WO2015016362A1 - Photosensitive-resin composition - Google Patents

Abstract

This invention pertains to a photosensitive-resin composition containing the following: (A) an acid-modified-vinyl-group-containing epoxy resin; (B) an acyl-phosphine-oxide photopolymerization initiator; (C) one or more additives selected from among (C1) alkylamino-benzene derivatives, (C2) pyrazoline sensitizers or anthracene sensitizers, (C3) one or more photopolymerization initiators selected from among imidazole photopolymerization initiators, acridine photopolymerization initiators, and titanocene photopolymerization initiators, (C4) one or more antioxidants selected from among hindered-phenol antioxidants, quinone antioxidants, amine antioxidants, sulfur antioxidants, and phosphorus antioxidants, and (C5) thiol-group-containing compounds; and (D) a photopolymerizable compound.

Description

Photosensitive resin composition

The present invention relates to a photosensitive resin composition, a photosensitive element using the photosensitive resin composition, a permanent mask resist, and a printed wiring board including the permanent mask resist.

In the field of manufacturing printed wiring boards, permanent mask resist is formed on printed wiring boards. The permanent mask resist has a role of preventing corrosion of the conductor layer and maintaining electrical insulation between the conductor layers when the printed wiring board is used. In recent years, permanent mask resists prevent solder from adhering to unnecessary portions of a conductor layer of a printed wiring board in a process of flip chip mounting, wire bonding mounting or the like of a semiconductor element on the printed wiring board via solder. It also has a role as a solder resist film.

Conventionally, permanent mask resists in the production of printed wiring boards have been produced by screen printing using a thermosetting resin composition or by photographic methods using a photosensitive resin composition. For example, in flexible wiring boards using mounting methods such as FC (Flip Chip), TAB (Tape Automated Bonding) and COF (Chip On Film), IC chips, electronic components, LCD (Liquid Crystal Display) panels, and connection wiring Except for the pattern portion, a thermosetting resin paste is screen-printed and thermally cured to form a permanent mask resist (for example, Patent Document 1).

Also, in semiconductor package substrates such as BGA (Ball Grid Array) and CSP (Chip Size Package) mounted on electronic components, (1) For flip chip mounting of semiconductor elements on the semiconductor package substrate via solder (2) To bond the semiconductor element and the semiconductor package substrate to each other by wire bonding, or (3) To solder-bond the semiconductor package substrate to the mother board, it is necessary to remove the permanent mask resist at the bonding portion. There is. Therefore, for the formation of this permanent mask resist, the photosensitive resin composition is coated and dried, and then selectively irradiated with an actinic ray such as ultraviolet rays to be cured, and only unexposed portions are removed with a developer to form an image. The law is used. Since the photographic method is suitable for mass production due to its good workability, it is widely used in the electronic material industry for image formation of a photosensitive resin composition (for example, Patent Documents 2 to 4).

JP 2003-198105 A Japanese Patent Laid-Open No. 11-240930 JP 2010-235739 A JP 2011-133851 A

However, when a photosensitive resin composition to which pigments, fillers and the like are added as described in Patent Documents 2 to 4, the pigments, fillers, etc. prevent the transmission of ultraviolet rays or absorb ultraviolet rays. When attempting to form a permanent mask resist with a thickness of ˜40 μm or more, the photo-curing of the photosensitive resin composition at the bottom may not be sufficiently obtained, resulting in an undercut where the bottom is removed after development. There is.
Increasing the amount of exposure to ultraviolet irradiation to improve the photocurability of the bottom increases the light diffraction and halation, and the middle part (center part) and deepest part with respect to the line width of the surface part (upper part) of the pattern cross section Since the line width of (bottom part) becomes large, there is a problem that the resist shape is deteriorated or the resolution is lowered. Further, there is a problem that the resist upper portion is lost due to insufficient photocuring in a region extending from the surface to about 3 μm in the resist depth direction due to oxygen inhibition, and the resist shape is deteriorated. Therefore, when forming a thick permanent mask resist having a thickness of 20 to 40 μm or more, there is currently no photosensitive resin composition having good photocurability at the bottom and excellent resolution.

Furthermore, in recent years, with the downsizing and high performance of electronic devices, the size of the hole diameter of the permanent mask resist and the pitch between the holes tend to become finer. For example, a high-definition pattern having a hole diameter of 100 μm and an interval pitch between holes of 100 μm, or a hole diameter of 80 μm and an interval between holes of 80 μm is used. Therefore, for example, in flip chip mounting, there is a demand for a permanent mask resist that has excellent resist shape stability from the viewpoint of solder filling properties as well as improved resolution.

The object of the present invention has been made in view of such a problem, and is excellent in curability at the bottom of the via opening, so that the occurrence of an undercut in which the bottom is removed and the lack of the top of the resist do not occur. In addition, since the exposure amount of ultraviolet irradiation is not increased, the line width of the middle part (center part) and the deepest part (bottom part) of the pattern cross section does not increase with respect to the line width of the surface part. Photosensitive resin composition that can form a pattern with good resist shape and excellent resolution, photosensitive element using the photosensitive resin composition, permanent mask resist, and printed wiring comprising the permanent mask resist Is to provide a board.
In addition, by using the photosensitive resin composition of the present invention, it was excellent in the miniaturization of electronic devices in recent years, and the formation stability of the finer hole diameter and the pitch between the holes due to higher performance, A photosensitive element capable of pattern formation, a permanent mask resist, and a printed wiring board including the permanent mask resist.

As a result of intensive studies to solve the above problems, the present inventors have found that the problem can be solved by the following invention. That is, the present invention provides the following photosensitive resin composition, photosensitive element, permanent mask resist, and printed wiring board.

[1] (A) acid-modified vinyl group-containing epoxy resin, (B) acylphosphine oxide photopolymerization initiator, (C1) alkylaminobenzene derivative, (C2) pyrazoline sensitizer or anthracene sensitizer (C3) at least one photopolymerization initiator selected from an imidazole photopolymerization initiator, an acridine photopolymerization initiator, and a titanocene photopolymerization initiator, (C4) a hindered phenol antioxidant, a quinone oxidation At least one antioxidant selected from an antioxidant, an amine-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant, and (C5) at least one (C) addition selected from thiol group-containing compounds Photosensitive resin composition comprising an agent and (D) a photopolymerizable compound.
[2] A photosensitive element comprising a support and a photosensitive layer using the photosensitive resin composition according to the above [1] on the support.
[3] A permanent mask resist formed by the photosensitive resin composition according to the above [1].
[4] A printed wiring board comprising the permanent mask resist according to [3].

According to the present invention, the photosensitivity that can form a pattern with excellent linearity of the pattern outline, excellent resist shape, and excellent resolution without occurrence of undercut that causes the bottom to be removed and lack of the upper part of the resist. Resin composition, photosensitive element capable of forming pattern with excellent formation stability of fine hole diameter and hole pitch, permanent mask resist, and printed wiring board having the same .

It is a schematic diagram of the cross section of the resist formed using the photosensitive resin composition of this invention. It is a figure which shows the pattern shape of the negative mask used in the Example. It is a figure which shows the pattern shape of the negative mask used in the Example.

[Photosensitive resin composition]
A photosensitive resin composition according to an embodiment of the present invention (hereinafter, also simply referred to as “this embodiment”) includes (A) an acid-modified vinyl group-containing epoxy resin (hereinafter also referred to as “component (A)”). (B) acylphosphine oxide photopolymerization initiator (hereinafter also referred to as “component (B)”), (C1) alkylaminobenzene derivative (hereinafter also referred to as “(C1) component”), (C2) pyrazoline Sensitizer or anthracene sensitizer (hereinafter also referred to as “component (C2)”), (C3) an imidazole photopolymerization initiator, an acridine photopolymerization initiator, and a titanocene photopolymerization initiator. At least one photopolymerization initiator (hereinafter also referred to as “component (C3)”), (C4) a hindered phenol-based antioxidant, a quinone-based antioxidant, an amine-based antioxidant, a sulfur-based antioxidant, and Selected from at least one antioxidant selected from phosphorus-based antioxidants (hereinafter also referred to as “(C4) component”) and (C5) thiol group-containing compound (hereinafter also referred to as “(C5) component”). Photosensitive resin composition comprising at least one (C) additive (hereinafter also referred to as “(C) component”) and (D) a photopolymerizable compound (hereinafter also referred to as “(D) component”). It is.
Hereinafter, each component will be described.

<(A) Acid-modified vinyl group-containing epoxy resin>
The photosensitive resin composition of this embodiment contains an acid-modified vinyl group-containing epoxy resin as the component (A).
(A) The acid-modified vinyl group-containing epoxy resin is not particularly limited as long as the epoxy resin is modified with a vinyl group-containing organic acid. The epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) An epoxy resin (a ′) obtained by reacting is preferable, and an epoxy resin (a ′) obtained by reacting the epoxy resin (a ′) with a saturated or unsaturated group-containing polybasic acid anhydride (c). ') Is more preferred.

The epoxy resin (a) is preferably at least one selected from epoxy resins having structural units represented by the following general formulas (I) to (V). The epoxy resin which has a structural unit shown by each general formula is demonstrated.

[Novolac type epoxy resin having the structural unit represented by the general formula (I)]
First, as an epoxy resin (a), the novolak-type epoxy resin which has a structural unit shown by the following general formula (I) is mentioned preferably, As an epoxy resin which has such a structural unit, the following general formula ( A novolak type epoxy resin represented by I ′) is preferred.

In the general formula (I), R ¹¹ represents a hydrogen atom or a methyl group, and Y ¹ represents a glycidyl group.
In the novolac type epoxy resin having the structural unit represented by the general formula (I), the content of the structural unit represented by the general formula (I) is preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably. It is 95 mass% or more.
In the general formula (I ′), R ¹¹ ′ represents a hydrogen atom or a methyl group, Y ¹ ′ represents a hydrogen atom or a glycidyl group, and the molar ratio of the hydrogen atom to the glycidyl group is preferably 0: 100 to 30:70, more preferably 0: 100 to 10:90, and still more preferably 0: 100. As can be seen from the molar ratio of hydrogen atom to glycidyl group, at least one Y ¹ ′ represents a glycidyl group. In general formula (I ′), n1 represents an integer of 1 or more. The plurality of R ¹¹ ′ may be the same or different, and the plurality of Y ¹ ′ may be the same or different.

N1 is an integer of 1 or more as described above, preferably 10 to 200, more preferably 30 to 150, and still more preferably 30 to 100. When n1 is within the above range, there is a tendency that a resist pattern that is superior due to the balance of resist shape, resolution, heat resistance, adhesion, and electrical insulation is obtained.

Preferred examples of the novolak type epoxy resin represented by the general formula (I ′) include a phenol novolak type epoxy resin and a cresol novolak type epoxy resin. These novolak-type epoxy resins can be obtained, for example, by reacting a phenol resin such as a phenol novolak resin or a cresol novolak resin with an epihalohydrin such as epichlorohydrin by a known method.

