JP2021103299A - Photosensitive resin composition - Google Patents

Abstract

To provide a photosensitive resin composition having excellent insulation reliability.SOLUTION: A photosensitive resin composition contains (A) a photo-base generator having a compound represented by formula (1) (where, at least one of R4 is an organic group having a thioether bond and the other is an organic group having a hydrogen atom or a thioether bond, and A is substituent represented by the formula (1-1) or (1-2)), (B) an alkali-developable resin, (C) a heat-reactive compound and (D) a photopolymerizable monomer.SELECTED DRAWING: None

Description

The present invention comprises an alkali-developed photosensitive resin composition containing a photobase generator having a specific structure and capable of forming a pattern by development, a cured product of the photosensitive resin composition, and a dry film containing the photosensitive resin. The present invention relates to a printed wiring board having the cured product.

In recent years, electronic devices have become smaller and more sophisticated, and the density of multilayer printed wiring boards has been increasing due to the increase in the number of circuit layers and the miniaturization of wiring. In particular, the density of semiconductor package substrates such as BGA (ball grid array) and CSP (chip size package) on which semiconductor chips are mounted has been remarkably increased. The diameter of the is being reduced. In such a semiconductor package substrate, a semi-additive method in which a circuit is formed by plating has become the mainstream as the circuit becomes finer.

In the semi-additive method, for example, (1) after forming an insulating film on a conductor circuit, via processing for interlayer connection is performed by laser irradiation, and then desmear treatment for removing resin residue is performed (2). After that, the substrate is subjected to electroless copper plating treatment, a pattern is formed with a dry film resist, and then electrolytic copper plating is performed to form a copper circuit layer. (3) Finally, the resist is peeled off to form the electroless layer. A semiconductor package substrate is formed by forming a copper circuit by flash etching.
However, recently, the via size required for high density has reached the limit that can be processed by laser irradiation, and the photovia method for collectively forming smaller diameter vias by the photolithography method is attracting attention.

However, the conventional photosensitive resin composition used in the photolithography method does not satisfy the characteristics required for a semiconductor package substrate that requires high reliability, particularly insulation reliability (HAST resistance). ..

Japanese Unexamined Patent Publication No. 2016-212258 Japanese Unexamined Patent Publication No. 2016-38587 Japanese Unexamined Patent Publication No. 2018-36651 Patent No. 5852633 JP-A-2019-066511

"Network Polymer" Vol. 35 No. 4 (2014)

An object of the present invention is to provide a photosensitive resin composition and a photovia material capable of forming a cured film having excellent insulation reliability (HAST resistance).

As a result of diligent studies by the present inventors, the above-mentioned photosensitive resin composition containing a photobase generator containing a compound having a specific structure, an alkali-developable resin, a heat-reactive compound, and a photopolymerizable monomer was used. We have found that the problems can be solved and have completed the present invention.
That is, the present invention
(1) (A) The following formula (1)

(In the formula (1), R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group or an organic group other than the above-mentioned substituent. R ₂ , R ₃ , R ₅ and R ₆ are independently hydrogen atom and halogen atom, respectively. , Hydroxy group, alkoxy group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, cyano group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonat group, amino group , Ammonio group or an organic group other than the above-mentioned substituent, and each of a plurality of R ₂ , R ₃ , R ₅ and R ₆ existing may be the same as or different from each other, and may be present on the same benzene ring. R ₂ and R ₃ may be bonded to form a ring structure, or R ₅ and R ₆ existing on the same benzene ring may be bonded to form a ring structure. R ₄ are independent of each other. to, it represents an organic group containing a hydrogen atom or a thioether bond, at least one of R ₄ is an organic group containing a thioether linkage. the binding an organic group and R ₃ or R ₅ containing a thioether bond R ₄ represents A ring structure may be formed by the following formula (1-1) or (1-2).

(In formula (1-1), R ₇ and R ₈ independently represent a hydrogen atom, an alkyl group or a heterocyclic group, respectively, or R ₇ and R ₈ may be bonded to form a heterocycle. In formula (1-2), R ₉ and R ₁₀ each independently represent an amino group or a substituted amino group). A photobase generator containing the compound represented by), (B) an alkali-developable resin, (C) a heat-reactive compound, and (D) a photosensitive resin composition containing a photopolymerizable monomer.
(2) The photosensitive resin composition according to the previous item (1), in which (B) an alkali-developable resin and (C) a heat-reactive compound undergo an addition reaction by heating after selective light irradiation to develop alkali. Photosensitive resin composition capable of forming a negative pattern by
(3) A dry film comprising the photosensitive resin composition according to the preceding item (1) or (2).
(4) The cured product of the photosensitive resin composition according to the preceding item (1) or (2).
(5) A cured product of the dry film according to the previous item (3), and (6) a printed wiring board having the cured product according to the previous item (4) or (5).
Regarding.

The compound represented by the formula (1) contained in the photobase generator contained in the photosensitive resin composition of the present invention can generate bases and radicals by irradiation with active energy rays, and contains the compound. The photosensitive resin composition can form a cured film having excellent insulation reliability (HAST resistance), specifically having a high resistivity and a low resistivity attenuation rate. The photosensitive resin composition of the present invention can form a fine pattern by alkaline development, and is useful as a material applicable as an interlayer insulating layer of a build-up structure such as a printed wiring board, a solder resist, and a coverlay. Is.

Hereinafter, the present invention will be described in detail. The active energy beam in the present invention includes not only visible light but also particle beams such as electron beams, and radiation or ionizing radiation that collectively refers to electromagnetic waves and particle beams, except when the wavelength is specified. .. In the present specification, irradiation with active energy rays is also referred to as exposure. The active energy rays having wavelengths of 365 nm, 405 nm, and 436 nm may also be referred to as i-line, h-line, and g-line, respectively.

The photosensitive resin composition of the present invention contains (A) a photobase generator containing a compound represented by the following formula (1).

In the formula (1), R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group or an organic group other than the above-mentioned substituent.
_{The alkoxy group represented by R 1 in the} formula (1) is preferably an alkoxy group having 1 to 18 carbon atoms, and specific examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, and n. Examples thereof include -butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group, iso-pentoxy group, neo-pentoxy group, n-hexyloxy group and n-dodecyloxy group.

_{Specific examples of the organic group represented by R 1 of the} formula (1) include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, and 6 to 12 carbon atoms. Examples thereof include an aryl group, an acyl group having 1 to 18 carbon atoms, an aloyl group having 7 to 18 carbon atoms, a nitro group, a cyano group, an alkylthio group having 1 to 18 carbon atoms and a halogen atom.

_{Specific examples of the organic group represented by R 1 in the} formula (1) include an alkyl group having 1 to 18 carbon atoms, which includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an iso-butyl group. , Se-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group and n-dodecyl group. Examples thereof include a linear or branched alkyl group such as, and a cyclic alkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group, and an alkyl group having 2 to 6 carbon atoms is preferable. More preferably, it is a linear or branched alkyl group having 2 to 6 carbon atoms.

_{Specific examples of the organic group represented by R 1 in the} formula (1) include a vinyl group, a propenyl group, a 1-butenyl group, an iso-butenyl group, a 1-pentenyl group, and a 2-alkenyl group having 2 to 18 carbon atoms. Pentenyl group, 2-methyl-1-butenyl group, 3-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2,2-dicyanovinyl group, 2-cyano-2-methylcarboxyvinyl group and 2 -Cyano-2-methylsulfone Vinyl group and the like can be mentioned.

_{Specific examples of the organic group represented by R 1 in the} formula (1) include an ethynyl group, a 1-propynyl group, a 1-butynyl group and the like as an alkynyl group having 2 to 18 carbon atoms.
_{Specific examples of the organic group represented by R 1 in the} formula (1) include an aryl group having 6 to 12 carbon atoms, such as a phenyl group, a naphthyl group and a tolyl group, which are aryl groups having 6 to 10 carbon atoms. Is preferable.
_{Specific examples of the organic group represented by R 1 in the} formula (1) include a formyl group, an acetyl group, an ethylcarbonyl group, an n-propylcarbonyl group, an iso-propylcarbonyl group and n. Examples thereof include a-butylcarbonyl group, an n-pentylcarbonyl group, an iso-pentylcarbonyl group, a neo-pentylcarbonyl group, a 2-methylbutylcarbonyl group and a nitrobenzylcarbonyl group.

_{Specific examples of the organic group represented by R 1 in the} formula (1) include a benzoyl group, a toluoil group, a naphthoyl group, a phthaloyl group and the like as an aloyl group having 7 to 18 carbon atoms.
_{Specific examples of the organic group represented by R 1 in the} formula (1) include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group and iso-butylthio as alkylthio groups having 1 to 18 carbon atoms. Group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, 2-methylbutylthio group, 1-methylbutylthio group, neo-pentylthio group, 1,2-dimethylpropylthio group and Examples thereof include a 1,1-dimethylpropylthio group.

_{Specific examples of the organic group represented by R 1 in the} formula (1) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
It The R _1, is preferably a hydroxyl group or an alkoxy group, an more preferably an alkoxy group having hydroxyl group or a carbon number 1 to 6, a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms in the formula (1) Is more preferable, and a hydroxyl group is particularly preferable.

