity of the film thickness is increased, the adhesion surfaces of the spacers 13 and the transparent substrate 12 after the patterning become uniform, and the adhesiveness is improved.

Example

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

≪ Examples 1 to 11 and Comparative Examples 1 to 4 >

The negative-working photosensitive resin composition of Examples 1 to 7 and Comparative Examples 1 and 2 was prepared by mixing an alkali-soluble resin, a photo acid generator, a crosslinking agent, an epoxy resin and a solvent according to the prescription (unit: parts by mass) Was prepared.

In addition, the alkali-soluble resin, the radical polymerization initiator, the polymerizable monomer, the epoxy resin and the solvent were mixed in accordance with the prescription (unit: parts by mass) described in Table 2 to obtain a negative electrode of Examples 8 to 11 and Comparative Examples 3 and 4 To prepare a photosensitive resin composition.

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 (mass average molecular weight: 2500) of hydroxystyrene / styrene = 80/20 (molar ratio)

Alkali-soluble resin C: Cresol novolak resin obtained by mixing m-cresol and p-cresol by m-cresol / p-cresol = 60/40 (mass ratio) Average molecular weight 20000)

Alkali soluble resin D: 2-methoxyethyl acrylate / n-butyl acrylate / dicyclopentyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate = 4/4/65/20/7 ) (Mass average molecular weight: 20000)

Alkali soluble resin E: 2-methoxyethyl acrylate / n-butyl acrylate / dicyclopentanyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate / N-vinylpyrrolidone = 66/16/9/1 (molar ratio) copolymer (mass average molecular weight 20000)

Photoacid generator A: IRGACURE PAG103 manufactured by Ciba Specialty Chemicals, Inc.) (2- (propylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] (o-

Photo acid generator B: diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotris pentafluoroethylphosphite (acid-CPO-210S,

Photo acid generator C: 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate (Adeka Optoma SP-

Photoacid generator D: α, α-bis (butylsulfonyloxyimino) -m-phenylenediazatnitrile (compound represented by the above formula (B1-3-3), Japanese Patent Application Laid-Open No. 9-208554 ≪ / RTI >

Photo acid generator E:? - (methylsulfonyloxyimino) -1- (p-methoxyphenyl) acetonitrile (synthesized based on the description of JP-A No. 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 (Mw-100LM manufactured by Sanwa Chemical Co., Ltd.)

Crosslinking agent B: 1,3,4,6-tetrakis (methoxymethyl) glycoluril (Mw-270, manufactured by Sanwa Chemical Co., Ltd.)

Polymerizable monomer A: dipentaerythritol tetraacrylate (DPHA)

Polymerizable monomer B: Trimethylolpropane tri (meth) acrylate (Aronix M309, Toagosei Co., Ltd.)

Polymerizable monomer C: Polyethylene glycol diacrylate (Aronix M240, manufactured by TOA Corporation)

Epoxy resin A: Resin (EXA4850-150, manufactured by DIC Corporation) having n = 1.6 (average value) in the above formula (D-1-1)

Epoxy resin B: Resin (EXA4850-1000, manufactured by DIC Corporation) having n = 1.2 (average value) in the above formula (D-1-1)

Epoxy resin C: bifunctional bisphenol A type epoxy resin (jER828, manufactured by Japan Epoxy Resin Co., Ltd.)

Solvent A: Propylene glycol monomethyl ether acetate

≪ Evaluation of Developability &

The negative photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 4 were applied on an 8-inch silicon wafer by a spin coater and dried at 120 占 폚 for 5 minutes to obtain a photosensitive resin layer having a thickness of 50 占 퐉. Subsequently, this photosensitive resin layer was irradiated with ghi rays at a dose of 250 mJ / cm 2 through a mask. Subsequently, after heating on a hot plate at 115 ° C for 5 minutes, the uncured portions were dissolved and removed by paddle development (60 seconds × 2) using a 2.38 mass% tetramethylammonium hydroxide aqueous solution to form a space with a line width of 40 μm A line and space pattern including a pattern was formed. Then, the developing property of the photosensitive resin layer was evaluated by & cir & that no residue was present in the space portion and & cir & 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 applied on an 8-inch silicon wafer by a spin coater and dried at 120 占 폚 for 5 minutes to obtain a photosensitive resin layer having a thickness of 50 占 퐉. Subsequently, the photosensitive resin layer was irradiated with ghi rays at an irradiation dose of 250 mJ / cm 2, and heated on a hot plate at 115 ° C for 5 minutes. Subsequently, a glass substrate having a thickness of 0.7 mm was heat-pressed on the photosensitive resin layer after heating under the conditions of 100 DEG C and 0.1 MPa. The adhesiveness of the photosensitive resin layer was evaluated by & cir & & cir & 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 applied on an 8-inch silicon wafer by a spin coater and dried at 120 占 폚 for 5 minutes to obtain a photosensitive resin layer having a thickness of 50 占 퐉. Subsequently, this photosensitive resin layer was irradiated with ghi rays at a dose of 250 mJ / cm 2 through a mask. Subsequently, after heating on a hot plate at 115 ° C for 5 minutes, the uncured portions were dissolved and removed by paddle development (60 seconds × 2) using a 2.38 mass% tetramethylammonium hydroxide aqueous solution to obtain a line and space pattern . Then, the mask resolution was changed to obtain the critical resolution. The results are shown in Tables 1 and 2.