Examples of the novolac type epoxy resin represented by the general formula (I ′) include YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, YDPN-602 (and above, NSSMC). Chemical Co., Ltd., trade name), DEN-431, DEN-439 (Dow Chemical Co., Ltd., trade name), EOCN-120, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012 , EOCN-1025, EOCN-1027, BREN (above, Nippon Kayaku Co., Ltd., trade name), EPN-1138, EPN-1235, EPN-1299 (above, BASF Japan Ltd., trade name), N-730, N-770, N-865, N-665, N-673, VH-4150, VH- 240 (or more, DIC (Ltd.), trade name) and the like are commercially available.

[Epoxy resin having structural unit represented by general formula (II)]
As the epoxy resin (a), an epoxy resin having a structural unit represented by the following general formula (II) is preferably exemplified. As an epoxy resin having such a structural unit, for example, the following general formula (II ′) Preferred are the bisphenol A type epoxy resins and bisphenol F type epoxy resins shown.

In the general formula (II), R ¹² represents a hydrogen atom or a methyl group, and Y ² represents a glycidyl group.
In the epoxy resin having the structural unit represented by the general formula (II), the content of the structural unit represented by the general formula (II) is preferably 70% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass. % Or more.
In the general formula (II ′), R ¹² ′ represents a hydrogen atom or a methyl group, Y ² ′ represents a hydrogen atom or a glycidyl group, and the molar ratio of the hydrogen atom to the glycidyl group is preferably 0: 100 to 30:70, more preferably 0: 100 to 10:90, and still more preferably 0: 100. As can be seen from the molar ratio between the hydrogen atom and the glycidyl group, at least one Y ² ′ represents a glycidyl group. In general formula (II ′), n2 represents an integer of 1 or more. The plurality of R ¹² ′ may be the same or different, and when n2 is 2 or more, the plurality of Y ² ′ may be the same or different.

N2 is an integer of 1 or more as described above, preferably 10 to 100, more preferably 10 to 80, and still more preferably 15 to 60. When n2 is within the above range, there is a tendency that a resist pattern that is superior in the balance of resist shape, resolution, adhesion, heat resistance, and electrical insulation is obtained.

The bisphenol A type epoxy resin or bisphenol F type epoxy resin represented by the general formula (II ′) and Y ² ′ is a glycidyl group is, for example, a bisphenol A type epoxy resin or bisphenol F represented by the following general formula (VII): It can be obtained by reacting a hydroxyl group of an epoxy resin with an epihalohydrin such as epichlorohydrin.

In general formula (VII), R ¹² and n2 are the same as described above.

The amount of epihalohydrin used depends on the general formula (VII) considering that a resist pattern that is superior in the balance of resist shape, resolution, film strength, heat resistance, insulation reliability, thermal shock resistance, and resolution can be obtained. The amount is preferably 2 to 10 moles per mole of the hydroxyl group in the epoxy resin represented by

From the same viewpoint, it is preferable to use a basic catalyst in the reaction between the epoxy resin represented by the general formula (VII) and epihalohydrin. Preferred examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides, and the like, and alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide. Is more preferable from the viewpoint of catalytic activity. Further, the amount used is preferably 0.9 to 2 moles relative to 1 mole of hydroxyl groups in the epoxy resin represented by the general formula (VII).

In the reaction of the epoxy resin represented by the general formula (VII) with epihalohydrin, from the viewpoint of further increasing the reaction rate, examples of the organic solvent include alcohols such as methanol and ethanol; cellosolves such as methyl cellosolve and ethyl cellosolve; tetrahydrofuran It is preferable to use ethers such as dioxane; polar organic solvents such as dimethylformamide, dimethylacetamide, and dimethylsulfoxide. Among these, one kind can be used alone, or two or more kinds can be used in combination. From the viewpoint of polarity adjustment, two or more kinds are preferably used in combination.

The reaction temperature is preferably 20 to 120 ° C., more preferably 50 to 120 ° C., and the reaction time is preferably 0.5 to 10 hours. When the reaction temperature and reaction time are within the above ranges, the reaction is unlikely to be slow and side reaction products are unlikely to occur.

After the above reaction, preferably, the unreacted epihalohydrin, the organic solvent, and the like are distilled off by distillation under heating and reduced pressure to obtain the epoxy resin represented by the general formula (II ′).
Further, from the viewpoint of obtaining a higher purity epoxy resin, the obtained epoxy resin can be dissolved again in an organic solvent, and a basic catalyst such as the above alkali metal hydroxide can be added and reacted. At this time, from the viewpoint of increasing the reaction rate, it is preferable to use a phase transfer catalyst such as a quaternary ammonium salt or crown ether in the range of 0.1 to 3% by mass with respect to the epoxy resin. In this case, a high-purity epoxy resin can be obtained by removing salts generated after completion of the reaction by filtration, washing with water, and the like, and further distilling off the organic solvent and the like under heating and reduced pressure.

Examples of the bisphenol A type epoxy resin or bisphenol F type epoxy resin represented by the general formula (II ′) include, for example, Epicoat 807, 815, 825, 827, 828, 834, 1001, 1004, 1007 and 1009 (above, Mitsubishi Chemical) (Trade name), DER-330, DER-301, DER-361 (above, manufactured by Dow Chemical Co., Ltd., trade name), YD-8125, YDF-170, YDF-175S, YDF-2001, YDF-2004, YDF-8170 (above, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name) and the like are commercially available.

[Epoxy resin having a structural unit represented by general formula (III)]
As the epoxy resin (a), an epoxy resin having a structural unit represented by the following general formula (III) is preferably exemplified. As an epoxy resin having such a structural unit, for example, the following general formula (III ′) The triphenolmethane type epoxy resin shown is preferable.

In the general formulas (III) and (III ′), Y ³ represents a hydrogen atom or a glycidyl group, and the molar ratio of the hydrogen atom to the glycidyl group is preferably 0: 100 to 30:70. As can be seen from the molar ratio of hydrogen atom to glycidyl group, at least one Y ³ represents a glycidyl group. In the formula (III ′), n3 represents an integer of 1 or more. The plurality of Y ³ may be the same or different.

N3 is an integer of 1 or more as described above, preferably 10 to 100, more preferably 15 to 80, and still more preferably 15 to 70. When n3 is within the above range, a resist pattern that is superior in the balance of resist shape, resolution, heat resistance, adhesion, and electrical insulation can be obtained.

In the epoxy resin having the structural unit represented by the general formula (III), the content of the structural unit represented by the general formula (III) is preferably 70% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass. % Or more.

As the triphenolmethane type epoxy resin represented by the general formula (III ′), for example, FAE-2500, EPPN-501H, EPPN-502H (above, Nippon Kayaku Co., Ltd., trade name) are commercially available. It is available.

[Bisphenol novolac-type epoxy resin having a structural unit represented by the general formula (IV)]
As the epoxy resin (a), a bisphenol novolac type epoxy resin having a structural unit represented by the following general formula (IV) is preferably exemplified.

In the general formula (IV), R ¹³ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a sulfonic group, or a trihalomethyl group, Y ⁴ represents a hydrogen atom or a glycidyl group. At least one Y ⁴ represents a glycidyl group, and a plurality of R ¹³ may be the same or different.

The alkyl group of R ¹³ preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 3 carbon atoms. The alkyl group may be linear or branched and may be substituted with a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amide group, an alkoxy group, or the like.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a sec-pentyl group, an isopentyl group, and a neopentyl group. Among them, a methyl group is more preferable.
Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and the like, preferably an aryl group having 6 to 20 ring carbon atoms, more preferably an aryl group having 6 to 14 ring carbon atoms. It is. The aryl group may be substituted with a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amide group, an alkoxy group, or the like.
The aralkyl group is not particularly limited as long as one of the hydrogen atoms of the alkyl group is substituted with the aryl group, and examples thereof include a benzyl group, a phenylethyl group, a phenylpropyl group, and a naphthylmethyl group. Is mentioned. The aralkyl group may be substituted with a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amide group, an alkoxy group, or the like.

In the epoxy resin having the structural unit represented by the general formula (IV), the content of the structural unit represented by the general formula (IV) is preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably 95%. It is at least mass%.
Within the above range, a resist pattern that is superior in the balance of resist shape, resolution, heat resistance, adhesion, and electrical insulation can be obtained.

[Bisphenol novolac-type epoxy resin having a structural unit represented by the general formula (V)]
Preferred examples of the epoxy resin (a) include bisphenol novolac type epoxy resins having a structural unit represented by the following general formula (V).

In the general formula (V), R ¹⁴ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a sulfone group, or a trihalomethyl group, and Y ⁵ represents a hydrogen atom or a glycidyl group. At least one Y ⁵ represents a glycidyl group, and a plurality of R ¹⁴ may be the same or different. Examples of the alkyl group, aryl group, and aralkyl group for R ¹⁴ are the same as those described for R ¹³ , and preferred embodiments are also the same.

In the epoxy resin having the structural unit represented by the general formula (V), the content of the structural unit represented by the general formula (V) is preferably 70% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass. % Or more. Within the above range, a resist pattern that is superior in the balance of resist shape, resolution, heat resistance, adhesion, and electrical insulation can be obtained.

In the general formula (V), when R ¹⁴ is a hydrogen atom and Y ⁵ is a glycidyl group, EXA-7376 series (manufactured by DIC Corporation, trade name), and R ¹⁴ is a methyl group, Y ⁵ having a glycidyl group is commercially available as EPON SU8 series (trade name, manufactured by Mitsubishi Chemical Corporation).

The bisphenol novolac type epoxy resin having the structural units represented by the general formulas (IV) and (V) includes, for example, a hydroxyl group of the bisphenol novolac resin represented by the following general formulas (VIII) and (IX) and an epihalohydrin such as epichlorohydrin. Can be obtained by reacting.

In the general formula (VIII), R ¹³ is the same as R ¹³ in the above the general formula (IV), in the general formula (IX), R ¹⁴ is a R ¹⁴ in the general formula (V) The same.

The bisphenol novolac resin having the structural units represented by the general formulas (VIII) and (IX) is preferably a molecular structure of, for example, a bisphenol compound and an aldehyde compound or a ketone compound, and an alkyl group having 1 to 4 carbon atoms. It can be obtained by reacting in the presence of sulfonic acid contained therein.

Here, the bisphenol compound is not particularly limited as long as it is a compound having two hydroxyphenyl groups. For example, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, Bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol TMC, bisphenol Z and the like are preferred, and bisphenol A and bisphenol F are more preferred.

