KR20110116988A - 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
Light receiving which comprises the negative photosensitive resin composition which can form the photosensitive resin layer excellent in developability, resolution, and the adhesiveness after patterning, the photosensitive dry film which has the photosensitive resin layer which consists of this composition, and the composition hardened | cured Provide a device.
Resolution
The negative photosensitive resin composition of this invention suitable for forming the spacer 13 of the light receiving device 1 is an alkali-soluble resin (A), the compound (B) which generate | occur | produces an acid or a radical by irradiation of an active line, an acid Or the compound (C) which can be bridge | crosslinked by a radical, the epoxy resin (D) represented by general formula (D-1), and a solvent (S) are contained.

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

Description

Negative photosensitive resin composition, photosensitive dry film and light receiving device {NEGATIVE PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE DRY FILM, AND LIGHT RECEIVING DEVICE}

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

In recent years, after bonding to a semiconductor wafer etc. and forming a pattern by exposure and development, the photosensitive dry film which can be crimped | bonded with transparent substrates, such as glass, is calculated | required (refer patent document 1, 2). When such a photosensitive dry film is used, the photosensitive dry film after patterning will have a spacer effect between a semiconductor wafer and a transparent substrate.

As a photosensitive resin layer of such a photosensitive dry film, what can be patterned by the photolithographic method and what can maintain shape as a spacer is calculated | required. Moreover, in order to crimp | bond with a transparent substrate after exposure and image development, it is also required to be excellent in developability and resolution, and the adhesiveness after patterning.

Japanese Unexamined Patent Publication No. 2006-323089 Japanese Unexamined Patent Publication No. 2008-297540

However, it was the present conditions that the photosensitive resin composition which can form the photosensitive resin layer which is excellent in all developability, resolution, and the adhesiveness after patterning so far is not proposed.

This invention is made | formed in view of such a conventional situation, The photosensitive water composition which consists of a negative photosensitive resin composition which can form the photosensitive resin layer excellent in developability, resolution, and the adhesiveness after patterning, and its negative photosensitive resin composition An object of the present invention is to provide a light-sensitive device having a photosensitive dry film having a ground layer and a spacer of which the negative photosensitive resin composition is cured.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly researched in order to solve the said subject. As a result, according to the negative photosensitive resin composition containing the epoxy resin of a specific structure, it discovered that the said subject could be solved and came to complete this invention. Specifically, the present invention provides the following.

1st aspect of this invention is alkali-soluble resin (A), the compound (B) which generate | occur | produces an acid or a radical by irradiation of an active line, and the compound (C) which can be bridge | crosslinked by the acid or radical which generate | occur | produces from said (B) component And a negative photosensitive resin composition containing the epoxy resin (D) represented by the following general formula (D-1) and a solvent (S).

[Formula 1]

[In formula (D-1), R <^d1> and R <^d2>. Each independently represents a hydrogen atom or a methyl group, and R ^d3 R ^d6 Each independently represents a hydrogen atom, a methyl group, a chlorine atom or a bromine atom. A is an ethyleneoxyethyl group, di (ethyleneoxy) ethyl group, tri (ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) propyl group, tri (propyleneoxy) propyl group, or an alkylene group having 2 to 15 carbon atoms Indicates. n is a natural number and its average is 1.2 to 5]

The 2nd aspect of this invention is a photosensitive dry film which has a base film and the photosensitive resin layer formed in the surface of this base film, and the said photosensitive resin layer consists of the negative photosensitive resin composition which concerns on this invention.

According to a third aspect of the present invention, there is provided 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 according to the present invention. It is a light receiving device which is a hardened | cured material of a type photosensitive resin composition.

According to this invention, the photosensitive dry film which has a negative photosensitive resin composition which can form the photosensitive resin layer excellent in developability, resolution, and the adhesiveness after patterning, the photosensitive resin layer which consists of this negative photosensitive resin composition, and its The light-receiving device provided with the spacer which the negative photosensitive resin composition hardened | cured can be provided.

1 is a diagram illustrating a schematic cross-sectional view of a light receiving device.
FIG. 2 is a diagram illustrating a line and space pattern obtained in Example 1. FIG.
3 is a diagram illustrating a line-and-space pattern obtained in Comparative Example 1. FIG.

≪Negative photosensitive resin composition≫

The negative photosensitive resin composition which concerns on this invention is alkali-soluble resin (A), the compound (B) which generate | occur | produces an acid or a radical by irradiation of an active line, and the compound which can be bridge | crosslinked by the acid or radical which generate | occur | produces from the said (B) component (C), an epoxy resin (D) and a solvent (S) of a specific structure are contained.

This negative photosensitive resin composition may be a chemically amplified type and a radical polymerization type, and in each case, the kind of said (A)-(C) component differs.

Hereinafter, each component contained in the negative photosensitive resin composition which concerns on this invention is demonstrated in detail.

<Alkali-soluble resin (A)>

As alkali-soluble resin, what is conventionally used for the negative type photosensitive resin composition of chemically amplified type or radical polymerization type can be used, without restrict | limiting. Specifically, in the case of the 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 structural unit derived from an unsaturated carboxylic acid can be used. .

(Alkali-soluble resin (A1) which has a phenolic hydroxyl group)

Although it does not specifically limit as alkali-soluble resin (A1), Polyhydroxy styrene resin, a novolak resin, a phenol- xylene glycol condensation resin, a cresol- xylylene glycol condensation resin, a phenol- dicyclopentadiene condensation resin, etc. are mentioned. Can be mentioned. Among these, polyhydroxy styrene resin and novolak resin are preferable, and polyhydroxy styrene resin is more preferable.