In formula (1), R ₂ , R ₃ , R ₅ and R ₆ are independently hydrogen atom, halogen atom, hydroxyl group, alkoxy group, mercapto group, sulfide group, silyl group, silanol group, nitro group and nitroso group. , a cyano group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group or an organic group other than the substituent, each of R ₂ there are a plurality of, R ₃ , R ₅ and R ₆ may be the same or different from each other. _{Further, R 2} and R ₃ existing on the same benzene ring may be bonded to form a ring structure, or R ₅ and R ₆ existing on the same benzene ring may be bonded to form a ring structure. The ring structure may contain a bond of a heteroatom.

Examples of the halogen atom represented by R ₂ , R ₃ , R ₅ and R ₆ of the formula (1) include the same halogen atom as a specific example of the organic group represented _{by R 1 of the formula (1).}
Examples of the alkoxy group represented by R ₂ , R ₃ , R ₅ and R ₆ of the formula (1) include the same alkoxy group represented by _{R 1 of the formula (1).}

_{Specific examples of the organic group represented by R 2} , R ₃ , R ₅ and R _{6 of the} formula (1) include an alkyl group, an aryl group, an aralkyl group, an alkyl halide group, an isocyano group, a cyanato group, an isocyanato group and a thiocyanato. Examples thereof include a group, an isothiocyanato group, an alkoxycarbonyl group, a carbamoyl group, a thiocarbamoyl group, a carboxy group, a carboxylate group, an acyl group, an acyloxy group and a hydroxyimino group.
Specific examples of the alkyl group, aryl group and acyl group as specific examples of the organic group represented by R ₂ , R ₃ , R ₅ and R ₆ of the formula (1) are the specific example of the organic group represented by _{R 1 of the formula (1).} The same as the alkyl group, aryl group and acyl group.

These organic groups may contain a bond such as a hetero atom other than a hydrocarbon in the organic group, and the organic group may have a substituent other than the hydrocarbon group, and these may be present. It may be linear or branched. The organic group in R ₂ , R ₃ , R ₅ and R ₆ is usually a monovalent organic group, but can be a divalent or higher organic group when forming a cyclic structure described later.

The bonds other than the hydrocarbons that may be contained in the organic groups represented by R ₂ , R ₃ , R ₅ and R ₆ are not particularly limited as long as the effects of the present invention are not impaired, and are, for example, ether bonds and thioethers. Examples thereof include a bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, a carbonate bond, a sulfonyl bond, a sulfinyl bond, and an azo bond. From the viewpoint of heat resistance, the bonds other than hydrocarbons in the organic group include ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, amide bond, urethane bond, imino bond (-N = C (-R)). )-, -C (= NR)-: where R represents a hydrogen atom or an organic group), carbonate bond, sulfonyl bond, sulfinyl bond are preferable.

Substituents other than the hydrocarbon group that the organic group represented by R ₂ , R ₃ , R ₅ and R ₆ may have are not particularly limited as long as the effect of the present invention is not impaired, but for example, a halogen atom, etc. Hydroxyl group, mercapto group, sulfide group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso Group, carboxy group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonat group, hydroxyimino group, saturated or unsaturated alkyl ether group, saturated or Unsaturated alkylthioether group, arylether group, arylthioether group, amino group (-NH ₂ , -NHR, -NRR': where R and R'independently represent hydrocarbon groups), ammonio group, etc. Can be mentioned. The hydrogen contained in the above substituents may be substituted with a hydrocarbon group. The hydrocarbon group contained in the substituent may be linear, branched or cyclic. Among _{them, the substituents other than the hydrocarbon group in the organic groups of R 2} , R ₃ , R ₅ and R ₆ include halogen atom, hydroxyl group, mercapto group, sulfide group, cyano group, isocyano group, cyanato group and isocyanato group. , Thiosianato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxy group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo Groups, sulfonato groups, phosphino groups, phosphinyl groups, phosphono groups, phosphonato groups, hydroxyimino groups, saturated or unsaturated alkyl ether groups, saturated or unsaturated alkyl thioether groups, aryl ether groups, and aryl thioether groups are preferred.

The _{cyclic structure formed by combining R 2} and R ₃ existing on the same benzene ring and the cyclic structure formed by combining R ₅ and R ₆ existing on the same benzene ring are saturated or unsaturated. The alicyclic hydrocarbon, the heterocycle, and the condensed ring of the above, and two or more kinds selected from the group consisting of the alicyclic hydrocarbon, the heterocycle, and the condensed ring may be combined. For example, naphthalene shares the atom of the benzene ring to which _{R 2} and R ₃ are bonded and / or R ₅ and R ₆ are bonded and R ₂ , R ₃ , R ₅ and R _{6 are bonded.} , Anthracene, phenanthrene, indene and the like may be formed.

Preferred specific examples of the organic group represented by R ₂ , R ₃ , R ₅ and R ₆ are an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group and a propyl group; and a cyclopentyl group and a cyclohexyl group and the like. 4 to 23 cycloalkyl groups; cycloalkenyl groups having 4 to 23 carbon atoms such as cyclopentenyl group and cyclohexenyl group; 7 to 26 carbon atoms such as phenoxymethyl group, 2-phenoxyethyl group and 4-phenoxybutyl group Alaryloxyalkyl group (-ROAr group); aralkyl group having 7 to 20 carbon atoms such as benzyl group and 3-phenylpropyl group; alkyl group having 2 to 21 carbon atoms having cyano group such as cyanomethyl group and β-cyanoethyl group. An alkyl group having 1 to 20 carbon atoms having a hydroxyl group such as a hydroxymethyl group, an alkoxy group having 1 to 20 carbon atoms such as a methoxy group and an ethoxy group, an acetamide group, and a benzenesulfonamide group (C ₆ H ₅ SO ₂ NH). An amide group having 2 to 21 carbon atoms such as −), an alkylthio group having 1 to 20 carbon atoms (-SR group) such as a methylthio group and an ethylthio group, and an acyl group having 1 to 20 carbon atoms such as an acetyl group and a benzoyl group. Ester groups having 2 to 21 carbon atoms (-COOR group and -OCOR group) such as methoxycarbonyl group and acetoxy group, aryl groups having 6 to 20 carbon atoms such as phenyl group, naphthyl group, biphenyl group and tolyl group, electron donating An aryl group having 6 to 20 carbon atoms substituted with a sex group and / or an electron-withdrawing group, a benzyl group, a cyano group, and a methylthio group (-SCH ₃ ) substituted with an electron-donating group and / or an electron-withdrawing group Can be mentioned. Further, the above-mentioned alkyl moiety may be linear, branched or cyclic.

_Further, dissolved in the R _2, R 3, if at least one of the compounds is a hydroxy group in _{R 5} and _{R 6,} R _2, R 3, compared to the _{R 5} and _{R 6} do not contain a hydroxyl group in the compound, a basic aqueous solution such as In addition to improving the properties, it is possible to lengthen the absorption wavelength of the compound represented by the formula (1).
It is preferable that all _{of R 2} , R ₃ , R ₅ and R ₆ in the formula (1) are hydrogen atoms.

In formula (1), R ₄ independently represents an organic group containing a hydrogen atom or a thioether bond, but _{at least one of R 4} is an organic group containing a thioether bond. Further, an organic group containing a thioether bond represented _{by R 4 and R 3} or R ₅ may be bonded to form a ring structure. The organic group containing a thioether bond includes the embodiment of "-SX (X is an organic group)", and in this case, the sulfur atom of the thioether bond constitutes the chemical formula of the formula (1). It will be directly bonded to the benzene ring of the skeleton.
Examples of the organic group represented by R ₄ include the same organic groups represented by R ₂ , R ₃ , R ₅ and R ₆ in the above formula (1), but an alkyl group or an aryl group is preferable. That is, the R ₄ of formula (1), preferably an alkylthio group or an arylthio group, more preferably an alkylthio group having 1 to 20 carbon atoms.

In the formula (1), A represents a substituent represented by the following formula (1-1) or (1-2).

In formula (1-1), R ₇ and R ₈ may independently represent a hydrogen atom, an alkyl group or a heterocyclic group, or R ₇ and R ₈ may be bonded to form a heterocycle. When R ₇ and R ₈ independently represent a hydrogen atom, an alkyl group, or a heterocyclic group, R ₇ and R ₈ may be the same or different from each other.
Specific examples of the alkyl group represented by _{R 7} and R ₈ of the formula (1-1) include an alkyl group having 1 to 18 carbon atoms as a specific example of the organic group represented _{by R 1 of the formula (1), which will be described later.} Examples thereof include the same alkyl groups as the substituents of the heterocyclic groups represented by _{R 7} and R ₈ of the formula (1-1).

_{The alkyl group represented by R 7} and R ₈ of the formula (1-1) may have a substituent.
_{The substituents represented by R 7} and R ₈ of the formula (1-1) may have no limitation, but for example, an alkoxy group, an aromatic group, a heterocyclic group, a halogen atom, a hydroxy group, and a mercapto. group, a nitro group, an alkyl-substituted amino group, an aryl-substituted amino group, an unsubstituted amino group (NH ₂ group), cyano group, isocyano group and the like, R of these embodiments is described below formula (1-1) ₇ and is a heterocyclic group represented by R ₈ is the same as the substituent having, for example 2-acryloyloxy group or 2-methacryloyloxy group are preferable, and 2-methacryloyloxy group is more preferable.