Preferred examples of the aldehyde compound to be reacted with the bisphenol compound include formaldehyde, acetaldehyde, benzaldehyde, 4-methylbenzaldehyde, 3,4-dimethylbenzaldehyde, biphenylaldehyde, naphthylaldehyde, and the like, and examples of the ketone compound include benzophenone, fluorenone, Indanone and the like are preferred. Among these, formaldehyde is preferable.

Examples of the sulfonic acid having an alkyl group having 1 to 4 carbon atoms in the molecular structure include alkane sulfonic acids such as methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid and butane sulfonic acid, and perfluoro having a fluorine atom in the alkane portion. Preferred examples include alkanesulfonic acid.

More specifically, the bisphenol novolac type epoxy resin having the structural units represented by the general formulas (IV) and (V) is preferably obtained as follows.
The above bisphenol compound and aldehyde compound or ketone compound are charged into a reaction vessel, and sulfonic acid is added continuously or intermittently so as to maintain the range of 20 to 200 ° C. while stirring in an inert gas atmosphere. Then, a bisphenol compound is reacted with an aldehyde compound or a ketone compound to obtain a crude bisphenol novolac resin. Next, the crude bisphenol novolak resin is extracted with a water-insoluble organic solvent to obtain a bisphenol novolak resin solution, which is washed with water and neutralized, and further, the water-insoluble organic solvent is distilled off to obtain a bisphenol novolak-type epoxy. A resin is obtained.

Here, as the water-insoluble organic solvent, those having a boiling point of 100 to 130 ° C. are preferable from the viewpoint of improving the working efficiency of extraction, washing and neutralization. Preferred examples of the water-insoluble organic solvent include butanol, pentyl alcohol, methoxyethanol, ethoxyethanol, diethylene glycol, and methyl isobutyl ketone. Among these, butanol, methoxyethanol, and methyl isobutyl ketone are more preferable, and methyl isobutyl is preferable. More preferred are ketones.

The above water washing is performed until the crude bisphenol novolak resin solution has a pH of 3 to 7, more preferably pH 5 to 7, and a basic substance such as sodium hydroxide, sodium carbonate, ammonia, triethylenetetramine is used as necessary. May be neutralized.
The distillation is preferably performed by distillation under reduced pressure under conditions of, for example, a temperature of 170 to 200 ° C. and a pressure of 3 kPa or less. A bisphenol novolac resin having a high purity can be obtained by performing such a condition. .

The epoxy resin (a) is a novolac type epoxy resin having a structural unit represented by the general formula (I) and a general formula (II) from the viewpoint of excellent process tolerance and improved solvent resistance. An epoxy resin having a structural unit and a bisphenol novolac type epoxy resin having a structural unit represented by the general formula (IV) are preferable, and a novolac type epoxy resin represented by the general formula (I ′) is represented by the general formula (II ′). Bisphenol A type epoxy resin or bisphenol F type epoxy resin, and bisphenol novolac A type epoxy resin or bisphenol F type epoxy resin having a structural unit represented by the general formula (IV) are more preferable.
In addition, from the viewpoint of further reducing the warpage of the thin film substrate and further improving the thermal shock resistance, an epoxy resin having a structural unit represented by the general formula (IV) and a structural unit represented by the general formula (V) It is preferable to use together with the epoxy resin which has.

(Vinyl group-containing monocarboxylic acid (b))
Examples of the vinyl group-containing monocarboxylic acid (b) to be reacted with the epoxy resin (a) include acrylic acid, a dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid. , Cinnamic acid, crotonic acid, acrylic acid derivatives such as α-cyanocinnamic acid; half-ester compounds, vinyl group-containing monoglycidyl ether or vinyl group-containing monoglycidyl which are reaction products of hydroxyl group-containing acrylate and dibasic acid anhydride Preferable examples include a half-ester compound which is a reaction product of an ester and a dibasic acid anhydride.

The half ester compound is obtained by reacting a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester with a dibasic acid anhydride in an equimolar ratio. These vinyl group-containing monocarboxylic acids (b) can be used singly or in combination of two or more.

Examples of the hydroxyl group-containing acrylate, vinyl group-containing monoglycidyl ether, and vinyl group-containing monoglycidyl ester used in the synthesis of the half ester compound as an example of the vinyl group-containing monocarboxylic acid (b) include hydroxyethyl (meth) Acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) Preferred examples include acrylate, vinyl glycidyl ether, glycidyl (meth) acrylate and the like.

As the dibasic acid anhydride used for the synthesis of the above half ester compound, one containing a saturated group or one containing an unsaturated group can be used. Specific examples of dibasic acid anhydrides include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride. Preferred are acid, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.

In the reaction of the epoxy resin (a) with the vinyl group-containing monocarboxylic acid (b), the vinyl group-containing monocarboxylic acid (b) is 0.6 to 0.6 to 1 equivalent of the epoxy group of the epoxy resin (a). The reaction is preferably performed at a ratio of 1.05 equivalents, more preferably at a ratio of 0.8 to 1.0 equivalents, and further at a ratio of 0.9 to 1.0 equivalents. preferable. By reacting at such a ratio, the photopolymerizability is improved and the photosensitivity is further improved.

The reaction between the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) can be performed by dissolving the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) in an organic solvent.
Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, Glycol ethers such as dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate; aliphatic carbonization such as octane and decane Hydrogen: petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha are preferred.

Furthermore, it is preferable to use a catalyst in order to promote the reaction. Preferred examples of the catalyst include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide, and triphenylphosphine. The amount of the catalyst used is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). The amount used is preferable because the reaction between the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) is promoted.

It is preferable to use a polymerization inhibitor for the purpose of preventing polymerization during the reaction. Preferred examples of the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like. The amount of the polymerization inhibitor used is preferably 0.01 to 1 part by mass with respect to 100 parts by mass in total of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). The amount used is preferable because the storage stability (shelf life) of the composition is improved. The reaction temperature is preferably 60 to 150 ° C., more preferably 80 to 120 ° C.

If necessary, a vinyl group-containing monocarboxylic acid (b) and a phenolic compound such as p-hydroxyphenethyl alcohol, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic acid A polybasic acid anhydride such as an anhydride can be used in combination.

The epoxy resin (a ′) thus obtained has a hydroxyl group formed by an addition reaction between the epoxy group of the epoxy resin (a) and the carboxyl group of the vinyl group-containing monocarboxylic acid (b). It is guessed.

(Polybasic acid anhydride (c))
(A) As an acid-modified vinyl group-containing epoxy resin, an epoxy resin (a ″) obtained by reacting the above-mentioned epoxy resin (a ′) with a polybasic acid anhydride (c) is also preferably mentioned. In (a ″), the hydroxyl group in the epoxy resin (a ′) (including the original hydroxyl group in the epoxy resin (a)) and the acid anhydride group of the polybasic acid anhydride (c) are half-esterified. It is presumed that

As the polybasic acid anhydride (c), those containing a saturated group and those containing an unsaturated group can be preferably used. Specific examples of the polybasic acid anhydride (c) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexa Preferred examples include hydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.

In the reaction of the epoxy resin (a ′) with the polybasic acid anhydride (c), the polybasic acid anhydride (c) is added in an amount of 0.1 to 1. By reacting with 0 equivalent, the acid value of the acid-modified vinyl group-containing epoxy resin can be adjusted.

(A) The acid value of the acid-modified vinyl group-containing epoxy resin is preferably 30 to 150 mgKOH / g, more preferably 40 to 120 mgKOH / g, and further preferably 50 to 100 mgKOH / g. When the acid value is 30 mgKOH / g or more, the solubility of the photosensitive resin composition in a dilute alkali solution is unlikely to decrease, and when it is 150 mgKOH / g or less, the electrical characteristics of the cured film are unlikely to decrease.

The reaction temperature between the epoxy resin (a ′) and the polybasic acid anhydride (c) is preferably 60 to 120 ° C.

Further, as necessary, as the epoxy resin (a), for example, a hydrogenated bisphenol A type epoxy resin can be partially used together. Furthermore, as the acid-modified vinyl group-containing epoxy resin (A), a styrene-maleic acid-based resin such as a hydroxyethyl (meth) acrylate modified product of a styrene-maleic anhydride copolymer may be used in combination.

(A) The weight average molecular weight of the acid-modified vinyl group-containing epoxy resin is preferably 3000 to 30000, more preferably 4000 to 25000, and still more preferably 5000 to 18000. When the weight average molecular weight of the component (A) is within the above range, a pattern excellent in balance of resist shape, resolution, heat resistance, adhesion, and electrical insulation can be obtained. Here, the weight average molecular weight is a polyethylene-converted weight average molecular weight measured by a gel permeation chromatography (GPC) method using tetrahydrofuran as a solvent. More specifically, for example, a value measured by the following GPC measurement apparatus and measurement conditions and converted using a standard polystyrene calibration curve can be used as the weight average molecular weight. The calibration curve is prepared by using 5 sample sets (“PStQuick MP-H” and “PStQuick B”, manufactured by Tosoh Corporation) as standard polystyrene.
(GPC measuring device)
GPC apparatus: High-speed GPC apparatus “HLC-8320GPC”, detector is a differential refractometer, manufactured by Tosoh Corporation Column: column TSKgel SuperMultipore HZ-H (column length: 15 cm, column inner diameter: 4.6 mm), Tosoh Corporation ) Made (measurement conditions)
Solvent: Tetrahydrofuran (THF)
Measurement temperature: 40 ° C
Flow rate: 0.35 ml / min Sample concentration: 10 mg / THF 5 ml
Injection volume: 20 μl

(A) As an acid-modified vinyl group-containing epoxy resin, a novolac type epoxy resin having a structural unit represented by general formula (I), preferably a novolac type epoxy resin represented by general formula (I ′), or a general formula ( II) An epoxy resin having a structural unit represented by formula (II), preferably a bisphenol A type epoxy resin and a bisphenol F type epoxy resin represented by formula (II ′), and a vinyl group-containing monocarboxylic acid (b) are reacted. The resulting epoxy resin (a ′) and the epoxy resin (a ″) obtained by reacting the epoxy resin (a ′) with a saturated or unsaturated group-containing polybasic acid anhydride (c) are preferred, Epoxy resin (a ″) is more preferable.

These epoxy resins (a ′) and (a ″) can be used singly or in combination of two or more, and are preferably used in combination of plural kinds. As a combination, an epoxy resin (a ′) or (a ″) obtained from a novolac type epoxy resin represented by the general formula (I ′), a bisphenol A type epoxy resin and a bisphenol represented by the general formula (II ′) Two types of combinations with epoxy resin (a ′) or (a ″) obtained from F-type epoxy resin are preferred, and epoxy resin (a ″ obtained from novolac type epoxy resin represented by general formula (I ′) ) And an epoxy resin (a ″) obtained from a bisphenol A type epoxy resin and a bisphenol F type epoxy resin represented by the general formula (II ′) are more preferable.
An epoxy resin (a ′) or (a ″) obtained from a novolac type epoxy resin represented by the general formula (I ′), a bisphenol A type epoxy resin and a bisphenol F type epoxy resin represented by the general formula (II ′) The mass mixing ratio with the epoxy resin (a ′) or (a ″) obtained from is preferably 95: 5 to 30:70, more preferably 90:10 to 40:60, and 80:20 to 45:55. Is more preferable.