The polyhydroxy styrene resin has at least a structural unit derived from hydroxy styrene.

Herein, "hydroxy styrene" means a hydroxy styrene and a hydroxy styrene derivative (monomer) substituted with another substituent such as a halogen atom, an alkyl group, a halogenated alkyl group, and a hydrogen atom bonded to the α position of the hydroxy styrene. Let the concept including the.

The "hydroxy styrene derivative" has at least the benzene ring and the hydroxyl group couple | bonded with this, For example, the hydrogen atom couple | bonded with the (alpha) position of hydroxy styrene is a halogen atom, a C1-C5 alkyl group, a halogenated alkyl group, etc. Which is substituted with another substituent of, and the C1-5 alkyl group couple | bonded with the benzene ring which the hydroxyl group of hydroxystyrene couple | bonded, or what 1-2 hydroxyl groups couple | bonded with the benzene ring which this hydroxyl group couple | bonded further (At this time, the total number of hydroxyl groups is 2-3.) Etc. shall be included.

As a halogen atom, a chlorine atom, a fluorine atom, a bromine atom, etc. are mentioned, A fluorine atom is preferable.

In addition, "the alpha-position of hydroxy styrene" means the carbon atom which the benzene ring couple | bonds unless there is particular notice.

The structural unit guide | induced from this hydroxy styrene is represented by following General formula (A1-1), for example.

[Formula 2]

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

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

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable.

As a halogenated alkyl group, one part or all part of the hydrogen atom of the C1-C5 alkyl group mentioned above is substituted by the halogen atom. Among these, it is preferable that all of the hydrogen atoms were substituted with the fluorine atom. Moreover, a linear or branched fluorinated alkyl group is preferable, trifluoromethyl group, hexafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, etc. are more preferable, and a trifluoromethyl group (-CF ₃ ) is most preferred.

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

As a C1-C5 alkyl group of R <^a2>, the same thing as the case of R <^a1> is mentioned.

q is an integer of 0-2. It is preferable that it is 0 or 1 among these, and it is preferable that it is 0 especially industrially.

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

p is an integer of 1-3, Preferably it is 1.

The substitution position of the hydroxyl group may be any of the o-position, the m-position, and the p-position when p is 1, but the p-position is preferable because it is easily available and inexpensive. In addition, when p is 2 or 3, arbitrary substitution positions can be combined.

The structural unit represented by the said general formula (A1-1) may be used independently, and may be used in combination of 2 or more type.

It is preferable that the ratio of the structural unit guide | induced from hydroxy styrene in the said polyhydroxy styrene resin is 60-100 mol% with respect to all the structural units which comprise polyhydroxy styrene resin, and 70-100 mol% It is more preferable that it is, and it is further more preferable that it is 80-100 mol%. If it is in the range, when it is set as negative photosensitive resin composition, moderate alkali solubility can be obtained.

It is preferable that the said polyhydroxy styrene resin further has a structural unit derived from styrene.

As used herein, the term "structural unit derived from styrene" includes a structural unit obtained by cleaving ethylenic double bonds of styrene and styrene derivatives (excluding hydroxystyrene).

The "styrene derivative" has a hydrogen atom bonded to the α position of styrene substituted with another substituent such as a halogen atom, an alkyl group or a halogenated alkyl group, and the hydrogen atom of the phenyl group of styrene is substituted with a substituent such as an alkyl group having 1 to 5 carbon atoms. It shall include what has been done.

As a halogen atom, a chlorine atom, a fluorine atom, a bromine atom, etc. are mentioned, A fluorine atom is preferable.

In addition, "the α-position of styrene" means the carbon atom which the benzene ring couple | bonds unless there is particular notice.

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

(3)

R ^a1 and R ^a2 roneun, R ^a1 and R ^a2 in the formula (A1-1) And the same thing as each.

q is an integer of 0-2. It is preferable that it is 0 or 1 among these, and it is preferable that it is 0 especially industrially.

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

The structural unit represented by the said general formula (A2-1) may be used independently, and may be used in combination of 2 or more type.

It is preferable that it is 40 mol% or less with respect to all the structural units which comprise polyhydroxy styrene resin, and, as for the ratio of the structural unit guide | induced from styrene in the said polyhydroxy styrene resin, it is more preferable that it is 30 mol% or less, It is more preferable that it is 20 mol% or less. When it is in the range, when it is set as a negative photosensitive resin composition, moderate alkali solubility can be obtained and the balance with another structural unit is also favorable.

Moreover, the said polyhydroxy styrene resin may have structural units other than the structural unit derived from hydroxy styrene, and the structural unit derived from styrene. More preferably, the polyhydroxystyrene resin is a polymer composed of only structural units derived from hydroxystyrene, or a copolymer composed of structural units derived from hydroxystyrene and structural units derived from styrene.

Although the mass mean molecular weight (polystyrene conversion basis by gel permeation chromatography. Hereinafter, it is the same in this specification) of the said polyhydroxy styrene resin is not specifically limited, 1500-40000 are preferable and 2000-8000 are more desirable.