≪ Evaluation of residual film ratio &

The negative photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 4 were applied on an 8-inch silicon wafer by a spin coater and dried at 120 占 폚 for 5 minutes to obtain a photosensitive resin layer having a thickness of 50 占 퐉. Subsequently, the photosensitive resin layer was irradiated with ghi rays at an irradiation dose of 250 mJ / cm 2, and heated on a hot plate at 115 ° C for 5 minutes. Further, it was heated at 180 DEG C for 2 hours using a clean oven. Then, the ratio (%) of the film thickness after heating to the original film thickness was determined to evaluate the remaining film ratio. The results are shown in Tables 1 and 2.

As can be seen from Table 1, in the case of the chemically amplified negative photosensitive resin composition, in Examples 1 to 7 using the negative-type photosensitive resin composition containing the epoxy resin represented by the general formula (D-1) The developability, the resolution, the adhesion after patterning, and the residual film ratio were all excellent. On the other hand, in Comparative Example 1 in which a negative photosensitive resin composition containing an epoxy resin different from the epoxy resin represented by the general formula (D-1) was used, the negative photosensitive resin composition containing no epoxy resin, In Comparative Example 2 used, the adhesion was poor.

In the " Evaluation of Developability ", 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 part that appears white 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.

Such a difference in developability is attributed to the fact that the conventional epoxy resin used in Comparative Example 1 easily reacts with the crosslinking agent upon heating of the photosensitive resin layer to remain as residues, It is presumed that the epoxy resin represented by the formula (D-1) is poor in reactivity with the cross-linking agent and does not remain as residue.

As can be seen from Table 2, in Examples 8 to 11 using a negative-type photosensitive resin composition containing an epoxy resin represented by the general formula (D-1) in the case of a negative-type photosensitive resin composition as a radical polymerization type, The developability of the resin layer, the resolution, the adhesion after patterning, and the residual film ratio were all excellent. On the other hand, in Comparative Examples 3 and 4 in which a negative photosensitive resin composition containing an epoxy resin different from the epoxy resin represented by the general formula (D-1) was used, developability and resolution were poor.

The reason for the difference in developability among them is that the conventional epoxy resin used in Comparative Examples 3 and 4 easily reacts with the carboxyl group of the alkali-soluble resin upon heating of the photosensitive resin layer to remain as residues, It is presumed that the epoxy resin represented by the above general formula (D-1) used in ~ 11 is poor in reactivity with a carboxyl group and does not remain as a residue.

1: Light receiving device
10: Support substrate
11:
12: transparent substrate
13: Spacer

Claims (5)

(D) represented by the following general formula (D-1), and a solvent (S), wherein the resin (A1), the photoacid generator (B1), the crosslinking agent A negative-working photosensitive resin composition containing no bisphenol-type epoxy resin.
[Chemical Formula 1]

In the 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 alkylene group having 2 to 15 carbon atoms, such as an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propylenoxy) . n is a natural number, the average being 1.2 to 5] The method according to claim 1,
Wherein the content of the component (D) is 5 to 40 parts by mass relative to 100 parts by mass of the component (A1). A photosensitive dry film comprising a base film and a photosensitive resin layer formed on a surface of the base film, wherein the photosensitive resin layer comprises the negative-type photosensitive resin composition according to claim 1 or 2. [ 1. A semiconductor device comprising: a support substrate on which a semiconductor element is mounted;
A transparent substrate facing the support substrate,
And a spacer formed between the support substrate and the transparent substrate,
Wherein the spacer is a cured product of the negative-working photosensitive resin composition according to any one of claims 1 to 3. [ delete

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