Moreover, when using the (C5) thiol group containing compound mentioned later as (C) component, the epoxy resin (a ') obtained from the bisphenol novolak-type epoxy resin which has a structural unit shown by general formula (IV), or (a '') And an epoxy resin (a ′) or (a ″) obtained from a bisphenol A type epoxy resin and a bisphenol F type epoxy resin represented by the general formula (II ′) are preferable, An epoxy resin (a ″) obtained from a bisphenol novolac A type epoxy resin or a bisphenol F type epoxy resin having a structural unit represented by the formula (IV), a bisphenol A type epoxy resin represented by the general formula (II ′), and Two combinations with an epoxy resin (a ″) obtained from a bisphenol F-type epoxy resin are more preferable.
Epoxy resin (a ′) or (a ″) obtained from bisphenol novolac type epoxy resin having a structural unit represented by general formula (IV) and bisphenol A type epoxy resin and bisphenol F represented by general formula (II ′) The mass mixing ratio with the epoxy resin (a ′) or (a ″) obtained from the type epoxy resin is preferably 90:10 to 30:70, more preferably 80:20 to 40:60, and 70:30 to 50:50 is more preferable.

The content of the component (A) in which the total solid content in the photosensitive resin composition is 100 parts by mass is preferably 20 to 80 parts by mass, more preferably 30 to 75 parts by mass, and even more preferably 40 to 75 parts by mass. When the content of the component (A) is within the above range, a coating film that is superior in heat resistance, electrical characteristics, and chemical resistance can be obtained. Here, the total amount of solid content in the present embodiment is the total amount of solid content contained in the components (A) to (F). For example, when the photosensitive resin composition of the present embodiment includes the components (A) to (D), the total amount of solids contained in the components (A) to (D) is the photosensitive property of the present embodiment. When the resin composition contains the components (A) to (E), the total amount of solids contained in the components (A) to (E) is the same as that of the photosensitive resin composition of the present embodiment. When the component (F) is included, the total amount of solids contained in the components (A) to (F) is the total amount of solids.

<(B) Acylphosphine oxide photopolymerization initiator>
The photosensitive resin composition of this embodiment contains an acylphosphine oxide photopolymerization initiator as the component (B).
The (B) acylphosphine oxide photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator having an acylphosphine oxide group (═P (═O) —C (═O) — group). 2,6-dimethoxybenzoyl) -2,4,6-trimethylbenzoyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl -2,4,6-trimethylbenzoylphenyl phosphinate, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, (2,5-dihydroxyphenyl) diphenylphosphine oxide, (p-hydroxyphenyl) diphenylphosphine Oxide, bis (p-hi Rokishifeniru) phenylphosphine oxide, and tris (p- hydroxyphenyl) phosphine oxide, and the like preferably can be used in combination either singly or in combination.

The content of the (B) acylphosphine oxide-based photopolymerization initiator is preferably 0.2 to 15 parts by mass with the total solid content in the photosensitive resin composition being 100 parts by mass. When the amount is 0.2 parts by mass or more, the exposed portion is hardly eluted during development, and when the amount is 15 parts by mass or less, the heat resistance is not easily lowered. For the same reason, the content of the (B) photopolymerization initiator is more preferably 0.2 to 10 parts by mass, further preferably 0.2 to 5 parts by mass, and particularly preferably 0.5 to 5 parts by mass. Preferably, 0.5 to 3 parts by mass is very preferable.

In addition, photopolymerization initiation aids such as tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine Can be used singly or in combination of two or more.

<(C) Additive>
The photosensitive resin composition of the present embodiment includes (C1) an alkylaminobenzene derivative, (C2) a pyrazoline sensitizer or anthracene sensitizer, (C3) an imidazole photopolymerization initiator, At least one photopolymerization initiator selected from acridine photopolymerization initiator and titanocene photopolymerization initiator, (C4) hindered phenol antioxidant, quinone antioxidant, amine antioxidant, sulfur It contains at least one antioxidant selected from an antioxidant and a phosphorus-based antioxidant, and at least one selected from (C5) thiol group-containing compounds. By using these additives in combination with (B) an acylphosphine oxide photopolymerization initiator, a photosensitive resin capable of forming a pattern having excellent linearity of the pattern outline, excellent resist shape, and excellent resolution. A composition can be obtained.

[(C1) alkylaminobenzene derivative]
The (C1) alkylaminobenzene derivative is not particularly limited as long as it has an alkylamino group in the benzene ring, and functions effectively as a hydrogen donor, and further improves the photosensitivity and aging stability of the photosensitive resin composition. It can be improved. Here, the hydrogen donor means a compound that can donate a hydrogen atom to a radical generated by the exposure treatment of the photopolymerization initiator. In the present embodiment, the combination of the (B) acylphosphine oxide photopolymerization initiator and the (C1) alkylaminobenzene derivative as a hydrogen donor has a particularly good pattern contour linearity and a resist shape. It is effective in that a pattern having excellent and excellent resolution can be formed.

Preferred examples of (C1) alkylaminobenzene derivatives include phenylglycine derivatives, aminobenzoic acid derivatives, aminobenzoic acid ester derivatives, and the like.
Preferable examples of the phenylglycine derivative include N-phenylglycine, N, N-diphenylglycine, N-naphthylglycine and the like.
Preferred examples of the aminobenzoic acid derivative include 2-methylaminobenzoic acid and 2-ethylaminobenzoic acid. As the aminobenzoic acid ester derivative, ethyl N, N-dimethylaminobenzoate, ethyl N, N-diethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate, isoamyl N, N-diethylaminobenzoate and the like are preferable. Can be mentioned.

In the present embodiment, an aromatic amine compound having an alkylamino group may be used. Specific examples include, for example, dialkyldiphenylamines having an alkyl group having 8 to 14 carbon atoms, octylated diphenylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, N-phenyl-N′-isopropyl- p-phenylenediamine, N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, and N-phenyl-N ′-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine Etc. are preferable.
Among these (C1) alkylaminobenzene derivatives, N-phenylglycine, 2-methylaminobenzoic acid, and ethyl N, N-diethylaminobenzoate are preferable.

These (C1) alkylaminobenzene derivatives can be used singly or in combination of two or more. Moreover, you may use an aliphatic amine compound simultaneously with said alkylaminobenzene derivative. Specific examples include, for example, triethanolamine, triethylamine and the like.

The total content of the solid content in the photosensitive resin composition is 100 parts by mass. The content of the (C1) alkylaminobenzene derivative is preferably 0.01-5 parts by mass, more preferably 0.1-3 parts by mass, and 0 2 to 1.5 parts by mass is more preferable, and 0.2 to 1.0 part by mass is particularly preferable. If the content is 0.1 parts by mass or more, the solution of the photosensitive resin composition is difficult to gel, and if it is 5 parts by mass or less, the photosensitivity is unlikely to decrease.

[(C2) pyrazoline sensitizer or anthracene sensitizer]
The component (C2) is a pyrazoline sensitizer or an anthracene sensitizer.
(C2) By adding a pyrazoline-based sensitizer, even in digital exposure, there is no occurrence of undercut that causes the bottom to be removed, and there is no loss of the upper part of the resist. And a photosensitive resin composition capable of forming a pattern with excellent resolution can be obtained.

(C2) The pyrazoline sensitizer is not particularly limited as long as it is a sensitizer having a pyrazole ring, but a pyrazoline sensitizer represented by the following general formula (VI) is preferable.

In general formula (VI), R represents an alkyl group having 4 to 12 carbon atoms, a, b and c each represents an integer of 0 to 2, and the sum of a, b and c is 1 to 6. When the sum of a, b and c is 2 to 6, a plurality of R in the same molecule may be the same or different. The alkyl group of R may be linear or branched, and may be substituted with a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amide group, an alkoxy group, or the like. R is preferably an alkyl group having 4, 8, and 12 carbon atoms, and more specifically, an n-butyl group, a tert-butyl group, a tert-octyl group, and an n-dodecyl group are preferable. It is preferable that they are the same or different selected from.

Examples of such pyrazoline sensitizers include 1- (4-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5. -(4-tert-butyl-phenyl) -pyrazoline, 1,5-bis- (4-tert-butyl-phenyl) -3- (4-tert-butyl-styryl) -pyrazoline, 1- (4-tert- Octyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1,5-bis -(4-tert-octyl-phenyl) -3- (4-tert-octyl-styryl) -pyrazoline, 1- (4-dodecyl-phenyl) -3-sty 5-phenyl-pyrazoline, 1-phenyl-3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4-dodecyl-phenyl) -3- (4-dodecyl) -Styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4-tert-octyl-phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) ) -Pyrazoline, 1- (4-tert-butyl-phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4-dodecyl-phenyl) ) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3 (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4-dodecyl-phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl) -Phenyl) -pyrazoline, 1- (4-tert-octyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (2,4-di-n -Butyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1-phenyl-3- (3,5-di-tert-butyl-styryl) -5 (3,5-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (2,6-di-tert-butyl-styryl) -5- (2,6-di-tert-butyl-phenyl) ) -Pyrazoline, 1-phenyl-3- (2,5-di-tert-butyl-styryl) -5- (2,5-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (2, 6-di-n-butyl-styryl) -5- (2,6-di-n-butyl-phenyl) -pyrazoline, 1- (3,4-di-tert-butyl-phenyl) -3-styryl-5 -Phenyl-pyrazoline, 1- (3,5-di-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4-tert-butyl-phenyl) -3- (3,5- Di-tert-butyl-styryl) -5- (3,5-di-tert-butyl-phenyl) -pyrazoline and 1- (3,5-di-tert-butyl-phenyl) -3- (3,5- Di-tert-butyl-styryl) 5- (3,5-di -tert- butyl - phenyl) - pyrazoline, and the like preferably.

The total amount of solid content in the photosensitive resin composition is 100 parts by mass. The content of the (C2) pyrazoline-based sensitizer is preferably 0.01 to 10.0 parts by mass, more preferably 0.01 to 5 parts by mass. Preferably, 0.02 to 1 part by mass is more preferable, 0.03 to 0.5 part by mass is particularly preferable, and 0.03 to 0.2 part by mass is extremely preferable. (C2) If the content of the pyrazoline sensitizer is 0.01 parts by mass or more, the exposed part is less likely to elute during development, and if it is 10 parts by mass or less, a decrease in heat resistance can be suppressed. .