_{The heterocyclic group represented by R 7} and R ₈ of the formula (1-1) is not particularly limited as long as it is a residue obtained by removing one hydrogen atom from the heterocycle of the heterocyclic compound, for example, a furanyl group or a thienyl group. , Thienothienyl group, pyrrolyl group, imidazolyl group, N-methylimidazolyl group, thiazolyl group, oxazolyl group, pyridyl group, pyrazil group, pyrimidyl group, quinolyl group, indolyl group, benzopyrazyl group, benzopyrimidyl group, benzothienyl group, naphthothienyl group Benzofuranyl group, benzothiazolyl group, pyridinothiazolyl group, benzoimidazolyl group, pyridinoimidazolyl group, N-methylbenzoimidazolyl group, pyridino-N-methylimidazolyl group, benzoxazolyl group, pyridinooxazolyl group, benzothia Examples thereof include a diazolyl group, a pyridinothiazolyl group, a benzoxaziazolyl group, a pyridinooxadiazolyl group, a carbazolyl group, a phenoxadinyl group and a phenothiazinyl group, and a pyridyl group, an imidazolyl group and an N-methylimidazolyl group. Preferably, a pyridyl group is more preferred.

_{The heterocyclic group represented by R 7} and R ₈ of the formula (1-1) may have a substituent.
_{The substituents of the heterocyclic groups represented by R 7} and R ₈ of the formula (1-1) are not limited, but for example, an alkyl group, an alkoxy group, an aromatic group, a heterocyclic group, a halogen atom, a hydroxy group and a mercapto group. , nitro group, alkyl-substituted amino group, an aryl-substituted amino group, an unsubstituted amino group (NH ₂ group), cyano group, isocyano group and the like, an alkyl group, an aromatic group, a heterocyclic group, more preferably a halogen atom , Aromatic groups, heterocyclic groups are more preferred.

_{Specific examples of the alkyl group as a substituent of the heterocyclic group represented by R 7} and R ₈ of the formula (1-1) include a methyl group, an ethyl group, a propyl group, an iso-propyl group and an n-butyl group. iso-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, t-pentyl group, sec-pentyl group, n-hexyl group, iso-hexyl group, n-heptyl group, sec-heptyl group, n-octyl group, n-nonyl group, sec-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, It is preferably an alkyl group having 1 to 20 carbon atoms such as an n-heptadecyl group, an n-octadecyl group, an n-nonadesyl group and an n-eicosyl group, and more preferably an alkyl group having 1 to 12 carbon atoms. It is more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

_{The alkoxy group as a substituent of the heterocyclic group represented by R 7} and R ₈ of the formula (1-1) is a substituent in which an oxygen atom and an alkyl group are bonded, and is a specific example of the alkyl group of the alkoxy group. Examples thereof include the same alkyl groups as those described in the section of alkyl groups as substituents of the heterocyclic groups represented by _{R 7} and R _{8 in} the formula (1-1), and preferred ones are also the same. Be done.

_{The aromatic group as a substituent of the heterocyclic group represented by R 7} and R ₈ of the formula (1-1) is particularly limited as long as it is a residue obtained by removing one hydrogen atom from the aromatic ring of the aromatic compound. However, for example, a phenyl group, a biphenyl group, a terphenyl group, a quarterphenyl group, a trill group, an indenyl group, a naphthyl group, an anthryl group, a fluorenyl group, a pyrenyl group, a phenanthyl group, a methyl group and the like can be mentioned, and a phenyl group and a biphenyl group can be mentioned. A group, a turphenyl group, a quarterphenyl group, a naphthyl group or an anthryl group is preferable, and a phenyl group, a biphenyl group, a terphenyl group or a naphthyl group is more preferable.
Specific examples of the heterocyclic group as a substituent of the heterocyclic group represented by _{R 7} and R ₈ of the formula (1-1) include the heterocyclic group represented by _{R 7} and R _{8 of the formula (1-1).} The same ones as those described in the section can be mentioned, and the same ones can be mentioned as preferable ones.

_{Specific examples of the halogen atom as the substituent of the heterocyclic group represented by R 7} and R ₈ of the formula (1-1) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and the fluorine atom or chlorine. Atoms are preferred, and fluorine atoms are more preferred.
_{The alkyl-substituted amino group as a substituent of the heterocyclic group represented by R 7} and R ₈ of the formula (1-1) is not limited to either a monoalkyl-substituted amino group or a dialkyl-substituted amino group, and these alkyl-substituted amino groups are used. Examples of the alkyl group in the amino group include the same alkyl groups as those described in the section of alkyl groups as substituents of the heterocyclic groups represented by _{R 7} and R _{8 in the formula (1-1), which are preferable.} The same can be mentioned.

_{The aryl-substituted amino group as a substituent of the heterocyclic group represented by R 7} and R ₈ of the formula (1-1) is not limited to either a monoaryl-substituted amino group or a diaryl-substituted amino group, and these aryl-substituted amino groups are used. Examples of the aryl group in the amino group include the aromatic group and the heterocyclic group described in the section of aromatic group and heterocyclic group as substituents of the heterocyclic group represented by _{R 7} and R _{8 of the formula (1-1).} The same as the group can be mentioned, and the same one can be mentioned as the preferable one.

Heterocycle R ₇ and R ₈ are formed by bonding of the formula (1-1) is long if not particularly restricted ring structure composed of two or more elements, for example a thiophene ring, a furan ring, a pyrrole ring , Pyridine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyrazine ring, thiazine ring and the like, and pyridine ring and imidazole ring are preferable, and pyridine ring is more preferable.
_{The heterocycle formed by combining R 7} and R ₈ of the formula (1-1) may have a substituent.
There is no limitation on the substituents contained in the heterocycle formed by combining R ₇ and R ₈ of the formula (1-1), but for example, the heterocyclic group represented by _{R 7} and R _{8 of the formula (1-1) has.} The same as the substituent can be mentioned.

_{R 7} and R ₈ in the formula (1-1) are preferably hydrogen atoms or alkyl groups having 1 to 18 carbon atoms, respectively, and one is a hydrogen atom and the other is an alkyl group having 1 to 18 carbon atoms. It is more preferably an alkyl group. In _{the category of compounds in which one of R 7} and R ₈ is a hydrogen atom and the other is an alkyl group having 1 to 18 carbon atoms, the compound represented by the following formula (2) or (3) is included. Is also included.

The category of compounds represented by the formula (1) and A represented by the formula (1-1) also includes, for example, the compounds represented by the following formula (2).

In formula (2), _{R 1} to _{R 6} have the same meanings as _{R 1} to _{R 6} in the formula (1), preferred ones are also the same as _{R 1} to _{R 6} in the formula (1). A ₁ represents a cycloalkylene group. D represents an alkylene group.
The cycloalkylene group A ₁ represents formula (2), cyclopropane ring, cyclobutane ring, cyclopentane ring, linked divalent excluding two hydrogen atoms from the cyclohexane ring and cyclic hydrocarbons, saturated, such as adamantane ring It is a group, preferably a 1,3-cyclopentylene group or a 1,4-cyclohexylene group, and more preferably a 1,4-cyclohexylene group.
The alkylene group represented by D in the formula (2) is a divalent linkage obtained by removing two hydrogen atoms from a saturated aliphatic hydrocarbon (for example, methane, ethane, propane, butane, pentane, hexane, heptane, octane, etc.). It is a group, preferably an alkylene group having 1 to 18 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms, and a linear alkylene group having 1 to 8 carbon atoms (specifically, a linear alkylene group having 1 to 8 carbon atoms). Methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group and octylene group) are more preferable, and an alkylene group having 1 to 4 carbon atoms is particularly preferable, and the alkylene group has 1 to 4 carbon atoms. Most preferably, it is an alkylene group (that is, a methylene group).
That is, as the compound represented by the formula (2), the compound represented by the following formula (3) is more preferable.

In the formula (3), _{R 1} to _{R 6} have the same meanings as _{R 1} to _{R 6} in the formula (2), preferred are also the same as _{R 1} to _{R 6} in the formula (2).

In formula (1-2), R ₉ and R ₁₀ independently represent an amino group or a substituted amino group, respectively.
As a specific example of the substituted amino group represented by _{R 9} and R ₁₀ of the formula (1-2), an alkyl substituted amino group as a substituent _{contained in the heterocyclic group represented by R 7} and R _{8 of the formula (1-1).} And the same as the aryl substituted amino group.

_{The R 9} and R ₁₀ of the formula (1-2) are preferably alkyl-substituted amino groups or aryl-substituted amino groups, respectively, and more preferably alkyl-substituted amino groups. R ₉ and R ₁₀ may be the same or different from each other.

As the substituent A in the formula (1), the substituent represented by the formula (1-1) is more preferable.
The compounds represented by the formula (1) include R _{1 to} R _{6 and A (R 7} to R 7 to A in the substituents represented by the formula (1-1) or (1-2) represented by A) described above. R ₁₀ ) A compound in which each preferable compound is combined is more preferable.