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

As said phenols, Cresol, such as a phenol, o-cresol, m-cresol, p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol Elenols; o-ethylphenol, m-ethylphenol, p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, p- alkyl phenols such as tert-butylphenol; Trialkyl phenols such as 2,3,5-trimethyl phenol and 3,4,5-trimethyl phenol; Polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phloroglycinol; Alkyl polyhydric phenols such as alkyl resorcin, alkyl catechol and alkyl hydroquinone (all alkyl groups have 1 to 4 carbon atoms); α-naphthol, β-naphthol, hydroxydiphenyl, bisphenol A and the like. These phenols may be used independently and may be used in combination of 2 or more type.

Among these phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol together. In this case, various characteristics, such as a sensitivity, can be adjusted by adjusting the compounding ratio of both.

Examples of the aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde and the like. These aldehydes may be used independently and may be used in combination of 2 or more type.

As said acid catalyst, Inorganic acids, such as hydrochloric acid, a sulfuric acid, nitric acid, phosphoric acid, a phosphoric acid; Organic acids such as formic acid, oxalic acid, acetic acid, diethyl sulfuric acid and paratoluenesulfonic acid; Metal salts such as zinc acetate; and the like. These acid catalysts may be used independently or may be used in combination of 2 or more type.

As a novolak resin obtained in this way, a phenol / formaldehyde condensation novolak resin, a cresol / formaldehyde condensation novolak resin, a phenol- naphthol / formaldehyde condensation novolak resin, etc. are mentioned specifically ,.

Although the mass mean 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))

Alkali-soluble resin (A2) has at least a structural unit guide | induced from unsaturated carboxylic acid.

As unsaturated carboxylic acid, Monocarboxylic acids, such as (meth) acrylic acid and a crotonic acid; And 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 independently and may be used in combination of 2 or more type.

In addition, in this specification, "(meth) acrylic acid" shows both methacrylic acid and acrylic acid. The same applies to "(meth) acrylate" and "(meth) acrylamide" described later.

It is preferable that the ratio of the structural unit guide | induced from unsaturated carboxylic acid in the said alkali-soluble resin (A2) is 2-30 mol% with respect to all the structural units which comprise alkali-soluble resin (A2), and it is 5-20 mol It is more preferable that it is%. If it is in the range, when it is set as negative photosensitive resin composition, moderate alkali solubility can be obtained.

It is preferable that the said alkali-soluble resin (A2) further has a structural unit guide | induced from other polymerizable monomers other than the said unsaturated carboxylic acid.

As such a polymerizable monomer, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, amyl (meth) acrylate, cyclohexyl (meth) Acrylate, dicyclopentanyl (meth) acrylate, 2-methyl cyclohexyl (meth) acrylate, isoboroyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydride Hydroxyethyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, (Meth) acrylic acid esters 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-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-di Phenyl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide, N-2-acetamide ethyl-N-acetyl (meth) acryl (Meth) acrylamides such as amides; Vinyl ethers such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxy ethyl vinyl ether, ethoxy ethyl vinyl ether, hydroxyethyl vinyl ether, benzyl vinyl ether, vinyl phenyl ether and vinyl tolyl ether Ryu; Vinyl esters such as vinyl butyrate, vinyl isobutylate, vinyl trimethyl acetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate and vinyl naphthoate; Other vinyl compounds, such as styrene and N-vinylpyrrolidone, etc. are mentioned. These polymerizable monomers may be used independently and may be used in combination of 2 or more type.

It is preferable that the ratio of the structural unit guide | induced from said polymerizable monomer in the said alkali-soluble resin (A2) is 70-98 mol% with respect to all the structural units which comprise alkali-soluble resin (A2), and is 80-95 It is more preferable that it is mol%. When it is in the range, when it is set as a negative photosensitive resin composition, moderate alkali solubility can be obtained and the balance with another structural unit is also favorable.

<Compound (B) which Generates Acid or Alkali by Irradiation of Active Line>

The compound which generates an acid or an alkali by irradiation of active rays is particularly limited as long as it generates an acid or a radical by irradiation of active rays such as ultraviolet rays, far ultraviolet rays, KrF, ArF, excimer laser light, X-ray, electron beam, etc. Can be used without. Specifically, in the case of the chemically amplified type, a compound which generates an acid by irradiation of active rays (hereinafter referred to as a "photoacid generator") (B1) is used. In the case of a radical polymerization type, a radical polymerization initiator (B2) is used. .

(Photoacid Generator (B1))

As a photoacid generator (B1), a conventionally well-known compound can be used without a restriction | limiting in particular. For example, onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, halogen-containing triazine compounds, diazomethane acid generators, nitrobenzylsulfonate acid generators (nitro Benzyl derivatives), iminosulfonate acid generators, disulfone acid generators, and the like.

Among these, a sulfonium salt type acid generator, an oxime sulfonate type acid generator, and a halogen containing triazine compound are preferable at the point which is excellent in the effect of this invention. Particularly, since the crosslinkability with the crosslinking agent (C1) described later is good and the reactivity with the epoxy resin (D) having a specific structure is dull and can impart higher adhesion after patterning, an oxime sulfonate-based acid generator and Halogen-containing triazine compounds are preferred.

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

[Formula 4]

In General Formula (B1-1), R ^b1 and R ^b2. Each independently represents a hydrogen atom, a halogen atom, an oxygen atom or a hydrocarbon group which may have a halogen atom, or an alkoxy group which may have a substituent, and R ^b3 Represents a p-phenylene group which may have a halogen atom or an alkyl group, and 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- toluene sulfonate, butane sulfonate nonafluoro flow, adamantane carboxylate, tetra-aryl borates, to fluorinated alkyl represented by the formula (B1-2) Fluorophosphate anion and the like.