It is preferable to add (C2) anthracene sensitizer to the photosensitive resin composition of this embodiment.
The (C2) anthracene-based sensitizer used in the photosensitive resin composition of the present embodiment can form a pattern having excellent resist shape and excellent resolution by improving photocurability. To do.
As the (C2) anthracene sensitizer, for example, a compound represented by the following general formula (XI) is preferably exemplified.

In general formula (XI), l ₁₁ is an integer of 1 to 10, R ³ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, or an alkyl group having 2 to 8 carbon atoms. An alkenyl group, an aryl group, a heteroaryl group, or a —N (R ⁴ ) ₂ group, wherein two or more R ³ may be bonded to each other to form a cyclic structure, and the cyclic structure may contain a hetero atom; In addition, the alkyl group and the alkenyl group may be linear or branched, and may be substituted with a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amide group, an alkoxy group, or the like. Good. A plurality of R ³ and R ⁴ may be the same or different.
X is a single bond, oxygen atom, sulfur atom, carbonyl group, sulfonyl group, —N (R ′) — group, —C (═O) —O— group, —C (═O) —S— group, — SO ₂ —O— group, —SO ₂ —S— group, —SO ₂ —N (R ′) — group, —O—CO— group, —S—C (═O) — group, —O—SO ₂ -Group or -S-SO ₂ -group. However, a combination in which X is a single bond and R ³ is a hydrogen atom (that is, unsubstituted anthracene) is excluded. A plurality of X may be the same or different.
Here, R ⁴ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an aryl group, or a heteroaryl group. ⁴ may be bonded to each other to form a cyclic structure. The cyclic structure may contain a hetero atom. The alkyl group or alkenyl group may be linear or branched, and may be a halogen atom or alkyl group. , An aryl group, an aralkyl group, an amino group, an amide group, an alkoxy group, or the like.

Examples of the alicyclic group having 3 to 20 carbon atoms in R ³ and R ⁴ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, for example, a norbornyl group, a tricyclodecanyl group, and a tetracyclododecyl group. Preferred examples include a bridged alicyclic hydrocarbon group having 6 to 20 carbon atoms such as a group, an adamantyl group, a methyladamantyl group, an ethyladamantyl group, and a butyladamantyl group.
Preferred examples of the aryl group include those exemplified as the aryl group for R ¹³ , and examples of the heteroaryl group include a sulfur atom, an oxygen atom, a nitrogen atom, etc. Preferred are those obtained by substituting with a heteroatom.

Examples of R ³ and R ⁴ are hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-pentyl group, n Preferred examples include -hexyl group, n-heptyl group, n-octyl group, cyclopentyl group, cyclohexyl group, camphoyl group, norbornyl group, p-toluyl group, benzyl group, phenyl group and 1-naphthyl group.

Examples of the (C2) anthracene sensitizer represented by the above general formula (XI) include 1-methylanthracene, 2-methylanthracene, 2-ethylanthracene, 2-t-butylanthracene, 9- Alkylanthracenes such as methylanthracene; dialkylanthracenes such as 9,10-dimethylanthracene, 9,10-dipropylanthracene, 9,10-dibutylanthracene; 9- (hydroxymethyl) anthracene, 9- (2-hydroxyethyl) anthracene Hydroxyalkylanthracenes such as 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-di (2-ethylhexyloxy) anthracene and the like; 9- Bini Anthracene such as anthracene and 9-allyl anthracene; Anthracene such as 1-aminoanthracene, 2-aminoanthracene and 9- (methylaminomethyl) anthracene; Anthracene such as 9-anthracaldehyde and 10-methyl-9-anthracaldehyde Aldehydes: other 9-phenylanthracene, 9-acetylanthracene, 9,10-diphenylanthracene, 1,2-benzanthracene, 1,8,9-triacetoxyanthracene, 1,4,9,10-tetrahydroxyanthracene, etc. These anthracene sensitizers can be used alone or in combination of two or more.

Of these, diphenylanthracene, dialkylanthracene, and dialkoxyanthracene are preferable, and 9,10-dimethylanthracene, 9,10-diphenylanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9, More preferred are 10-dibutoxyanthracene and 9,10-di (2-ethylhexyloxy) anthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9, More preferred is 9,10-dialkoxyanthracene such as 10-di (2-ethylhexyloxy) anthracene. In the present embodiment, when these anthracene sensitizers are used, a photosensitive resin composition having photosensitivity particularly to radiation having a wavelength of 300 to 450 nm can be obtained, and photocurability can be improved. And a pattern with excellent resolution can be formed.

The content of the (C2) anthracene sensitizer with the total solid content in the photosensitive resin composition being 100 parts by mass is preferably 0.001 to 10 parts by mass. (C2) If the content of the anthracene sensitizer is within the above range, the photocurability can be improved, so that a pattern having excellent resist shape and excellent resolution can be formed. For the same reason, the content of the (C2) anthracene sensitizer is more preferably 0.01 to 5 parts by mass, further preferably 0.03 to 3 parts by mass, and 0.1 to 1.5 parts by mass. Particularly preferred.
Further, the content of (C2) anthracene sensitizer with respect to 100 parts by mass of (A) acid-modified vinyl group-containing epoxy resin is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass. 0.03 to 3 parts by mass is more preferable.

[(C3) At least one photopolymerization initiator selected from imidazole photopolymerization initiator, acridine photopolymerization initiator, and titanocene photopolymerization initiator]
The component (C3) is at least one photopolymerization initiator selected from an imidazole photopolymerization initiator, an acridine photopolymerization initiator, and a titanocene photopolymerization initiator.
In the present embodiment, the combination of the (B) acylphosphine oxide photopolymerizable initiator and the component (C3), in particular, has good pattern contour linearity, excellent resist shape, and excellent resolution. This is effective in forming a different pattern.

The imidazole photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator having an imidazole ring in the molecule, but 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5 ′. -Tetraphenyl-1,2'-biimidazole and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) Imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) ) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) 4,5-diphenyl imidazole dimer, and a 2-(p- methyl) -4,5-such as diphenyl imidazole dimer triarylimidazole dimer are preferably exemplified.

In the 2,4,5-triarylimidazole dimer, even though the two 2,4,5-triarylimidazoles constituting the dimer have the same structure, they have different structures. You may have. That is, the type of triaryl group in the 2,4,5-triarylimidazole dimer may be the same or different.

Examples of such a 2,4,5-triarylimidazole dimer include 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′- Biimidazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-chlorophenyl) imidazole Dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′- Tetra (p-fluorophenyl) imidazole dimer, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (p-chlorop-methoxyphenyl) imidazole dimer, 2,2'-bis o-chlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) imidazole dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′- Tetra (o, p-dibromophenyl) imidazole dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-chloronaphthyl) imidazole dimer, 2, 2′-bis (m, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylimidazole dimer, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5 5′-tetraphenylimidazole dimer, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) imidazole dimer, 2- ( o-Fluorophenyl) -4,5 Diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di ( p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methylmercaptophenyl) -4,5-diphenyl Imidazole dimer, 2,2′-bis (p-bromophenyl) -4,4 ′, 5,5′-tetraphenylimidazole dimer, 2,2′-bis (o-bromophenyl) -4, 4 ', 5,5'-tetra (o, p-dichlorophenyl) imidazole dimer, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetra (p-iodof Phenyl) imidazole dimer, 2,2′-bis (m-bromophenyl) -4,4 ′, 5,5′-tetraphenylimidazole dimer, 2,2′-bis (m, p-dibromophenyl) ) -4,4 ′, 5,5′-tetraphenylimidazole dimer and the like are preferred.

In these 2,4,5-triarylimidazole dimers, the aryl group further includes a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an aryl having 6 to 14 carbon atoms. Group, amino group, alkylamino group having 1 to 10 carbon atoms, nitro group, cyano group, mercapto group, alkylmercapto group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, allyl group, carbon number 1 A hydroxyalkyl group having 20 carbon atoms, a carboxyalkyl group having 1-10 carbon atoms in an alkyl group, an acyl group having 1-10 carbon atoms in an alkyl group, an alkoxyl group having 1-20 carbon atoms, or a group containing a heterocyclic ring, etc. May be substituted.

The acridine photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator having an acridine ring in the molecule, but 1,4-butylenebis-β- (acridin-9-yl) acrylate, p-xylylenebis [ β- (acridin-9-yl) acrylate], triethylene glycol bis [β- (acridin-9-yl) acrylate, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc. are preferable Can be mentioned.

The titanocene photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator of a metallocene compound having titanium as a metal, but bis (η ⁵ -cyclopentadienyl) -bis (2,6-difluoro-3 Preferred examples include-(1H-pyrrol-1-yl) phenyl) titanium, bis (2,4-cyclopentadienyl) -bis (2,6-difluoro-3- (1-pyryl) phenyl) titanium, and the like. These photoinitiators can be used individually by 1 type or in combination of 2 or more types.

The total content of the solid content in the photosensitive resin composition is 100 parts by mass. The content of the (C3) photopolymerization initiator is preferably 0.01 to 15 parts by mass, more preferably 0.01 to 5 parts by mass. The content is more preferably 01 to 3.5 parts by mass, and particularly preferably 0.02 to 1.0 parts by mass. When the content is 0.01 parts by mass or more, the solution of the photosensitive resin composition is hardly gelled, and when the content is 15 parts by mass or less, the photosensitivity is hardly lowered, which is preferable.
The total content of (B) acylphosphine oxide-based photopolymerization initiator and (C3) photopolymerization initiator in which the total solid content in the photosensitive resin composition is 100 parts by mass is preferably 0.2 to 15 parts by mass. It is. When the amount is 0.2 parts by mass or more, the exposed portion is hardly eluted during development, and when the amount is 15 parts by mass or less, the heat resistance is not easily lowered. For the same reason, the total content of (B) the photopolymerization initiator and (C3) the photopolymerization initiator is more preferably 0.2 to 10 parts by mass, and further preferably 0.2 to 5 parts by mass. 0.5 to 5 parts by mass is particularly preferred, and 0.5 to 3 parts by mass is very particularly preferred.
The mass ratio of the (B) acylphosphine oxide photopolymerization initiator to the (C3) photopolymerization initiator is preferably 100: 0.5 to 100: 8, more preferably 100: 1 to 100: 6. 100: 1 to 100: 5 is more preferable. A mass ratio within the above range is preferable because the resist shape is excellent and bottom curability and via hole diameter accuracy tend to be improved.

[(C4) at least one antioxidant selected from hindered phenolic antioxidants, quinone antioxidants, amine antioxidants, sulfur antioxidants, and phosphorus antioxidants]
The component (C4) is at least one antioxidant selected from a hindered phenol antioxidant, a quinone antioxidant, an amine antioxidant, a sulfur antioxidant, and a phosphorus antioxidant.
By using the component (C4), it is possible to obtain a photosensitive resin composition capable of forming a pattern having excellent resist shape and resolution and capable of forming a pattern having excellent solder heat resistance and flux corrosion resistance. it can.