When the compound represented by the formula (1) is irradiated with active energy rays, a radical and a basic compound are generated by a cleavage reaction and a decarbonation reaction as shown by the following formula, and the generated radical is generated. Can initiate radical polymerization of a polymer precursor having a radically polymerizable group.

Next, a method for synthesizing the compound represented by the formula (1) will be described.
The compound represented by the formula (1) can be synthesized by applying a known method. For example, first, a benzoin derivative represented by the following formula (21) is reacted with paraformaldehydes at room temperature for 30 minutes in the presence of a metal hydroxide to form an intermediate compound represented by the formula (22-1). After that, sodium nitrite is reacted in the presence of sulfuric acid or the like to obtain an intermediate compound represented by the following formula (23). Next, carbon monoxide and chlorine are reacted with the intermediate compound represented by the above formula (23) in the presence of a catalyst to obtain an intermediate compound represented by the following formula (24), and finally an amine. The compound represented by the formula (1) can be obtained by reacting the compound AH. As a purification method, a crystallization method having high crystallinity of the compound obtained by synthesis is suitable, but it can also be purified by washing with a solvent or the like. Incidentally, _{R 1} to _{R 6} and A of formula (21) to (24) and the amine compound AH have the same meanings as _{R 1} to _{R 6} and A in the formula (1).

When A in the formula (1) is a compound having a substituent represented by the formula (1-1), J.I. Photopolym. Sci. Applying the method described in Technol 27, 2, 2014, for example, a benzoin derivative represented by the following formula (21) is reacted with paraformaldehydes in the presence of a metal hydroxide at room temperature for 30 minutes. After the intermediate compound represented by the formula (22-2) is obtained, the intermediate compound is reacted with isocyanates in the presence of a catalyst of an organic compound such as tin or lead to be represented by the formula (1). Compounds can be obtained. The purification method is the same as above. Incidentally, formula (21), _{R 1} to _{R 8} in (22-2) and isocyanates have the same meanings as _{R 1} to _{R 8} in the formula (1). Even when A represents the formula (1-2), it can be synthesized by using a known method such as the method described in Example 2 of WO2019 / 168089.

Specific examples of the compound represented by the formula (1) are shown in the following formulas (a) to (g), but the compound represented by the formula (1) is not limited thereto.

When the compound represented by the formula (1) is used as a photobase generator, radical polymerization of an alkali-developable resin, a heat-reactive compound and a photopolymerizable monomer and a radical capable of sufficiently contributing to a radical (condensation) reaction. In order to generate a basic compound, it is necessary to have absorption for at least a part of the exposure wavelength. Since the wavelengths of a high-pressure mercury lamp, which is a general exposure light source, are 365 nm, 405 nm, and 436 nm, it is preferable to have absorption for at least one of the active energy rays of these wavelengths.

When the compound represented by the formula (1) is used as a photobase generator, its molar extinction coefficient is 100 or more with respect to an active energy ray having a wavelength of 365 nm, or 1 with respect to an active energy ray having a wavelength of 405 nm. The above is preferable.

The fact that the compound represented by the formula (1) has absorption in the wavelength region means that the compound represented by the formula (1) is 1 in a solvent (for example, acetonitrile) having no absorption in the wavelength region. Dissolve at a concentration of × 10 ^-4 mol / L or less (usually about 1 × 10 ^{-5 to} 1 × 10 ^-4 mol / L. It may be appropriately adjusted so as to have an appropriate absorption intensity). , It can be confirmed by measuring the absorbance with an ultraviolet-visible spectrophotometer (for example, UV-2550 manufactured by Shimadzu Corporation).

The photosensitive resin composition of the present invention contains (B) an alkali-developable resin.
(B) The alkaline developable resin is an essential component for a photosensitive resin composition that is soluble in an alkaline solution. (B) The alkaline developable resin is a resin (resin that can be dissolved in an alkaline solution) that contains at least one functional group selected from a phenolic hydroxyl group, a thiol group and a carboxy group and can be developed with an alkaline solution. Examples thereof include a compound having two or more phenolic hydroxyl groups, a carboxy group-containing resin, a compound having a phenolic hydroxyl group and a carboxy group, and a compound having two or more thiol groups.

Examples of the compound having two or more phenolic hydroxyl groups include phenol novolac resin, alkylphenol novolak resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene-modified phenol resin, polyvinylphenols, bisphenol F, and bisphenol. Examples thereof include known and commonly used phenol resins such as S-type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, and condensate of dihydroxynaphthalene and aldehydes.
Further, as a phenol resin, a compound having a biphenyl skeleton, a phenylene skeleton, or both skeletons, and a phenolic hydroxyl group-containing compound such as phenol, orthocresol, paracresol, metacresol, 2,3-xylenol, 2,4- Xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, fluoroglucolcinol Phenolic resins having various skeletons synthesized by using and the like may be used.
These may be used individually by 1 type, and may be used in combination of 2 or more type.

As the carboxy group-containing resin, a known resin containing a carboxy group can be used. The presence of the carboxy group allows the photosensitive resin composition to be alkaline developable. Further, in addition to the carboxy group, a compound having an ethylenically unsaturated bond in the molecule may be used, but in the present invention, only a carboxy group-containing resin having no ethylenically unsaturated double bond is used. Is preferable.

Specific examples of the carboxy group-containing resin that can be used in the present invention include compounds (either oligomers and polymers) listed below.

(1) A carboxy group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, or isobutylene. The lower alkyl refers to an alkyl group having 1 to 5 carbon atoms.

(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, carboxy group-containing dialcoic compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate-based polyols and polyether-based compounds. A carboxy group-containing urethane resin obtained by a double addition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic-based polyol, a bisphenol A-based alkylene oxide adduct diol, and a compound having a phenolic hydroxy group and an alcoholic hydroxy group.

(3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, and polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, and bisphenol A-based An end carboxy group-containing urethane resin obtained by reacting an acid anhydride with an acid anhydride at the end of a urethane resin by a double addition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxy group and an alcoholic hydroxy group.

(4) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenel type epoxy resin, biphenol type epoxy resin ( Meta) A carboxy group-containing urethane resin obtained by a double addition reaction of an acrylate or a modified partial acid anhydride thereof, a carboxy group-containing dialcohol compound and a diol compound.

(5) During the synthesis of the resin of (2) or (4) above, a compound having one hydroxyl group and one or more (meth) acryloyl groups is added to a molecule such as hydroxyalkyl (meth) acrylate, and the terminal is added. (Meta) Acryloylated carboxy group-containing urethane resin.

(6) During the synthesis of the resin according to (2) or (4) above, one isocyanate group and one or more (meth) acryloyl groups are added to the molecule, such as an isophorone diisocyanate and pentaerythritol triacrylate equimolar reaction product. A carboxy group-containing urethane resin whose terminal is (meth) acrylicized by adding the compound.

(7) An unsaturated monocarboxylic acid such as (meth) acrylic acid is reacted with the above-mentioned polyfunctional (solid) epoxy resin, and phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are phthalic anhydride on the hydroxyl groups existing in the side chain. A carboxy group-containing resin to which a dibasic anhydride such as an acid is added.

(8) A saturated monocarboxylic acid is reacted with the polyfunctional (solid) epoxy resin as described above, and a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is formed on the hydroxyl group existing in the side chain. A carboxy group-containing resin to which is added.

(9) Carboxylic acid obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl groups of a bifunctional (solid) epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the generated hydroxyl groups. Group-containing resin.

(10) A carboxy group-containing polyester resin obtained by reacting a polyfunctional oxetane resin as described later with a dicarboxylic acid and adding a dibasic acid anhydride to the generated primary hydroxyl group.

(11) A carboxy group-containing resin obtained by reacting a polybasic acid anhydride with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with alkylene oxides such as ethylene oxide and propylene oxide. ..

(12) A saturated monocarboxylic acid is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, and the obtained reaction product is abundant. A carboxy group-containing resin obtained by reacting a basic acid anhydride.

(13) Reaction production obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide with an unsaturated group-containing monocarboxylic acid. A carboxy group-containing resin obtained by reacting a compound with a polybasic acid anhydride.

(14) A reaction product obtained by reacting a saturated monocarboxylic acid with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate. A carboxy group-containing resin obtained by reacting with a polybasic acid anhydride.

(15) A carboxy group obtained by reacting a polybasic acid anhydride with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate. Containing resin.

(16) Obtained by reacting an unsaturated group-containing monocarboxylic acid with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate. A carboxy group-containing resin obtained by reacting a reaction product with a polybasic acid anhydride.

(17) An epoxy compound having a plurality of epoxy groups in one molecule is reacted with at least one alcoholic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol and a compound having one phenolic hydroxyl group. A carboxy group obtained by reacting the alcoholic hydroxyl group of the obtained reaction product with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic acid. Containing resin.

(18) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (meth). Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine with respect to the alcoholic hydroxyl group of the obtained reaction product. A carboxy group-containing resin obtained by reacting a polybasic anhydride such as an acid.

(19) In addition to the resin according to any one of (1) to (18) above, one epoxy group and one or more (meth) acryloyl in a molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate. A carboxy group-containing resin obtained by adding a compound having a group.