[Chemical Formula 5]

In said general formula (B1-2), Rf represents the alkyl group in which 80% or more of a hydrogen atom was substituted by the fluorine atom. m is the number and shows the integer of 1-5. m pieces of Rf may be the same or different, respectively.

As a photoacid generator represented by the said General formula (B1-1), 4- (2-chloro-4- benzoylphenylthio) phenyl diphenyl sulfonium hexafluoro antimonate, 4- (2-chloro-4- Benzoylphenylthio) phenylbis (4-fluorophenyl) sulfoniumhexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfoniumhexafluoroantimo Nate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-methylphenyl) sulfoniumhexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4- ( β-hydroxyethoxy) phenyl) sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4 -(3-methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfoniumhexafluoroantimonate, 4- (2-fluoro4-benzoylphenylthio) phenylbis (4-fluoro Phenyl) sulfonium hexafluoroantimo Nitrate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfoniumhexafluoroantimonate, 4- (2,3,5,6-tetramethyl-4-benzoyl Phenylthio) phenylbis (4-fluorophenyl) sulfoniumhexafluoroantimonate, 4- (2,6-dichloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoro Antimonate, 4- (2,6-dimethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfoniumhexafluoroantimonate, 4- (2,3-dimethyl-4-benzoylphenyl Thio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (3-methyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfoniumhexafluoroantimonate, 4- (2-fluoro4-benzoylphenylthio) phenylbis (4-chlorophenyl Sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoyl Nylthio) phenylbis (4-chlorophenyl) sulfoniumhexafluoroantimonate, 4- (2,3,5,6-tetramethyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium Hexafluoroantimonate, 4- (2,6-dichloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfoniumhexafluoroantimonate, 4- (2,6-dimethyl-4- Benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,3-dimethyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroanti Monate, 4- (2-chloro-4-acetylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenyldiphenylsul Phonohexahexafluoromonate, 4- (2-chloro-4- (4-fluorobenzoyl) phenylthio) phenyldiphenylsulfoniumhexafluoroantimonate, 4- (2-chloro-4- (4 -Methoxybenzoyl) phenylthio) phenyldiphenylsulfonium hexafluor Antimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenylbis (4-fluor Rophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-fluorobenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfoniumhexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl ) Phenylthio) phenylbis (4-fluorophenyl) sulfoniumhexafluoroantimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenylbis (4-fluorophenyl) sulfoniumhexafluoro Roantimonate, 4- (2-chloro-4-acetylphenylthio) phenylbis (4-chlorophenyl) sulfoniumhexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) Phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroan Timonate, 4- (2-chloro-4- (4-fluorobenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfoniumhexafluoroantimonate, 4- (2-chloro-4- (4 -Methoxybenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfoniumhexafluoroantimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenylbis (4-chlorophenyl) sulfonium Hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfoniumtetrafluoro Roborate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium perchlorate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfoniumtrifluoromethanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulphate Phosphorus tetraflu Orborate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium perchlorate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl ) Sulfoniumtrifluoromethanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium p-toluenesulfonate, 4- (2-chloro-4-benzoyl Phenylthio) phenylbis (4-fluorophenyl) sulfonium camphorsulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium nonafluorobutanesulfonate, 4 -(2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfoniumhexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium Tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfoniumperchlorate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl Sulfonium triple Oromethanesulfonate, diphenyl [4- (phenylthio) phenyl] sulfoniumtrifluorotrispentafluoroethylphosphite, diphenyl [4- (p-terphenylthio) phenyl] sulfoniumhexafluoroantimo Nate, diphenyl [4- (p-terphenylthio) phenyl] sulfonium trifluoro trispentafluoro ethyl phosphite, etc. are mentioned.

As another onium salt type acid generator, the cation part of the said General formula (B1-1) is mentioned, for example, triphenylsulfonium, (4-tert- butoxyphenyl) diphenylsulfonium, and bis (4-tert- Butoxyphenyl) 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-thiophenoxyphenyl) 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, trimethyl Sulfonium cations such as sulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, tribenzylsulfonium, diphenyliodonium, bis (4-tert-butylphenyl) iodium, ( The thing substituted by iodonium cation, such as aryl iodonium cation, such as 4-tert- butoxyphenyl) phenyl iodonium and (4-methoxyphenyl) phenyl iodonium, is mentioned.

Examples of the oxime sulfonate acid generator include [2- (propylsulfonyloxyimino) -2,3-dihydrothiophen-3-ylidene] (o-tolyl) acetonitrile and α- (p-toluenesul Ponyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- ( 2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, (alpha)-(ethylsulfonyloxyimino) -1-cyclopentenyl acetonitrile, etc. are mentioned.

Moreover, the compound represented by the following general formula (B1-3) besides the above is mentioned.

[Formula 6]

In formula (B1-3), R ^{b5 Represents a} monovalent, divalent, or trivalent organic group, R ^b6 represents a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic compound group, and r represents an integer of 1 to 6;

As R <^b5>, it is especially preferable that it is an aromatic compound group, As such an aromatic compound group, Heterocyclic groups, such as aromatic hydrocarbon groups, such as a phenyl group and a naphthyl group, and a furyl group, thienyl group, etc. are mentioned. These may have one or more suitable substituents, for example, a halogen atom, an alkyl group, an alkoxy group, a nitro group, etc. on a ring. Moreover, as R <^b6> , a C1-C6 alkyl group is especially preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are mentioned. Moreover, the integer of 1-3 is preferable, and, as for r, 1 or 2 is more preferable.