As a hindered phenol-based antioxidant, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan Ltd., Irganox 1010 (trade name)) Thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan Ltd., Irganox 1035 (trade name)), octadecyl [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan Ltd., Irganox 1076 (trade name)), octyl 1-3,5-di-t-butyl-4-hydroxy-hydro cinnamon Acid (manufactured by BASF Japan Ltd., Irganox 1135 (trade name)), and 4,6-bis (octyl) Omethyl-o-cresol) (manufactured by BASF Japan Ltd., Irganox 1520L), etc., and n-octadecyl-3- (3′5′-di-t-butyl-4′-hydroxyphenyl) -propionate N-octadecyl-3- (3′-methyl-5′-t-butyl-4′-hydroxyphenyl) -propionate, n-tetradecyl-3- (3 ′, 5′-di-t-butyl-4 ′ -Hydroxyphenyl) -propionate, 1,6-hexanediol-bis- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate), 1,4-butanediol-bis- (3 -(3,5-di-t-butyl-4-hydroxyphenyl) -propionate), triethylene glycol-bis- (3- (3-t-butyl-5-methyl) -4-hydroxyphenyl) -propionate), tetrakis- (methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate methane, 3,9-bis (2- ( 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) 2,4,8,10-tetraoxaspiro (5,5) undecane, N, N '-Bis-3- (3'5'-di-t-butyl-4-hydroxyphenol) pripionylhexamethylenediamine, N, N'-tetramethylenebis-3- (3'-methyl-5'- t-butyl-4-hydroxyphenol) propionyldiamine, N, N′-bis- (3- (3,5-di-t-butyl-4-hydroxyphenol) propionyl) hydrazine, N-sa Lithylyl-N′-salicylidenehydrazine, 3- (N-salicyloyl) amino-1,2,4-triazole, and N, N′-bis (2- (3- (3,5-di-butyl-4 -Hydroxyphenyl) propionyloxy) ethyl) oxyamide and the like are preferred, and these can be used alone or in combination of two or more. In addition, preferable examples of the quinone antioxidant include quinone antioxidants such as hydroquinone, 2-t-butylhydroquinone, hydroquinone monomethyl ether, metaquinone, and benzoquinone. These may be used alone or in combination of two or more. Can be used in combination. These antioxidants having a phenolic hydroxyl group can be expected to capture peroxy radicals (ROO.), Alkyl radicals (R.), and the like.

Amine-based antioxidants include phenylnaphthylamine, 4,4′-dimethoxydiphenylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, di-t-butyldiphenylamine, N, N′-di (octyl). Phenyl) amine, 4-isopropoxydiphenylamine, N, N′-di (2-naphthyl) -p-phenylenediamine, bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, phenothiazine, etc. These are preferably mentioned, and these can be used alone or in combination of two or more. The amine-based antioxidant can be expected to capture peroxy radicals (ROO.).

As sulfur-based antioxidants, didodecyl-3,3′-thiodipropionate, ditetradecyl-3,3′-thiodipropionate, dioctadecyl-3,3′-thiodipropionate, ditridecyl-3,3 '-Thiodipropionate, pentaerythrityltetrakis (3-dodecylthiopropionate), pentaerythrityltetrakis (3-tetodecylthiopropionate), pentaerythrityltetrakis (3-tridecylthiopropionate) , Dilauryl-3,3-thiodipropionate, dimyristyl-3,3-thiodipropionate, distearyl-3,3-thiodipropionate, pentaerythrityltetrakis (3-laurylthiodipropionate, 2- Mercaptobenzimidazole, lauryl stearyl thiodip Pionate, zinc salt of 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc dibutylthiocarbamate and the like are preferred, and these may be used alone or in combination of two or more. Can be used in combination.

Phosphorous antioxidants include triphenyl phosphite, tris (methylphenyl) phosphite, triisooctyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tris (nonylphenyl) phosphite, tris (Octylphenyl) phosphite, tris [decylpoly (oxyethylene) phosphite, tris (cyclohexylphenyl) phosphite, tricyclohexylphosphite, tri (decyl) thiophosphite, triisodecylthiophosphite, phenyl-bis (2 -Ethylhexyl) phosphite, phenyl-diisodecyl phosphite, tetradecyl poly (oxyethylene) -bis (ethylphenyl) phosphato, phenyl-dicyclohexyl phosphite, phenyl-di Sooctyl phosphite, phenyl-di (tridecyl) phosphite, diphenyl-cyclohexyl phosphite, diphenyl-isooctyl phosphite, diphenyl-2-ethylhexyl phosphite, diphenyl-isodecyl phosphite, diphenyl-cyclohexyl phenyl phosphite, diphenyl Preferred are-(tridecyl) thiophosphite and the like, and these can be used alone or in combination of two or more.

As a sulfur-based antioxidant and a phosphorus-based antioxidant, an effect of decomposing peroxide can be expected. Commercially available products of sulfur-based antioxidants and phosphorus-based antioxidants include, for example, ADK STAB TPP (trade name, manufactured by ADEKA Corporation), Mark AO-412S (trade name, manufactured by ADEKA Corporation), Sumilyzer TPS ( And commercial products such as Sumitomo Chemical Co., Ltd., trade name).

In the present embodiment, (C4) a combination of a hindered phenolic antioxidant, a sulfurous antioxidant, a phosphorous antioxidant, etc. as the antioxidant can improve the resist shape. And particularly preferable in terms of obtaining excellent solder heat resistance and flux corrosion resistance.

The total content of the solid content in the photosensitive resin composition is 100 parts by mass (C4) The content of the antioxidant is preferably 0.2 to 15 parts by mass. When the amount is 0.2 parts by mass or more, the exposed portion is hardly eluted during development, and when the amount is 15 parts by mass or less, the heat resistance is not easily lowered. For the same reason, the content of the (C4) antioxidant is more preferably 0.2 to 10 parts by mass, further preferably 0.5 to 5 parts by mass, and particularly preferably 0.5 to 3 parts by mass. .

[(C5) thiol group-containing compound]
The component (C5) is a thiol group-containing compound, and the thiol group-containing compound functions effectively as a hydrogen donor and is considered to have an effect of further improving the photosensitivity and aging stability of the photosensitive resin composition. It is done.

Examples of (C5) thiol group-containing compounds include mercaptobenzoxazole, mercaptobenzothiazole, mercaptobenzimidazole, ethanethiol, benzenethiol, mercaptophenol, mercaptotoluene, 2-mercaptoethylamine, mercaptoethyl alcohol, mercaptoxylene, thiolenol. , 2-mercaptoquinoline, mercaptoacetic acid, α-mercaptopropionic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thiosalicylic acid, mercaptocyclohexane, α-mercaptodiphenylmethane, C-mercaptotetrazole, mercaptonaphthalene, mercaptonaphthol, 4-mercapto Biphenyl, mercapto hypoxanthine, mercaptopyridine, 2-mercaptopyrimidine, merc Captopurine, Thiocoumazone, Thiocumothiazone, Butane-2,3-dithiol, Thiocyanuric acid, 2,4,6-Trimercapto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2-anilino-4 , 6-dimercapto-s-triazine and the like.
These (C5) thiol group-containing compounds can be used singly or in combination of two or more. Among these, mercaptobenzoxazole, mercaptobenzothiazole and mercaptobenzimidazole are preferable, and mercaptobenzoimidazole is more preferable from the viewpoint of effectively functioning as a hydrogen donor and further improving the sensitivity and aging stability of the photosensitive resin composition. Benzimidazole.

The content of the (C5) thiol group-containing compound in the photosensitive resin composition is based on the total solid content of the photosensitive resin composition from the viewpoint of obtaining a photosensitive resin composition that can form a pattern with excellent resolution. Is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and still more preferably 0.2 to 1.5 parts by mass. (C5) If the content of the thiol group-containing compound is 0.01 parts by mass or more, the solution of the photosensitive resin composition tends to be difficult to gel, and if it is 5 parts by mass or less, a decrease in sensitivity is suppressed. Can do.

<(D) Photopolymerizable compound>
The photosensitive resin composition of this embodiment contains a photopolymerizable compound as component (D).
(D) The photopolymerizable compound is not particularly limited as long as it has a photopolymerizable functional group. For example, a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group , A compound having an ethylene oxide unsaturated group such as a nadiimide group or a (meth) acryloyl group is preferred, and a compound having a (meth) acryloyl group is more preferred from the viewpoint of reactivity.

(D) Examples of the photopolymerizable compound include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and the like Mono- or di (meth) acrylates of glycols; (meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; N, N-dimethylaminoethyl (meth) acrylate and the like Aminoalkyl (meth) acrylates; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tris-hydroxyethyl isocyanurate, etc. Polyhydric (meth) acrylates of these ethylene oxide or propylene oxide adducts; Phenolic ethylene oxide or propylene oxide adduct (meth) acrylates such as phenoxyethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenolΑ Preferred examples include (meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate; and melamine (meth) acrylate. These (D) photopolymerizable compounds can be used singly or in combination of two or more.

The content of the photopolymerizable compound (D) with the total solid content in the photosensitive resin composition being 100 parts by mass is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably. 1 to 15 parts by mass, particularly preferably 1.5 to 10 parts by mass. When the amount is 0.1 parts by mass or more, the exposed part is less likely to be eluted during development, and the sensitivity and resolution of the photosensitive resin composition tend to be improved. When the amount is 30 parts by mass or less, the heat resistance tends to be improved. It is in.

<(E) Inorganic filler>
The photosensitive resin composition of the present embodiment preferably contains an inorganic filler as the component (E).
(E) The inorganic filler is preferably used for the purpose of improving various properties such as adhesion, heat resistance and coating film hardness of the photosensitive resin composition. (E) Examples of the inorganic filler include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), and silicon nitride (Si ₃ ). N ₄ ), barium titanate (BaO · TiO ₂ ), barium carbonate (BaCO ₃ ), magnesium carbonate, aluminum hydroxide, magnesium hydroxide, lead titanate (PbO · TiO ₂ ), lead zirconate titanate (PZT) , lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga ₂ O _3), spinel _{(MgO · Al 2 O 3)} , mullite _{(3Al 2 O 3 · 2SiO 2} ), cordierite (2MgO · 2Al ₂ O ₃ · 5SiO _2), talc _{(3MgO · 4SiO 2 · H 2} O), aluminum titanate _{(TiO 2 · Al 2 O 3} ), yttria-containing Jill Near _{(Y 2 O 3 · ZrO 2} ), barium silicate (BaO · 8SiO _2), boron nitride (BN), calcium carbonate (CaCO _3), barium sulfate (BaSO _4), calcium sulfate (CaSO _4), zinc oxide (ZnO), magnesium titanate (MgO.TiO ₂ ), hydrotalcite, mica, calcined kaolin, carbon and the like are preferable. These (E) inorganic fillers can be used singly or in combination of two or more.