Since the alkaline developable resin as described above has a plurality of carboxy groups, hirodoxy groups, etc. in the side chain of the backbone polymer, it can be developed with an alkaline aqueous solution.
The hydroxy group equivalent or carboxy group equivalent of the carboxy group-containing resin is 80 to 900 g / eq. Is more preferable, and more preferably 100 to 700 g / eq. Is. Hydroxy group equivalent or carboxy group equivalent is 900 g / eq. If it exceeds, the adhesion of the pattern layer may not be obtained or alkaline development may be difficult. On the other hand, the hydroxy group equivalent or the carboxy group equivalent is 80 g / eq. If it is less than, the line is thinned more than necessary because the developing solution dissolves the light-irradiated part, and in some cases, the developing solution dissolves and peels off the light-irradiated part and the unirradiated part without distinction. It is not preferable because it may be difficult to draw a normal resist pattern. Further, when the carboxy group equivalent or the phenol group equivalent is large, the photosensitive resin composition can be developed even when the content of the (B) alkali-developable resin is small, which is preferable.

The weight average molecular weight of the alkali-developable resin (B) used in the present invention varies depending on the resin skeleton, but is preferably in the range of 2,000 to 150,000, preferably in the range of 5,000 to 100,000. If the weight average molecular weight is less than 2,000, the tack-free performance may be inferior, the moisture resistance of the resin layer after light irradiation is poor, the film is reduced during development, and the resolution may be significantly inferior. On the other hand, if the weight average molecular weight exceeds 150,000, the developability may be significantly deteriorated and the storage stability may be deteriorated.
The weight average molecular weight in the present specification means a value calculated in terms of polystyrene based on the measurement result of gel permeation chromatography.

As used herein, (meth) acrylate is a generic term for acrylates, methacrylates and mixtures thereof, and the same applies to other similar expressions.

Examples of the compound having a thiol group include trimethylolpropantristhiopropionate, pentaerythritol tetraxthiopropionate, ethylene glycol bisthioglycolate, 1,4-butanediol bisthioglycolate, and trimethylolpropanetristhio. Glycolate, pentaerythritol tetraxthioglycolate, di (2-mercaptoethyl) ether, 1,4-butanedithiol, 1,3,5-trimercaptomethylbenzene, 1,3,5-trimercaptomethyl-2,4 , 6-trimethylbenzene, terminal thiol group-containing polyether, terminal thiol group-containing polythioether, thiol compound obtained by reaction of epoxy compound with hydrogen sulfide, terminal thiol group obtained by reaction of polythiol compound and epoxy compound. Examples include thiol compounds.

The alkali-developable resin (B) is preferably a carboxy group-containing resin or a compound having a phenolic hydroxyl group.
Further, the alkali developable resin (B) is preferably non-photosensitive, which does not have a photocurable structure such as epoxy acrylate. Since such a non-photosensitive alkaline developable resin does not have an ester bond derived from an epoxy acrylate, it has high resistance to a desmear liquid. Therefore, when the photosensitive resin composition contains (B) an alkali-developable resin, a pattern layer having excellent curing characteristics can be formed. Moreover, since it does not have a photocurable structure, curing shrinkage can be suppressed.
(B) When the alkaline developable resin is a carboxy group-containing resin, the photosensitive resin composition can be developed with a weak alkaline aqueous solution as compared with the case of a phenolic resin. Examples of the weakly alkaline aqueous solution include those in which sodium carbonate and the like are dissolved. By developing with a weak alkaline aqueous solution, it is possible to prevent the light-irradiated portion from being developed. Further, the light irradiation time in the following step (b) and the heating time in the step (d) can be shortened.
As the (B) alkali-developable resin contained in the photosensitive resin composition of the present invention, the carboxy group-containing resin described in (7) is particularly preferable.

The photosensitive resin composition of the present invention contains (C) a heat-reactive compound.
The heat-reactive compound (C) is a resin having a functional group (heat-reactive group) capable of a curing reaction by heat, and examples thereof include an epoxy resin and a polyfunctional oxetane compound.

The epoxy resin is a resin having an epoxy group, and any known resin can be used. Examples thereof include a bifunctional epoxy resin having two epoxy groups in the molecule, a polyfunctional epoxy resin having many epoxy groups in the molecule, and the like. It may be a hydrogenated bifunctional epoxy compound.

Examples of the polyfunctional epoxy resin include bisphenol A type epoxy resin, brominated epoxy resin, novolak type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy resin, hidden in type epoxy resin, and oil ring. Formula epoxy resin, trihydroxyphenylmethane type epoxy resin, bixilenol type or biphenol type epoxy resin or a mixture thereof, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylol ethane type epoxy resin, heterocyclic epoxy Resin, diglycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin, epoxy resin having a dicyclopentadiene skeleton, glycidyl methacrylate copolymer epoxy resin, cyclohexyl maleimide and glycidyl methacrylate copolymer epoxy resin , CTBN modified epoxy resin and the like.

Other liquid bifunctional epoxy resins include vinylcyclohexene diepoxide, (3', 4'-epoxycyclohexylmethyl) -3,4-epoxycyclohexanecarboxylate, and (3', 4'-epoxy-6'-methyl. Alicyclic epoxy resins such as cyclohexylmethyl) -3,4-epoxy-6-methylcyclohexanecarboxylate can be mentioned. A naphthalene group-containing epoxy resin is preferable because it can suppress thermal expansion of the cured product.

The epoxy resin preferably has an epoxy equivalent of 200 or more. When the epoxy equivalent is 200 or more, the warp of the cured film is suppressed, and the developability is excellent even when the cured film is left in high humidity for a long time.
Examples of epoxy resins having an epoxy equivalent of 200 or more include HP-4770 (naphthalene type, equivalent 205 g / eq.), HP-7200 (dicyclopentadiene skeleton-containing novolac epoxy, 255 g / eq.), EXA-4850, manufactured by DIC. -150 (flexible skeleton-containing liquid epoxy, 440 g / eq.), EXA-4850-1000 (340 g / eq.), HP-820 (aralkylphenol epoxy, 225 g / eq.), PG- manufactured by Osaka Gas Chemical Co., Ltd. 100 (fluorene skeleton-containing epoxy, 250 g / eq.) And EG-200 (flexible epoxy, 292 g / eq.), Mitsubishi Chemicals 1001 (475 g / eq.), 1002 (650 g / eq.), 4004P ( 900g / eq.), 4005P (1075g / eq.) And 157S70 (Biz-A Novolac Epoxy, 210g / eq.), ESN-475V (naphthol aralkyl type, 325g / eq.) Manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., Japan EOCN-104S (cresol novolac epoxy, 210 g / eq.), NC-7000 (naphthalene skeleton-containing novolac epoxy, 230 g / eq.), NC3000 (biphenyl aralkyl type epoxy resin, 275 g / eq.), NC- 3000H (phenol aralkyl type epoxy resin, 289 g / eq.), NC-3000-FH (phenolbiphenyl aralkyl type epoxy resin, 320 g / eq.), NC-2000L (238 g / eq.), NC-3100 (258 g / eq.) ), NC-3000S (284 g / eq.), NC-3000SH (290 g / eq.) And the like.
The above epoxy resins may be used alone or in combination of two or more.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, and 1,4-bis [(3-methyl). -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) ) Methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and polyfunctional oxetane such as oligomers or copolymers thereof, as well as oxetane alcohol and novolak resin, Examples thereof include poly (p-hydroxystyrene), cardo-type bisphenols, calix arrayes, calix resorcinarenes, etherified products with a resin having a hydroxyl group such as silsesquioxane, and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate can also be mentioned.
Here, when the (C) heat-reactive compound has a benzene skeleton, heat resistance is improved, which is preferable. When the photosensitive resin composition contains a white pigment, the (C) heat-reactive compound preferably has an alicyclic skeleton. Thereby, the photoreactivity of the photosensitive resin composition can be improved.

The amount of the heat-reactive compound (C) is preferably 1: 0.1 to 1:10 in terms of the equivalent ratio (heat-reactive group: alkali-developable group) with the alkali-developable resin (B). , 1: 0.2 to 1: 5 is more preferable. When it is within the range of such a compounding ratio, the development becomes good.
As the (C) heat-reactive compound contained in the photosensitive resin composition of the present invention, an epoxy resin is preferable.

The photosensitive resin composition of the present invention contains (D) a photopolymerizable monomer.
Examples of the photopolymerizable monomer (D) include alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and the like. Hydroxyalkyl (meth) acrylates; mono or di (meth) acrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol; hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, di Polyhydric alcohols such as pentaerythritol and trishydroxyethyl isocyanurate or polyvalent (meth) acrylates of these ethylene oxide or propylene oxide adducts; phenols such as phenoxyethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenol A (Meta) acrylates of ethylene oxide or propylene oxide adducts; (meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate; and melamine (meth) acrylate. be able to.

Further, a compound having a maleimide group can also be used as the (D) photopolymerizable monomer. The maleimide compound in the embodiment means a compound having at least one maleimide group in one molecule. Further, the maleimide compound may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily set.
As such a maleimide compound, a compound represented by the following formula (MR-1) or formula (MR-2) is preferable from the viewpoint of glass transition temperature, coefficient of thermal expansion and storage stability.