As a photoacid generator represented by the said General formula (B1-3), when r = 1, it is R ^b5 Is a phenyl group, a methylphenyl group, or a methoxyphenyl group, and the compound whose R <^b6> is a methyl group is mentioned. More specifically, as a photo acid generator represented by the said general formula (B1-3), (alpha)-(methylsulfonyloxyimino) -1-phenylacetonitrile and (alpha)-(methylsulfonyloxyimino) -1- ( p-methylphenyl) acetonitrile and (alpha)-(methylsulfonyloxyimino) -1- (p-methoxyphenyl) acetonitrile are mentioned.

As a photo acid generator represented by said general formula (B1-3), when r = 2, the photo acid generator represented by following formula (B1-3-1)-(B1-3-8) is mentioned.

[Formula 7]

Examples of the halogen-containing triazine compound include 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine and 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-diethoxyphenyl) 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 (trichloro Rhomethyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl]- s-triazine, 2,4-bis (trichloromethyl) -6- (3,4-methylenedioxyphenyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bro Parent-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-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) sty Arylphenyl-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 -Dimethoxyphenyl) 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- Tris (trichloromethyl) -1,3,5-triazine, tris (1,3-dibromopropyl) -1,3,5-triazine, tris (2,3-dibromopropyl) -1 Halogen-containing triazine compounds, such as a 3, 5- triazine, and halogen containing triazine compounds represented by following General formula (B1-4), such as a tris (2, 3- dibromopropyl) isocyanurate, are mentioned. Can be.

[Formula 8]

In said general formula (B1-4), R <^b7> , R <^b8> , and R <^b9> represent a C1-C6 halogenated alkyl group each independently.

In addition, as other photoacid generators, bis (p-toluenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1- (1,1-dimethyl Ethylsulfonyl) 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 Bissulfonyldiazomethanes such as bis (4-fluorophenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane and bis (4-tert-butylphenylsulfonyl) diazomethane Ryu; 2-methyl-2- (p-toluenesulfonyl) propiophenone, 2- (cyclohexylcarbonyl) -2- (p-toluenesulfonyl) propane, 2-methanesulfonyl-2-methyl- (p- Sulfonylcarbonyl alkanes such as methylthio) propiophenone and 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one; 1-p-toluenesulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-methylsulfonyl-4-phenyl-2-butanone, 1-cyclohexylsulfonyl-1-cyclohexylcar Bonyldiazomethane, 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-dia Crude-2- (p-toluenesulfonyl) cyclohexyl, 2-diazo-2-benzenesulfonylacetic acid-tert-butyl, 2-diazo-2-methanesulfonylacetic acid isopropyl, 2-diazo- Sulfonylcarbonyl diazomethanes such as 2-benzenesulfonyl acetate cyclohexyl and 2-diazo-2- (p-toluenesulfonyl) acetic acid-tert-butyl; nitrobenzyl derivatives such as p-toluenesulfonic acid-2-nitrobenzyl, p-toluenesulfonic acid-2,6-dinitrobenzyl and p-trifluoromethylbenzenesulfonic acid-2,4-dinitrobenzyl; Methane sulfonic acid ester of pyrogallol, benzene sulfonic acid ester of pyrogallol, p-toluene sulfonic acid ester of pyrogallol, p-methoxybenzene sulfonic acid ester of pyrogallol, mesitylene sulfonic acid ester of pyrogallol, benzyl sulfonic acid ester of pyrogallol, and gallic acid Alkyl methanesulfonic acid ester, Alkyl galbenzene benzene sulfonic acid ester, Alkyl gallate p-toluene sulfonic acid ester, Alkyl gallate (The alkyl group has 1 to 15 carbon atoms), Mesitylene sulfonic acid ester of alkyl gallate And esters of polyhydroxy compounds such as benzyl sulfonic acid esters of alkyl gallates and aliphatic or aromatic sulfonic acids.

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

It is preferable that it is 0.05-30 mass parts with respect to 100 mass parts of alkali-soluble resin (A1), and, as for content of a photoacid generator (B1), it is more preferable that it is 0.1-10 mass parts. If it is in the range, the curability of a negative photosensitive resin composition will become favorable.

(Radical polymerization initiator (B2))

As a radical polymerization initiator (B2), a conventionally well-known compound can be used without a restriction | limiting in particular.

Specifically, Thioxanthone derivatives, such as 2, 4- diethyl thioxanthone, isopropyl thioxanthone, 2-chloro thioxanthone, and 2, 4- dimethyl thioxanthone; Benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzo Phenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone Aromatic ketones such as -1; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-di Phenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl1,4-naphthoquinone, 2,3-dimethylanthraquinone Quinones, such as these; 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-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4 2,4,5-triaryl imidazole dimers, such as a, 5-diphenyl imidazole dimer and a 2,4,5-triaryl imidazole 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]-, and 1- (O-acetyl oxime); N-phenylglycine; Coumarin-based compounds and the like.

These radical polymerization initiators may be used independently and may be used in combination of 2 or more type.

It is preferable that it is 0.05-30 mass parts with respect to 100 mass parts of alkali-soluble resin (A2), and, as for content of a radical polymerization initiator (B2), it is more preferable that it is 0.5-10 mass parts. If it is in the range, the curability of a negative photosensitive resin composition will become favorable.