(E) The inorganic filler preferably has a maximum particle size of 0.1 to 20 μm, more preferably 0.1 to 10 μm, still more preferably 0.1 to 5 μm, and more preferably 0.1 to 1 μm. Particularly preferred. When the maximum particle size is 20 μm or less, a decrease in electrical insulation can be suppressed. Here, the maximum particle diameter of the (E) inorganic filler was measured by a laser diffraction method (based on JIS Z8825-2 (2001)).

(E) Among inorganic fillers, silica is preferable from the viewpoint of improving heat resistance, solder heat resistance, crack resistance (thermal shock resistance), and adhesive strength between the underfill material after the PCT test and the cured film. From the viewpoint of improving the above, barium sulfate is preferable. Moreover, it is preferable that the said barium sulfate is surface-treated with 1 or more types chosen from an alumina and an organosilane type compound from a viewpoint which can improve the aggregation prevention effect.

The elemental composition of aluminum on the surface of barium sulfate surface-treated with one or more selected from alumina and organosilane compounds is preferably 0.5 to 10 atomic%, more preferably 1 to 5 atomic%. 5 to 3.5 atomic% is more preferable. The elemental composition of silicon on the surface of barium sulfate is preferably 0.5 to 10 atomic%, more preferably 1 to 5 atomic%, and further preferably 1.5 to 3.5 atomic%. Further, the elemental composition of carbon on the surface of barium sulfate is preferably 10 to 30 atomic%, more preferably 15 to 25 atomic%, and further preferably 18 to 23 atomic%. These elemental compositions can be measured using XPS.

As barium sulfate surface-treated with at least one selected from alumina and organosilane compounds, for example, NanoFine BFN40DC (trade name, manufactured by Nippon Solvay Co., Ltd.) is commercially available.

(E) When the inorganic filler is contained, the total solid content in the photosensitive resin composition is 100 parts by mass. The content of the (E) inorganic filler is preferably 15 to 80 parts by mass, and 15 to 70 parts by mass. More preferably, 20 to 70 parts by mass is further preferable, 20 to 50 parts by mass is particularly preferable, and 20 to 45 parts by mass is extremely preferable. (E) If the content of the inorganic filler is within the above range, the film strength, heat resistance, insulation reliability, thermal shock resistance, resolution, etc. of the photosensitive resin composition can be further improved.

When (E) barium sulfate is used as the inorganic filler, the content of barium sulfate with the total solid content in the photosensitive resin composition being 100 parts by mass is preferably 5 to 60 parts by mass, and 10 to 50 parts by mass. Part is more preferable, 10 to 40 parts by weight is further preferable, and 10 to 35 parts by weight is particularly preferable. When the content of barium sulfate is within the above range, the solder heat resistance and the adhesion strength between the underfill material after the PCT (Pressure Cooker Test) test and the cured film can be further improved.

<(F) Pigment>
The photosensitive resin composition of the present embodiment preferably contains a pigment as the component (F).
(F) The pigment is preferably used according to a desired color when the wiring pattern is concealed. As the (F) pigment, a colorant that develops a desired color may be appropriately selected and used. Examples of the colorant include known phthalocyanine blue, phthalocyanine green, iodin green, diazo yellow, crystal violet, and the like. Coloring agents are preferred.

(F) When the pigment is contained, the total solid content in the photosensitive resin composition is 100 parts by mass. The content of (F) pigment is preferably 0.1 to 5 parts by mass, and 0.1 to 3 parts by mass. Part is more preferred. (F) It is preferable from a viewpoint of concealing a wiring pattern that content of a pigment is in the said range.

<Other ingredients>
In the photosensitive resin composition of the present embodiment, a diluent can be used as necessary to adjust the viscosity. Preferred examples of the diluent include organic solvents and photopolymerizable monomers. For example, the organic solvent can be appropriately selected from the solvents exemplified as the organic solvent that can be used in the reaction of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). Moreover, as a photopolymerizable monomer, what was illustrated by said (D) photopolymerizable compound is mentioned preferably.

The amount of the diluent used is preferably such that the total solid content in the photosensitive resin composition is 50 to 90% by mass, more preferably 60 to 80% by mass, and 65 to 75% by mass. Further preferred. That is, when the diluent is used, the content of the diluent in the photosensitive resin composition is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, and further preferably 25 to 35% by mass. By making the usage-amount of a diluent into the said range, the applicability | paintability of the photosensitive resin composition improves and formation of a higher definition pattern is attained.

The photosensitive resin composition of the present embodiment may contain a curing agent. As the curing agent, a compound that cures itself by heat, ultraviolet light, or the like, or a photocurable resin component in the composition of the present embodiment (A) carboxy group, hydroxyl group and heat of the acid-modified vinyl group-containing epoxy resin. A compound that is cured by ultraviolet rays or the like is preferable. By using a curing agent, the heat resistance, adhesion, chemical resistance, etc. of the final cured film can be improved.

As the curing agent, for example, as a thermosetting compound, an epoxy compound, a melamine compound, a urea compound, an oxazoline compound and the like are preferably exemplified. Examples of the epoxy compound include bisphenol A type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol S type epoxy resins and the like; novolak type epoxy resins Preferred examples include resins; biphenyl type epoxy resins; heterocyclic epoxy resins such as triglycidyl isocyanurate; and bixylenol type epoxy resins. Preferred examples of the melamine compound include triaminotriazine, hexamethoxymelamine, hexabutoxylated melamine and the like. Preferred examples of the urea compound include dimethylol urea.

As a hardening | curing agent, it is preferable to contain 1 or more types chosen from an epoxy compound (epoxy resin) and block type isocyanate from a viewpoint which can improve the heat resistance of a cured film more, An epoxy compound and block type isocyanate are included. It is more preferable to use together.
As the block type isocyanate, an addition reaction product of a polyisocyanate compound and an isocyanate blocking agent is used. Examples of the polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, naphthylene diisocyanate, bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, and isophorone diisocyanate. Preferred are polyisocyanate compounds and adducts, burettes and isocyanurates of these.

Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid And alcohol blocking agents such as ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetoaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol Mercaptan blocking agents such as methylthiophenol and ethylthiophenol; acid amide blocking agents such as acetic acid amide and benzamide; imide blocking agents such as succinimide and maleic imide; xylidine, aniline, butylamine, dibutylamine, etc. Amine-based blocking agents; imidazole-based blocking agents such as imidazole and 2-ethylimidazole; imine-based blocking agents such as methyleneimine and propyleneimine are preferred. Good mention.

The curing agent is used singly or in combination of two or more. When a curing agent is used, the content thereof is preferably 2 to 50 parts by weight, more preferably 2 to 40 parts by weight, and more preferably 3 to 30 parts by weight with respect to 100 parts by weight of the total solid content in the photosensitive resin composition. Is more preferable, and 5 to 20 parts by mass is particularly preferable. By making content of a hardening | curing agent in the said range, the heat resistance of the cured film formed can be improved more, maintaining favorable developability.

In the photosensitive resin composition of the present embodiment, an epoxy resin curing agent can be used in combination for the purpose of further improving various properties such as heat resistance, adhesion, and chemical resistance of the final cured film.

Specific examples of such epoxy resin curing agents include, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl Imidazoles such as -5-hydroxymethylimidazole; guanamines such as acetoguanamine and benzoguanamine; diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polybasic hydrazide, etc. One or more selected from these organic acid salts and epoxy adducts; amine complexes of boron trifluoride; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino- 6- Triazine derivatives such as silyl-S-triazine; trimethylamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris ( Tertiary amines such as dimethylaminophenol), tetramethylguanidine, m-aminophenol; polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolak, alkylphenol novolak; tributylphosphine, triphenylphosphine, tris-2-cyanoethyl Organic phosphines such as phosphine; phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosnium chloride; Quaternary ammonium salts such as trimethylammonium chloride and phenyltributylammonium chloride; the above polybasic acid anhydrides; diphenyliodonium tetrafluoroborate; triphenylsulfonium hexafluoroantimonate; 2,4,6-triphenylthiopyrylium hexafluoro Preferred examples include phosphate.

The epoxy resin curing agent is used alone or in combination of two or more, and is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass in the photosensitive resin composition.

The photosensitive resin composition of the present embodiment includes, if necessary, polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol; thickeners such as benton and montmorillonite; silicone-based, fluorine-based, vinyl Various known and commonly used additives such as resin-based antifoaming agents; silane coupling agents and the like can be used.
Furthermore, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphate compounds phosphate compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters can be used.

(Elastomer)
The photosensitive resin composition of this embodiment can contain an elastomer. The elastomer is particularly preferably used when the photosensitive resin composition of the present embodiment is used for manufacturing a semiconductor package substrate. By adding an elastomer to the photosensitive resin composition of the present embodiment, the curing reaction proceeds by ultraviolet rays, heat, etc., so that (A) distortion inside the resin due to curing shrinkage of the acid-modified vinyl group-containing epoxy resin (internal Decrease in flexibility and adhesiveness due to stress) can be suppressed.

Preferred examples of the elastomer include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, and silicone elastomers. These elastomers are composed of a hard segment component and a soft segment component, and it is generally considered that the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness.

In addition to the above elastomer, a rubber-modified epoxy resin can be used. The rubber-modified epoxy resin includes, for example, a part or all of epoxy groups of the above-described bisphenol F type epoxy resin, bisphenol A type epoxy resin, triphenolmethane type epoxy resin, phenol novolac type epoxy resin or cresol novolac type epoxy resin. It can be obtained by modification with a carboxylic acid-modified butadiene-acrylonitrile rubber or a terminal amino-modified silicone rubber. Among these elastomers, from the viewpoint of shear adhesiveness, both end carboxyl group-modified butadiene-acrylonitrile copolymer, Espel which is a polyester-based elastomer having a hydroxyl group (manufactured by Hitachi Chemical Co., Ltd., Espel 1612 and 1620 (trade names) )) Is preferred.

The amount of the elastomer is preferably 2 to 30 parts by mass, more preferably 4 to 20 parts by mass, and further preferably 10 to 20 parts by mass with respect to 100 parts by mass of the (A) acid-modified vinyl group-containing epoxy resin. . If it is 2 parts by mass or more, the elastic modulus in the high temperature region of the cured film tends to be low, and if it is 30 parts by mass or less, the unexposed part tends to be eluted with the developer.

The photosensitive resin composition of the present embodiment can be obtained by uniformly kneading and mixing various components used as desired, including the components (A) to (F) described above, using a roll mill, a bead mill, or the like. it can.
Moreover, it is preferable that the photosensitive resin composition of this embodiment is a liquid form. By making it liquid, a permanent mask resist can be easily formed by various coating methods described later.