In formula (MR-1), R ₁₁ is, for example, a phenyl, 2-methylphenyl, 4-methylphenyl, 2,6-diethylphenyl group.
In the formula (MR-2), R ₁₂ is, for example, a group represented by the following formula (A2-i), formula (A2-ii) or formula (A2-iii).

The maleimide compound used as the (D) photopolymerizable monomer of the photosensitive resin composition of the present invention is not particularly limited as long as it contains one or more maleimide groups in the molecule, but for example, N. -Substituted maleimide compounds can be used, and examples of the N-substituted maleimide compounds include N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, and N- (2,6). -Diethylphenyl) maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmethylmaleimide, N- (4-hydroxyphenyl) maleimide, N-( 1-Hydroxyphenyl) Maleimide, 1-methyl-2,4-bismaleimidebenzene, N, N'-m-phenylene bismaleimide, N, N'-p-phenylene bismaleimide, N, N'-m-toluylene Bismaleimide, N, N'-4,4'-biphenylene Bismaleimide, N, N'-4,4'-[3,3'-dimethylbiphenylene] Bismaleimide, N, N'-4,4'-[ 3,3'-Dimethyldiphenylmethane] bismaleimide, N, N'-4,4'-[3,3'-diethyldiphenylmethane] bismaleimide, N, N'-4,4'-diphenylmethane bismaleimide, N, N '-4,4'-diphenylpropane bismaleimide, N, N'-4,4'-diphenyl ether bismaleimide, N, N'-3,3'-diphenylsulfone bismaleimide, N, N'-4,4' −Diphenylsulfone bismaleimide, 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidephenoxy) phenyl] hexafluoropropane, 2,2-bis [ 3-Methyl-4- (4-maleimidephenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-maleimidephenoxy) phenyl] hexafluoropropane, 2,2-bis [3,5- Dimethyl-4- (4-maleimidephenoxy) phenyl] propane, 2,2-bis [3,5-dimethyl-4- (4-maleimidephenoxy) phenyl] hexafluoropropane, 2,2-bis [3-ethyl- 4- (4-Maleimidephenoxy) phenyl] propane, 2,2-bis [3-ethyl-4- (4-maleimidephenoxy) phenyl] hexafluoropropane , Bis [3-methyl-4- (4-maleimidephenoxy) phenyl] methane, bis [3,5-dimethyl-4- (4-maleimidephenoxy) phenyl] methane, bis [3-ethyl-4- (4-) Maleimide phenoxy) phenyl] methane, 3,8-bis [4- (4-maleimide phenoxy) phenyl] -tricyclo- [5.2.1.0 ^2,6 ] decane, 4,8-bis [4- (4) -Maleimidephenoxy) phenyl] -tricyclo- [5.2.1.0 ^2,6 ] decane, 3,9-bis [4- (4-maleimidephenoxy) phenyl] -tricyclo- [5.2.1.0 ^2,6 ] decane, 4,9-bis [4- (4-maleimidephenoxy) phenyl] -tricyclo- [5.2.1.0 ^2,6 ] decane, 1,8-bis [4- (4- (4- (4- (4-)4-) Maleimide phenoxy) phenyl] mentan, 1,8-bis [3-methyl-4- (4-maleimide phenoxy) phenyl] mentan, 1,8-bis [3,5-dimethyl-4- (4-maleimide phenoxy) phenyl ] Mentan, Daiwa Kasei Co., Ltd. BMI-1000, -1000H, -1100, -1100H, -2000, -2300, -3000, -3000H, -4000, -5100, -7000, -7000H, -TMH, Designer Maleimide Inc. BMI-689, -1400, -1500, -1700, -2500, -3000 manufactured by Nippon Kayaku Co., Ltd., MIR-3000, MIZ-001 manufactured by Nippon Kayaku Co., Ltd. and the like can be mentioned. Among these, those having less aromatic conjugate are preferable from the viewpoint of compatibility with the epoxy resin. The above compounds may be of only one kind, of two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily set.

The blending amount of the photopolymerizable monomer (D) is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, based on the solid content of the photosensitive resin composition excluding the solvent. More preferably, it is 1 to 15% by mass. When the blending amount of the photopolymerizable monomer (D) exceeds 50% by mass, the curing shrinkage becomes large, so that the warp may become large. When the (D) photopolymerizable monomer is derived from (meth) acrylate, it contains an ester bond. In this case, the desmear treatment causes hydrolysis of the ester bond, which may reduce the electrical properties.

The photosensitive resin composition of the present invention may be used in combination with a photobase generator other than the photobase generator (A) containing the compound represented by the formula (1). The photobase generator is a catalyst for an addition reaction between a (meth) acrylate compound having an epoxy group and a thermosetting component when the molecular structure is changed by irradiation with light such as ultraviolet rays or visible light or the molecule is cleaved. A compound that produces one or more basic substances that can function as. Examples of the generated basic substance include secondary amines and tertiary amines.

Examples of photobase generators that can be used in combination include α-aminoacetophenone compounds, oxime ester compounds, acyloxyimino groups, N-formylated aromatic amino groups, N-acylated aromatic amino groups, nitrobenzyl carbamate groups, and alcohols. Examples thereof include compounds having a substituent such as an oxybenzyl carbamate group. Of these, oxime ester compounds and α-aminoacetophenone compounds are preferable. As the α-aminoacetophenone compound, those having two or more nitrogen atoms are particularly preferable. Other photobase generators include WPBG-018 (trade name: 9-anthraquinone, N'-diethylcarbamate, manufactured by Wako Pure Chemical Industries, Ltd.), WPBG-027 (trade name: (E) -1- [3- (2-hydroxyphenyl)). ) -2-Propenoyl] piperidine), WPBG-082 (trade name: guanidinium2- (3-benzoylphenyl) propionate), WPBG-140 (trade name: 1- (anthraquinone-2-yl) ethylimidazole. it can. The α-aminoacetophenone compound has a benzoin ether bond in the molecule, and when it is irradiated with light, cleavage occurs in the molecule to generate a basic substance (amine) that acts as a curing catalyst. Specific examples of the α-aminoacetophenone compound include (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, manufactured by BASF Japan) and 4- (methylthiobenzoyl) -1-methyl. -1-morpholinoetan (Irgacure 907, trade name, manufactured by BASF Japan), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl]- Commercially available compounds such as 1-butanone (Irgacure 379, trade name, manufactured by BASF Japan) or a solution thereof can be used.

As the oxime ester compound that can be used in combination, any compound that produces a basic substance by light irradiation can be used. Examples of commercially available products of such oxime ester compounds include CGI-325 manufactured by BASF Japan Ltd., Irgacure OXE01, Irgacure OXE02, N-1919 manufactured by ADEKA CORPORATION, NCI-831 and the like. Further, the compound described in Japanese Patent No. 4344400, which has two oxime ester groups in the molecule, can also be preferably used.

In addition, JP-A-2004-359639, JP-A-2005-097141, JP-A-2005-22097, JP-A-2006-160634, JP-A-2008-09470, JP-A-2008-50967, Examples thereof include carbazole oxime ester compounds described in JP-A-2009-040762 and JP-A-2011-80036.

(A) A base proliferating agent that generates a base by decomposing or rearranging due to the action of a small amount of base generated from the photobase generator may be used in combination. Examples of the base proliferation agent include a compound having a 9-fluorenylmethylcarbamate bond and a 1,1-dimethyl-2-cyanomethylcarbamate bond ((CN) CH ₂ C (CH ₃ ) ₂ OC (O) NR _2). ), A compound having a paranitrobenzyl carbamate bond, a compound having a 2,4-dichlorobenzyl carbamate bond, and other urethane compounds described in paragraphs 0010 to 0032 of JP-A-2000-330270. , Urethane-based compounds described in paragraphs 0033 to 0060 of JP-A-2008-250111.

A photobase generator other than the photobase generator (A) or a photopolymerization initiator may be used in combination with the photosensitive resin composition of the present invention.
The photobase generator and photopolymerization initiator that can be used in combination are not particularly limited, and for example, a photoradical polymerization initiator can be used. As the photoradical polymerization initiator, any compound that can generate radicals by light, a laser, an electron beam, or the like to initiate a radical polymerization reaction can be used.

Examples of the photopolymerization initiator that can be used in combination include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether and benzoin alkyl ethers; 2-hydroxy-2-methyl-1-phenyl-propane-1-. Alkylphenone type such as on; acetphenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2-methyl-1- [4 -(Methylthio) Phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, N, N-dimethylaminoacetophenone and other amino acids Acetphenones; Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2, Thioxanthones such as 4-diisopropylthioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; 2,4,5-triarylimidazole dimer; riboflavin tetrabutyrate; 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole , 2-Mercaptobenzothiazole and other thiol compounds; 2,4,6-tris-s-triazine, 2,2,2-tribromoethanol, tribromomethylphenylsulfone and other organic halogen compounds; benzophenone, 4,4' -Benzophenones or xanthones such as bisdiethylaminobenzophenone; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; bis ( Cyclopentadienyl) diphenyltitanium, bis (cyclopentadienyl) dichlorotitanium, bis (cyclopentadienyl) -bis (2,3,4,5,6 pentafluorophenyl) titanium, bis (cyclopentadienyl) Examples thereof include titanosenes such as −bis (2,6-difluoro-3- (pyrrole-1-yl) phenyl) titanium.