<Compound (C) which can be crosslinked by acid or radical>

As a compound which can be bridge | crosslinked with an acid or a radical, if it can bridge | crosslink with another compound or the compounds with the acid or radical which generate | occur | produced from the said (B) component, it can use without particular limitation. Specifically, the crosslinking agent (C1) is used in the case of the chemically amplified type, and the polymerizable monomer (C2) is used in the case of the radical polymerization type.

(Cross-linking system (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).

Although it does not specifically limit as such a crosslinking agent, For example, the compound which has at least 2 alkyl etherified amino group in a molecule | numerator can be used. Examples of the compound include alkyl etherification of some or all of the active methylol groups such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, and (poly) methylolated urea Nitrogen compounds are mentioned. Examples of the alkyl group include a methyl group, an ethyl group, a butyl group, or a mixture of these, and may contain an oligomer component formed by partial self-condensation. Specifically, hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, etc. are mentioned.

These crosslinking agents may be used independently and may be used in combination of 2 or more type.

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. If it is in the range, the hardenability and patterning characteristic of a negative photosensitive resin composition will become favorable.

(Polymerizable monomer (C2))

The polymerizable monomer (C2) is crosslinked with each other by the action of radicals generated from the radical polymerization initiator (B2) to polymerize.

Such a polymerizable monomer includes a monofunctional monomer and a polyfunctional monomer.

As a monofunctional monomer, (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymeth Methoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, Citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylic Latex, 2-phenoxy-2-hydroxypropyl (meth) Acrylate, 2- (meth) acryloyloxy-2-hydroxypropylphthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl ( Meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, half (meth) acrylate of phthalic acid derivatives, and the like. Can be mentioned. These monofunctional monomers may be used independently and may be used in combination of 2 or more type.

In addition, as a polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethyleneglycol di (meth) acrylate, and 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, trimethylol Propane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol pentaacrylate, dipenta Pentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) 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 ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (Meth) acrylate (ie, tolylene diisocyanate), a reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylic 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 polyfunctional monomers may be used independently and may be used in combination of 2 or more type.

It is preferable that it is 10-100 mass parts with respect to 100 mass parts of alkali-soluble resin (A2), and, as for content of a polymerizable monomer (C2), it is more preferable that it is 30-80 mass parts. If it is in the range, the hardenability and patterning characteristic of a negative photosensitive resin composition will become favorable.

<Epoxy resin (D) of specific structure>

The epoxy resin of a specific structure is represented by the following general formula (D-1). By adding such an epoxy resin to a negative photosensitive resin composition, when it is set as a negative photosensitive resin composition, the photosensitive resin layer excellent in developability, resolution, and adhesiveness after patterning can be formed.

[Formula 9]

In said general formula (D-1), R <^d1> and R <^d2> represent a hydrogen atom or a methyl group each independently. 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, di (ethyleneoxy) ethyl group, tri (ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) propyl group, tri (propyleneoxy) propyl group, or an alkylene group having 2 to 15 carbon atoms Indicates. n is a natural number and the average is 1.2-5.

As a specific example of the epoxy resin represented by the said General formula (D-1), resin represented by following formula (D-1-1) (D-1-14) is mentioned.

These compounds may be used independently and may be used in combination of 2 or more type.

[Formula 10]

[Formula 11]

It is preferable that it is 1-40 mass parts with respect to 100 mass parts of (A) component, and, as for content of (D) component, it is more preferable that it is 5-35 mass parts. If it is in the range, when it is set as a negative photosensitive resin composition, the photosensitive resin layer excellent in developability, resolution, and the adhesiveness after patterning can be formed.

<Solvent (S)>

As a solvent (S), what is conventionally known as a solvent of a negative photosensitive resin composition can be used, without restrict | limiting.

Specific examples 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; Cellosolves 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; Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; Lactones, such as (gamma) -butyrolactone, etc. are mentioned.

These solvents may be used independently and may be used in combination of 2 or more type.

Although content of (S) component is not specifically limited, Generally, the quantity which solid content concentration of a negative photosensitive resin composition becomes 10-60 mass% is preferable, and the quantity which becomes 20-50 mass% is more preferable.

&Lt; Other components &gt;

The negative photosensitive resin composition which concerns on this invention may contain additional resin, a stabilizer, a coloring agent, surfactant, etc. as needed.

≪Photosensitive dry film≫

The photosensitive dry film which concerns on this invention has a base film and the photosensitive resin layer formed in the surface of this base film, and this photosensitive resin layer consists of the negative photosensitive resin composition which concerns on this invention.

As a base film, what has a light transmittance is preferable. Specifically, a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyethylene (PE) film, etc. are mentioned, A polyethylene terephthalate (PET) film is preferable at the point which is excellent in the balance of light transmittance and breaking strength. Do.

When forming the photosensitive resin layer on a base film, it uses an applicator, a bar coater, a wire bar coater, a roll coater, a curtain flow coater, etc., and it concerns on this invention so that a dry film thickness may be 5-100 micrometers on a base film. The negative photosensitive resin composition is applied and dried.

The photosensitive dry film which concerns on this invention may have a protective film further on the photosensitive resin layer. As this protective film, a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyethylene (PE) film, etc. are mentioned.

≪Receiving device≫

The 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 member according to the present invention. It is hardened | cured material of a resin composition.

Typical sectional drawing of a light receiving apparatus is shown in FIG. As shown in FIG. 1, the light receiving device 1 includes a light receiving unit 11 made of a support element 10 and a semiconductor element mounted on the support substrate 10, and a transparent substrate 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 as follows, for example.

First, the photosensitive dry film is affixed on the support substrate 10 so that the light receiving part 11 and the photosensitive resin layer may contact. Next, active rays, such as an ultraviolet-ray, are irradiated to the part used as a spacer among the photosensitive resin layers, and a photosensitive resin layer is heated at 40-200 degreeC as needed. Subsequently, the base film of the photosensitive dry film is peeled off, and the spacer 13 is formed by melt | dissolving and removing the unhardened part with developing solutions, such as aqueous tetramethylammonium hydroxide (TMAH) solution. Thereafter, the light receiving device 1 can be obtained by placing the transparent substrate 12 on the spacer 13 and heating and crimping it. The conditions of hot pressing are 100-200 degreeC and 0.05-100 Mpa, for example.

In addition, in the said example, although the photosensitive resin layer was formed on the light receiving part 11 by affixing the photosensitive dry film, it is not limited to this. For example, you may make it form the photosensitive resin layer on the light receiving part 11 by apply | coating said negative photosensitive resin composition on the light receiving part 11, and drying. As a coating method, spin coating is preferable at the point which film uniformity becomes high. As the film thickness uniformity becomes higher, the adhesion surface of each spacer 13 and the transparent substrate 12 becomes even after patterning, and adhesiveness becomes favorable.

Example

Hereinafter, although the Example of this invention is described, the scope of the present invention is not limited to these Examples.

<Examples 1-11, Comparative Examples 1-4>

According to the prescription (unit is a mass part) of Table 1, alkali-soluble resin, a photoacid generator, a crosslinking agent, an epoxy resin, and a solvent are mixed, and the negative photosensitive resin composition of Examples 1-7, Comparative Examples 1 and 2 Was prepared.

Moreover, according to the prescription (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 the negative type of Examples 8-11 and Comparative Examples 3 and 4 are carried out. The photosensitive resin composition was prepared.

The detail of each component in Table 1, 2 is as follows.

Alkali-soluble resin A: Polyhydroxy styrene (mass average molecular weight 2500)

Alkali-soluble resin B: Copolymer of hydroxy styrene / 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), and addition condensation by a conventional method by adding formalin. Average molecular weight 20000)

Alkali-soluble resin D: 2-methoxyethyl acrylate / n-butyl acrylate / dicyclopentanyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate = 4/4/65/20/7 (molar ratio Copolymer of (mass average molecular weight 20000)

Alkali-soluble resin E: 2-methoxyethyl acrylate / n-butyl acrylate / dicyclopentanyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate / N-vinylpyrrolidone = 4/4 / 66/16/9/1 (molar ratio) copolymer (mass average molecular weight 20000)

Photoacid generator A: [2- (propylsulfonyloxyimino) -2,3-dihydrothiophen-3-ylidene] (o-tolyl) acetonitrile (manufactured by Chiba Specialty Chemicals, IRGACURE PAG103)

Photoacid generator B: diphenyl [4- (phenylthio) phenyl] sulfonium trifluoro tris pentafluoroethyl phosphite (manufactured by San-Apro Co., Ltd., CPI-210S)

Photoacid generator C: 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate (manufactured by ADEKA Corporation, Adeka Optoma-SP-172)

Photoacid generator D: α, α-bis (butylsulfonyloxyimino) -m-phenylenediacetonitrile (a compound represented by the above formula (B1-3-3), described in JP-A-9-208554) Synthesized based on

Photoacid generator E: α- (methylsulfonyloxyimino) -1- (p-methoxyphenyl) acetonitrile (synthesized based on the description of JP-A-9-95479)

Radical polymerization initiator A: ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (made by Chiba Specialty Chemicals, Inc.) , CGI242)

Crosslinking agent A: 2,4,6-tris [bis (methoxymethyl) amino] -1,3,5-triazine (Sanwa Chemical Co., Ltd. product, 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 (Toa Synthetic Co., Ltd., aronix M309)

Polymerizable monomer C: Polyethylene glycol diacrylate (manufactured by Toa Synthetic Co., Ltd., Aronix M240)

Epoxy resin A: Resin whose n = 1.6 (average value) in said Formula (D-1-1) (made by DIC Corporation, EXA4850-150)

Epoxy resin B: Resin whose n = 1.2 (average value) in said Formula (D-1-1) (made by DIC Corporation, EXA4850-1000)

Epoxy Resin C: Bifunctional Bisphenol A Type Epoxy Resin (manufactured by Japan Epoxy Resin, Inc., jER828)

Solvent A: Propylene Glycol Monomethyl Ether Acetate

<Evaluation of developability>

The negative photosensitive resin composition of Examples 1-11 and Comparative Examples 1-4 was apply | coated on a 8-inch silicon wafer with a spin coater, it dried at 120 degreeC for 5 minutes, and the photosensitive resin layer of 50 micrometers in thickness was obtained. Subsequently, the ghi line was irradiated at 250 mJ / cm <2> irradiation amount through this mask through the photosensitive resin layer. Subsequently, after heating on a hotplate for 5 minutes at 115 degreeC, the uncured part was melt | dissolved and removed by the paddle phenomenon (60 second x 2) using 2.38 mass% tetramethylammonium hydroxide aqueous solution, and the space of 40 micrometers of line widths is carried out. A line and space pattern including the pattern was formed. And the developability of the photosensitive resin layer was evaluated by making (circle) and the thing which a residue exist that x which does not have a residue in a space part. The results are shown in Tables 1 and 2.