These known and commonly used photopolymerization initiators can be used alone or as a mixture of two or more kinds, and further, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4- Photoinitiator aids such as tertiary amines such as dimethylaminobenzoate, triethylamine and triethanolamine can be added.

Examples of commercially available photopolymerization initiators are Irgacure 261, 184, 369, 651, 500, 819, 907, 784, 2959, DaroCure 1116, 1173, CGI1700, CGI1750, CGI1850, CG-24-61, Lucillin. TPO, CGI-784 (above, product name manufactured by BASF Japan), DAICATII (product name manufactured by Daicel Chemical Industry Co., Ltd.), UVAC1591 (product name manufactured by Daicel UCB), Lord Sill Photo Initiator 2074 (Rhodia) Product name manufactured by UCB), Yubekrill P36 (product name manufactured by UCB), EzaCure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B, ONE (product name manufactured by Flatetsuri Lamberti), etc. Be done.

When a photobase generator other than the (A) photobase generator and / or a photopolymerization initiator other than the (A) photobase generator containing the compound represented by the formula (1) is used in combination, the photobase to be used in combination is used. The blending ratio of the generator and / or the photopolymerization initiator is preferably in the range of 0.5 to 10 parts by mass in 100 parts by mass of the photosensitive resin composition of the present invention.

Further, it is preferable to use a thermocuring catalyst for the photosensitive resin composition of the present invention. For example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4 Imidazole derivatives such as −phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N Amine compounds such as -dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; A phosphorus compound or the like can be used.

Commercially available products include, for example, 2MZ-A, 2MZOK, 2PHZ, 2P4BHZ, 2P4MHZ (both are trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT (registered trademark) manufactured by San Apro Co., Ltd. Examples thereof include 3503N, U-CAT3502T (all trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, UCATSA102, U-CAT5002 (all bicyclic amidine compounds and salts thereof). In particular, the present invention is not limited to these, as long as it is a thermosetting catalyst of an epoxy compound or an oxetane compound, or one that promotes the reaction of an epoxy group and / or an oxetanyl group and a carboxy group, and may be used alone or in combination of two or more. You may use it.

In addition, guanamine, acetguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid adduct can also be used, preferably as these adhesion-imparting agents. A compound that also functions is used in combination with a thermocuring catalyst.

The blending amount of these thermosetting catalysts is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 15.0 parts by mass with respect to 100 parts by mass of the (C) heat-reactive compound component.

When it is desired to utilize the energy of the active energy ray having a wavelength transmitted through the polymer for the photobase generator with high efficiency, that is, when it is desired to improve the sensitivity of the photobase generator, the addition of the sensitizer is effective. It may be demonstrated. In particular, when the polyimide precursor has absorption even in the wavelength region of 360 nm or more, the effect of adding the sensitizer is large. Specific examples of the compound called a sensitizer include thioxanthone, diethylthioxanthone and the like and their derivatives, coumarin and its derivatives, ketocumarin and its derivatives, ketobiscumarin and its derivatives, cyclopentanone and its derivatives, cyclohexanone and its derivatives. Examples thereof include thiopyrrium salts and derivatives thereof, thioxanthene and xanthene and derivatives thereof. Specific examples of coumarin, ketocoumarin and its derivatives include 3,3'-carbonylbis coumarin, 3,3'-carbonylbis (5,7-dimethoxycoumarin) and 3,3'-carbonylbis (7-acetoxycoumarin). And so on. Specific examples of thioxanthone and its derivatives include diethyl thioxanthone and isopropyl thioxanthone. Further, benzophenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphten, benzoquinone, 2-ethylanthraquinone, 2-tertiary butyl anthraquinone, 1,2-benzanthraquinone, 1,2-naphthoquinone and the like can be mentioned. .. Since these exert particularly excellent effects when combined with (A) a photobase generator, a sensitizer exhibiting an optimum sensitizing effect is appropriately selected depending on the structure of (A) the photobase generator.

A solvent may be used in combination with the photosensitive resin composition of the present invention.
Examples of general-purpose solvents that can be used include ethers such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, and diethylene glycol dimethyl ether; ethylene glycol monomethyl ether and ethylene glycol mono. Glycol monoethers such as ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether (so-called cellosolves); ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclopentanone and cyclohexanone. Classes: ethyl acetate, butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, acetate esters of the glycol monoethers (eg, methyl cellosolve acetate, ethyl cellosolve acetate), propylene glycol. Esters such as monomethyl ether acetate, propylene glycol monoethyl ether acetate, dimethyl oxalate, methyl lactate, ethyl lactate; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin; methylene chloride, 1 , 1-dichloroethane, 1,2-dichloroethylene, 1-chloropropane, 1-chlorobutane, 1-chloropentane, chlorobenzene, brombenzene, o-dichlorobenzene, m-dichlorobenzene and other halogenated hydrocarbons; N, N- Amidos such as dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide; N-methyl-2-pyrrolidone, N-acetyl-2- Pyrrolidones such as pyrrolidone; lactones such as γ-butyrolactone and α-acetyl-γ-butyrolactone; sulfoxides such as dimethyl sulfoxide, sulfones such as dimethyl sulfone, tetramethylene sulfone and dimethyl tetramethylene sulfone, hexamethylphosphoamide Phosphate amides such as, and other organic polar solvents, and aromatic hydrocarbons such as benzene, toluene, xylene, and pyridine, and the like. Other organic non-polar solvents and the like can also be mentioned. These solvents are used alone or in combination.

The photosensitive resin composition of the present invention is useful for forming a pattern layer as a permanent coating of a printed wiring board such as a solder resist, a coverlay, and an interlayer insulating layer, and is particularly useful for forming a solder resist. Further, since the photosensitive resin composition of the present invention is excellent in resolution, it can be suitably used for forming a pattern layer of an IC package, which is required to form a fine pattern.

[Pattern formation method]
The method of using the photosensitive resin composition of the present invention will be described below with reference to an example used for pattern formation of the solder resist, but the method of using the photosensitive resin composition of the present invention is not limited thereto. Absent.
The pattern forming method using the photosensitive resin composition of the present invention is a step (a) of forming a resin layer made of a photosensitive resin composition on a substrate, and a negative type patterned light irradiation is performed on the photosensitive resin composition. The present invention includes a step (b) of activating the photobase generator contained in the above to cure the light-irradiated portion, and a step (c) of forming a negative pattern layer by removing the unirradiated portion by development. The light-irradiated portion is cured by generating a base in the light-irradiated portion of the photosensitive resin composition by pattern-shaped light irradiation. Then, by developing with an organic solvent or an alkaline aqueous solution, the unirradiated portion is removed and a negative pattern layer is formed.
Here, in the present invention, it is preferable to have a step (d) of heating the resin layer after the step (b) and before the step (c) or after the step (c). As a result, the resin layer can be sufficiently cured to obtain a pattern layer having further excellent curing characteristics.

[Step (a)]
The step (a) is a step of forming a resin layer (dry film) made of a photosensitive resin composition on the base material. Examples of the method for forming the resin layer include a method of applying and drying a liquid photosensitive resin composition on a substrate, and a method of laminating a dry film of a photosensitive resin composition on a substrate. Be done.

As a method for applying the photosensitive resin composition to the substrate, a known coating device such as a blade coater, a lip coater, a comma coater, or a film coater can be appropriately adopted. Further, as a drying method, a method using a known drying device such as a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven, and a method equipped with a steam heating type heat source can be mentioned, and hot air in the dryer can be used. By adopting a known method such as a method of countercurrent contact and a method of spraying the support from a nozzle, the photosensitive resin composition can be appropriately dried.
As the base material, in addition to the pre-circuit-formed printed wiring base material and flexible printed wiring base material, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy All grades (FR-4, etc.) copper-clad laminates, polyimide films, using composite materials such as resin, glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, fluororesin, polyethylene, PPO, cyanate ester, etc. A PET film, a glass base material, a ceramic base material, a wafer base material, or the like can be used.

[Step (b)]
In the step (b), the resin layer formed in the step (a) is irradiated with light in a negative pattern to activate the (A) photobase generator contained in the photosensitive resin composition constituting the resin layer. This is a process of forming and curing the light-irradiated portion. In the step (b), it is considered that the base generated in the light irradiation unit destabilizes the photobase generator (A) and further generates a base. By chemically multiplying the base in this way, it is possible to sufficiently cure the deep part of the light-irradiated portion.
As the light irradiator used for light irradiation, for example, a direct drawing device capable of irradiating laser light, lamp light, or LED light can be used. A negative type mask can be used as the patterned light irradiation mask.

As the active energy ray, it is preferable to use laser light or scattered light having a maximum wavelength in the range of 350 to 410 nm. By setting the maximum wavelength in this range, the thermal reactivity of the photosensitive resin composition can be efficiently improved. As long as the maximum wavelength is laser light in this range, either a gas laser or a solid-state laser may be used. The amount of light irradiation varies depending on the film thickness and the like, but can generally be in the range of 100 to 1500 mJ / cm ² , preferably 300 to 1500 mJ / cm ² .

As the direct drawing device, for example, one manufactured by Orbotech Japan, Pentax, etc. can be used, and any device may be used as long as it oscillates a laser beam having a maximum wavelength of 350 to 410 nm. ..

[Step (c)]
The step (c) is a step of forming a negative pattern layer by removing the unirradiated portion by development. As the developing method, a known method such as a dipping method, a shower method, a spray method, and a brush method can be used. The developing solution includes an aqueous solution of potassium hydroxide, an aqueous solution of sodium hydroxide, an aqueous solution of sodium carbonate, an aqueous solution of potassium carbonate, an aqueous solution of sodium phosphate, an aqueous solution of sodium silicate, an aqueous solution of ammonia, amines such as ethanolamine, and tetramethylammonium hydroxide. An alkaline aqueous solution such as an aqueous solution (TMAH) or a mixed solution thereof can be used. If it can be developed using an appropriate organic solvent, it may be developed using an organic solvent.

[Step (d)]
The pattern forming method preferably includes a thermosetting (post-cure) step (d) by heating after the step (c).
In the step (d), the pattern layer can be sufficiently thermoset by the base generated from the (A) photobase generator in the step (b). Step (d) can be carried out at a temperature equal to or higher than the curing reaction start temperature of the unreacted (C) heat-reactive compound. As a result, the pattern layer can be sufficiently thermoset. The heating temperature is, for example, 160 ° C. or higher.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples. Unless otherwise specified, "part" and "%" in the text are based on mass.

Synthesis Example 1 (Synthesis of compound represented by formula (1) (component (A-1)))
A compound (A-1) represented by the formula (1) was obtained according to the description of Example 6 of JP-A-2017-1054749.

Synthesis Example 2 (Synthesis of compound represented by formula (1) (component (A-2)))
(Step 1) Synthesis of Intermediate Compound Represented by Formula (31) 10 parts of water and 53 parts of ethanol were added to 1.9 parts of potassium cyanide to dissolve it, and then the reaction was carried out by ultrasonic treatment in a nitrogen atmosphere. The liquid was degassed. 10 parts of 4- (methylthio) benzaldehyde represented by the following formula (30) was added dropwise to this solution, and the reaction was started by heating at 80 ° C. After stirring for 30 minutes, the reaction solution was cooled to 3 ° C., and the precipitated crystals were collected by suction filtration. The recovered crystals were purified by recrystallization using a large amount of ethanol to obtain 7.6 parts of an intermediate compound represented by the following formula (31).

(Step 2) Synthesis of intermediate compound represented by formula (32) To a flask equipped with a stirrer, a reflux condenser and a stirrer, 9.0 parts of paraformaldehyde and 170 parts of dimethylsulfoxide are added and stirred, and then water is added. A solution prepared by dissolving 1.4 parts of potassium oxide in 5 parts of ethanol was added dropwise, and the mixture was stirred until paraformaldehyde was completely dissolved. A solution prepared by dissolving 50 parts of the intermediate compound represented by the formula (31) obtained in step 1 in 30 parts of dimethyl sulfoxide was added dropwise to the dimethyl sulfoxide solution obtained above over 30 minutes, and the solution was added dropwise at room temperature. Stirred for hours. Then, 2.6 parts of 35% hydrochloric acid was added dropwise to neutralize the reaction, and the reaction was terminated. Toluene and saturated brine are added to this reaction solution to extract the reaction product into the organic layer, and then the separated and concentrated organic layer is crystallized to obtain 40 parts of the intermediate compound represented by the following formula (32). It was.

(Step 3) Synthesis of compound represented by formula (1) 10.0 parts of intermediate compound represented by formula (32) obtained in step 2, 28 parts of toluene and octyl 0.08 part of tin acetate was placed in a flask and refluxed and stirred until uniform. Subsequently, 5.6 parts of 2-methacryloyloxyethyl isocyanate (Kalens MOI manufactured by Showa Denko KK) was added at a liquid temperature of 60 ° C., stirring was continued for 3 hours, and then the reaction liquid was crystallized by cooling to formulate the following formula (A). 10.7 parts of the compound represented by -2) was obtained.

Synthesis Example 3 (Synthesis of compound represented by formula (1) (component (A-3)))
66 parts of the intermediate compound represented by the formula (32) obtained in step 2, 182 parts of toluene, 2.0 parts of triethylamine and 1.3 parts of dibutylhydroxytoluene (BHT) are placed in a flask and 80 parts until uniform. Stirring was performed at ° C. Subsequently, 33 parts of 2-isocyanatoethylacryllate (Kalens AOI-VM manufactured by Showa Denko KK) was added at a liquid temperature of 80 ° C., stirring was continued for 3 hours, and then the reaction liquid was crystallized by cooling to formulate the following formula. 86 parts of the compound represented by A-3) were obtained.

Examples 1 to 4 and Comparative Examples 1 to 4 (preparation of photosensitive resin composition)
(A) photobase generator, (B) alkali-developable resin, (C) heat-reactive compound, (D) photopolymerizable monomer, other additives, and diethylene glycol mono in an amount that gives the solid content concentration shown in Table 1. After stirring and mixing ethyl ether acetate, each photosensitive resin composition was prepared by defoaming using a defoaming device. Table 1 shows the types of the respective constituent raw materials and the blending amount (parts by mass) in terms of solid content.

(Electrical insulation reliability evaluation)
Using nitoflon tape (thickness 90 μm) for film thickness control, the photosensitive resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4 in an amount such that the thickness after distilling off the solvent became 50 μm were used. Each was applied to a substrate and allowed to stand in a dryer at 80 ± 5 ° C. for 30 minutes to distill off the solvent. An integrated exposure amount of 1,200 mJ / cm was applied to the obtained coating film under the condition that the exposure amount of one pass was 100 mJ / cm ² (height from the belt conveyor to the high-pressure mercury lamp 100 mm) using a belt conveyor type high-pressure mercury lamp exposure machine. ^{After the exposure of No. 2} , spray development was carried out for 90 seconds with a 1 mass% sodium carbonate aqueous solution at 30 ° C. Then, a sample for evaluation was prepared by heating and curing in an oven at 150 ° C. for 1 hour. The base material is a copper foil of non-adhesive polyimide copper-clad laminate (Espanex (manufactured by Nittetsu Chemical & Materials Co., Ltd., copper foil thickness 18 μm, polyimide film thickness 25 μm)) line width / space. The one processed into a comb-shaped pattern having a width = 100 μm / 100 μm was used.
The resistance value (maximum resistance value) when a DC current of 100 V was applied to both terminal portions of the comb-shaped pattern of each evaluation sample obtained above was measured, and the results are shown in Table 1.
In addition, the resistance value after 100 hours was measured by allowing the sample to stand in an environmental tester at 130 ° C. and 85% RH while applying a DC current of 100 V to both terminals of the comb-shaped pattern of each evaluation sample, and measuring "130 ° C." The damping factor was calculated by the formula of "resistance value after 100 hours of 85% RH / maximum resistance value x 100", and the results are shown in Table 1.

The photosensitive resin composition of the present invention is useful for forming a pattern layer as a permanent coating of a printed wiring board such as a solder resist, a coverlay, and an interlayer insulating layer, and is particularly useful for forming a solder resist. Further, since the photosensitive resin composition of the present invention is excellent in insulation reliability, it can be suitably used as an interlayer insulating material used for forming a pattern layer of an IC package.

Claims (6)

(A) The following formula (1)

(In the formula (1), R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group or an organic group other than the above-mentioned substituent. R ₂ , R ₃ , R ₅ and R ₆ are independently hydrogen atom and halogen atom, respectively. , Hydroxy group, alkoxy group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, cyano group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonat group, amino group , Ammonio group or an organic group other than the above-mentioned substituent, and each of a plurality of R ₂ , R ₃ , R ₅ and R ₆ existing may be the same as or different from each other, and may be present on the same benzene ring. R ₂ and R ₃ may be bonded to form a ring structure, or R ₅ and R ₆ existing on the same benzene ring may be bonded to form a ring structure. R ₄ are independent of each other. to, it represents an organic group containing a hydrogen atom or a thioether bond, at least one of R ₄ is an organic group containing a thioether linkage. the binding an organic group and R ₃ or R ₅ containing a thioether bond R ₄ represents A ring structure may be formed by the following formula (1-1) or (1-2).

(In formula (1-1), R ₇ and R ₈ independently represent a hydrogen atom, an alkyl group or a heterocyclic group, respectively, or R ₇ and R ₈ may be bonded to form a heterocycle. In formula (1-2), R ₉ and R ₁₀ each independently represent an amino group or a substituted amino group). A photobase generator containing a compound represented by),
A photosensitive resin composition containing (B) an alkali-developable resin, (C) a heat-reactive compound, and (D) a photopolymerizable monomer. The photosensitive resin composition according to claim 1, wherein (B) an alkali-developable resin and (C) a heat-reactive compound undergo an additional reaction by heating after selective light irradiation, and the negative type is developed by alkali development. A photosensitive resin composition capable of forming a pattern. A dry film comprising the photosensitive resin composition according to claim 1 or 2. A cured product of the photosensitive resin composition according to claim 1 or 2. The cured product of the dry film according to claim 3. A printed wiring board having the cured product according to claim 4 or 5.