<Evaluation of adhesiveness>

The negative photosensitive resin composition of Examples 1-11 and Comparative Examples 1-4 was apply | coated on a 8-inch silicon wafer with a spin coater, it dried at 120 degreeC for 5 minutes, and the photosensitive resin layer of 50 micrometers in thickness was obtained. Subsequently, ghi ray was irradiated to this photosensitive resin layer at the irradiation amount of 250 mJ / cm <2>, and it heated on the hotplate at 115 degreeC for 5 minutes. Subsequently, the glass substrate of thickness 0.7mm was heat-compression-bonded on 100 degreeC and 0.1 Mpa conditions on the photosensitive resin layer after heating. And the adhesiveness of the photosensitive resin layer was evaluated as what made the glass substrate affixed (circle) and what is not affixed x. The results are shown in Tables 1 and 2.

<Evaluation of resolution>

The negative photosensitive resin composition of Examples 1-11 and Comparative Examples 1-4 was apply | coated on a 8-inch silicon wafer with a spin coater, it dried at 120 degreeC for 5 minutes, and the photosensitive resin layer of 50 micrometers in thickness was obtained. Subsequently, the ghi line | wire was irradiated to this photosensitive resin layer through the mask at the irradiation amount of 250 mJ / cm <2>. Subsequently, after heating on a hotplate for 5 minutes at 115 degreeC, the unhardened part was melt | dissolved and removed by the paddle phenomenon (60 second x 2) using 2.38 mass% tetramethylammonium hydroxide aqueous solution, and a line and space pattern was removed. Formed. And limit resolution was calculated | required by changing mask dimension. The results are shown in Tables 1 and 2.

<Evaluation of residual rate>

The negative photosensitive resin composition of Examples 1-11 and Comparative Examples 1-4 was apply | coated on a 8-inch silicon wafer with a spin coater, it dried at 120 degreeC for 5 minutes, and the photosensitive resin layer of 50 micrometers in thickness was obtained. Subsequently, ghi ray was irradiated to this photosensitive resin layer at the irradiation amount of 250 mJ / cm <2>, and it heated on the hotplate at 115 degreeC 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 heating was calculated | required, and the residual film rate was evaluated. 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 photosensitive resin composition containing the epoxy resin represented by the general formula (D-1), the photosensitive resin layer Developability, resolution, adhesion after patterning, and residual film ratio were all excellent. On the other hand, in the comparative example 1 using the negative photosensitive resin composition containing the epoxy resin different from the epoxy resin represented by the said General formula (D-1), developability is bad and the negative photosensitive resin composition which does not contain an epoxy resin is shown. In the used comparative example 2, adhesiveness was bad.

In said <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 the comparative example 1 is shown in FIG. In the figure, the part which looks whitest is the space part. As can be seen from these figures 2 and 3, in Example 1, much residue is present in Comparative Example 1, while no residue is present in the space portion.

The difference in developability as described above is that the general epoxy resin used in Comparative Example 1 reacts with the crosslinking agent at the time of heating the photosensitive resin layer and is likely to remain as a residue, whereas the general epoxy resin used in Examples 1 to 7 The epoxy resin represented by Formula (D-1) is presumably because the reactivity with the crosslinking agent is dull and hardly remains as a residue.

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

The difference in developability among them is that the conventional epoxy resins used in Comparative Examples 3 and 4 react with the carboxyl groups of alkali-soluble resins at the time of heating of the photosensitive resin layer and are likely to remain as residues. The epoxy resin represented by the said General formula (D-1) used by -11 is presumably because the reactivity with a carboxy group is dull and hardly remains as a residue.

1: light receiving device
10: support substrate
11: light receiver
12: transparent substrate
13: spacer

Claims (5)

Alkali-soluble resin (A), the compound (B) which generate | occur | produces an acid or a radical by irradiation of an active line, the compound (C) which can be bridge | crosslinked by the acid or radical which generate | occur | produces from the said (B) component, the following general formula (D-1) The negative photosensitive resin composition containing the epoxy resin (D) and solvent (S) represented by).
[Formula 1]

[In formula (D-1), R <^d1> and R <^d2>. Each independently represents a hydrogen atom or a methyl group, and R ^d3 R ^d6 Each independently represents a hydrogen atom, a methyl group, a chlorine atom or a bromine atom. A is an ethyleneoxyethyl group, di (ethyleneoxy) ethyl group, tri (ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) propyl group, tri (propyleneoxy) propyl group, or an alkylene group having 2 to 15 carbon atoms Indicates. n is a natural number and its average is 1.2 to 5] The method of claim 1,
The negative photosensitive resin composition whose content of the said (D) component is 5-40 mass parts with respect to 100 mass parts of said (A) component. The method of claim 1,
The negative photosensitive resin composition whose said (A) component is alkali-soluble resin (A2) which has a structural unit derived from alkali-soluble resin (A1) which has a phenolic hydroxyl group, or unsaturated carboxylic acid. The photosensitive dry film which has a base film and the photosensitive resin layer formed in the surface of this base film, and the said photosensitive resin layer consists of a negative photosensitive resin composition in any one of Claims 1-3. A support substrate on which semiconductor elements are mounted;
A transparent substrate facing the support substrate;
A spacer formed between the support substrate and the transparent substrate,
The light-receiving device whose said spacer is hardened | cured material of the negative photosensitive resin composition of any one of Claims 1-3.

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