[Photosensitive element, permanent mask resist and printed wiring board]
The photosensitive resin composition of the present embodiment is suitably used for forming a photosensitive element and a permanent mask resist, and the photosensitive element and the permanent mask resist of the present embodiment are the photosensitive resin composition of the present embodiment. It is formed using.
The photosensitive element of this embodiment is provided with a support and a photosensitive layer using the photosensitive resin composition of this embodiment on the support. As the support, for example, a resin film having heat resistance and solvent resistance, such as a polyester resin film such as polyethylene terephthalate, and a polyolefin resin film such as polyethylene and polypropylene, is preferably mentioned. From the viewpoint of transparency, a polyethylene terephthalate film Is preferably used. The thickness of the support is preferably 1 to 100 μm, more preferably 1 to 50 μm, and even more preferably 1 to 30 μm in view of mechanical strength, good resolution, and the like.

For example, the photosensitive element of the present embodiment is prepared by applying the photosensitive resin composition of the present embodiment on the support by a method such as dipping, spraying, bar coating, roll coating, or spin coating. The photosensitive resin composition of the embodiment is applied at a film thickness (after drying: 10 to 200 μm) according to the application to form a coating film, and dried at about 70 to 150 ° C. for about 5 to 30 minutes to form a photosensitive layer. Can be obtained.

The permanent mask resist of this embodiment and the printed wiring board provided with the permanent mask resist are imaged as follows, for example. First, on a base material on which a resist is to be formed (for example, a copper-clad laminate for a printed wiring board), a screen printing method, a spray method, a roll coating method, a curtain coating method, an electrostatic coating method, etc. The photosensitive resin composition of the embodiment is applied at a film thickness (after drying: 10 to 200 μm) according to the application to form a coating film, and the coating film is dried at 60 to 110 ° C. Further, instead of the coating film, the photosensitive layer of the photosensitive element may be transferred (laminated) onto the substrate on which the resist is to be formed. In this case, the dried coating film on the support is pasted on the substrate using an atmospheric laminator or a vacuum laminator as necessary.
After forming a photosensitive layer (coating film) on a substrate, an active ray such as ultraviolet rays is preferably applied in an energy amount of 10 to 1,000 mJ / cm ² by directly contacting a negative film or through a transparent film. When the resin film is applied by irradiation, the resin film is peeled off, and the unexposed part is dissolved and removed (developed) with a dilute alkaline aqueous solution.
Next, the exposed portion is sufficiently cured by post-exposure (ultraviolet light exposure), post-heating, or post-exposure and post-heating to obtain a cured film. For example, the post-exposure is preferably 1 to 5 J / cm ² , and the post-heating is preferably 100 to 200 ° C. for 30 minutes to 12 hours.

The permanent mask resist thus obtained is less likely to cause an undercut where the bottom is removed, and the upper portion of the resist is less likely to be lost. Therefore, the line at the middle (center) and deepest (bottom) of the pattern cross section Since the width does not increase with respect to the line width of the surface portion, the pattern outline has good linearity, excellent resist shape, and a pattern with excellent resolution. In addition, this permanent mask resist has a pattern that is excellent in the formation stability of the finer hole diameter and the interval pitch between holes due to the recent downsizing and higher performance of electronic devices.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

(Evaluation methods)
(1) Evaluation of surface curability The photosensitive resin composition of each Example and Comparative Example was applied to a PET film having a thickness of 35 μm with an applicator so that the film thickness after drying was 35 μm. Formed. Subsequently, it was dried using a hot air circulation dryer at 80 ° C. for 20 minutes. The infrared absorption spectrum (ATR (Attenuated Total Reflection) method) of the surface of the obtained coating film was measured under the following conditions.
Measurement device: manufactured by Thermo Fisher Scientific Co., Ltd., trade name: Nicolet iS50R
-Number of integrations: 128 times Next, exposure was performed at an exposure amount of 600 mJ / cm ² using an ultraviolet exposure device (trade name: HTE-5102S, manufactured by Hitec Corporation). The infrared absorption spectrum (ATR method) of the surface of the coated film after exposure was measured under the same conditions as described above, and the change rate of the carbon-carbon double bond appearing at 1470 cm ⁻¹ before and after exposure was obtained from the following formula. The average value of 3 times of accumulation was defined as surface curability (%).
Change rate of double bond (%) = 100- (carbon-carbon double bond amount after exposure / carbon-carbon double bond amount before exposure × 100)

(2) Photosensitivity evaluation The photosensitive resin composition of each Example and Comparative Example was applied to a 35 μm thick PET film with an applicator so that the film thickness after drying was 35 μm to form a coating film. did. Subsequently, it was dried using a hot air circulation dryer at 80 ° C. for 20 minutes. Next, 41 steps of Step Tablet (manufactured by Hitachi Chemical Co., Ltd.) are brought into close contact with the coating film, and a predetermined integrated exposure amount of ultraviolet rays (Dainippon Screen Manufacturing Co., Ltd. direct drawing machine, “LI9200 (model number)”). Was irradiated on the entire surface at 50 mJ / cm ² . Subsequently, after developing for 60 seconds with a 1% by mass aqueous sodium carbonate solution, the number of stages of the coating film remaining without being developed was confirmed. Evaluation was made according to the following criteria depending on the number of steps.
A (excellent): 10 steps or more B (good): 6 to 9 steps C (defect): 5 steps or less

(3) Evaluation of bottom curability The photosensitive resin composition of each Example and Comparative Example was applied to a 35 μm thick PET film with an applicator so that the film thickness after drying was 35 μm. Formed. Subsequently, it was dried using a hot air circulation dryer at 80 ° C. for 20 minutes. The infrared absorption spectrum (ATR method) of the surface of the obtained coating film was measured under the following conditions.
Measurement device: manufactured by Thermo Fisher Scientific Co., Ltd., trade name: Nicolet iS50R
-Number of integrations: 128 times Next, exposure was performed at an exposure amount of 600 mJ / cm ² using an ultraviolet exposure device (trade name: HTE-5102S, manufactured by Hitec Corporation). Then, the exposed coating film was peeled off from the PET film, and the infrared absorption spectrum (ATR method) of the coating film on the PET film surface side after the exposure was measured under the same conditions as described above. The rate of change of the carbon-carbon double bond appearing at 1470 cm ⁻¹ before and after the exposure was determined from the following formula, and the average value of 3 times of integration was defined as the coating bottom curability (%).
Change rate of double bond (%) = 100- (carbon-carbon double bond amount after exposure / carbon-carbon double bond amount before exposure × 100)

(4) Evaluation of resist shape Each of the photosensitive resin compositions of Examples and Comparative Examples was 50 cm × 50 cm in thickness and 0.6 mm thick copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., trade name: A coating film was formed on MCL-E-67) by a screen printing method so that the film thickness after drying was 35 μm, and then dried at 80 ° C. for 20 minutes using a hot air circulating dryer.
Next, a negative mask having a pattern with a hole diameter of 100 μm and a hole pitch of 100 μm and a hole diameter of 80 μm and a hole pitch of 80 μm shown in FIG. The film was brought into close contact with the film, and exposed using a UV exposure apparatus (trade name: HTE-5102S, manufactured by Hitec Co., Ltd.) at a predetermined exposure amount shown in Tables 1 to 6.
Thereafter, spray development was performed with a 1% by mass aqueous sodium carbonate solution for 60 seconds at a pressure of 0.18 MPa (1.8 kgf / cm ² ), and the unexposed area was dissolved and developed. Next, using an ultraviolet exposure device (manufactured by GS Yuasa Lighting Co., Ltd., trade name: conveyor type UV irradiation device), the exposure was performed at an exposure amount of 1000 mJ / cm ² , and then the test was performed by heating at 150 ° C. for 1 hour. A piece was made.
The test piece on which the pattern was formed was cast with an epoxy resin (manufactured by Mitsubishi Chemical Corporation, Epicoat 828 (trade name)) and a thermosetting resin using triethylenetetramine as a curing agent. Polished by Refine Tech Co., Ltd., trade name: Refine Polisher ”), the cross section of the pattern was cut out, the resist shape was observed with a metal microscope, and evaluated according to the following criteria. FIG. 1 schematically shows the cross-sectional shape of the resist.
A (excellent): The resist shape was rectangular or trapezoidal, and the linearity of the pattern outline was good.
B (defect): The resist shape was confirmed to be undercut, skirted or thickened, or the linearity of the pattern outline was poor.

(5) Evaluation of via diameter accuracy The photosensitive resin compositions of the examples and comparative examples were 50 cm × 50 cm in size and 0.6 mm thick copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., trade name) : MCL-E-67) was applied by screen printing so that the film thickness after drying was 35 μm to form a coating film, and then dried at 80 ° C. for 20 minutes using a hot air circulating dryer. .
Next, each negative mask having the pattern shown in FIG. 2 was brought into close contact with the coating film, and exposed using an ultraviolet exposure device (trade name: HTE-5102S, manufactured by Hitec Co., Ltd.) at an exposure amount of 600 mJ / cm ² . Thereafter, spray development was performed with a 1% by mass aqueous sodium carbonate solution for 60 seconds at a pressure of 0.18 MPa (1.8 kgf / cm ² ), and the unexposed portion was dissolved and developed to prepare a test piece. The pattern of the obtained test piece was evaluated according to the following criteria.
A (excellent): 100 μm and 80 μm patterns were reproduced 80%.
B (Poor): 100 μm and 80 μm patterns were reproduced with less than 80%.
Here, using a microscope, it is magnified 700 times, and patterns of 100 μm and 80 μm are observed. In the case of a pattern of 100 μm, the bottom of the pattern is 80 μm or more (80% or more with respect to the pattern diameter). The pattern was able to be reproduced when it was formed. In the case of an 80 μm pattern, the pattern was reproduced when the pattern bottom was formed with a size of 64 μm or more. In the determination of “A” and “B”, the case where the total number of formed patterns was 80% or more with respect to the total number of patterns of 100 μm and 80 μm was evaluated as “A”.

(6) Evaluation of solder heat resistance (i)
(4) A water soluble flux (trade name: K-183, manufactured by Alpha Metals Co., Ltd.) is applied to a test piece prepared under the same conditions as the test piece used in the resist shape evaluation, and a solder bath at 265 ° C. And dipped in the solder layer for 10 seconds. After dipping and taking out as one cycle and repeating 6 cycles, the appearance of the coating film was visually observed and evaluated according to the following criteria.
A (excellent): Appearance change was not confirmed within the range of the coating film 30 cm × 30 cm.
B (good): Within 1 to 5 cm of the coating film, 1 to 5 coating films were found to have swells or blisters.
C (defect): Six or more coatings were found to be in the range of 30 cm × 30 cm.

(7) Evaluation of solder heat resistance (ii)
(4) A non-cleaning type flux (manufactured by Senju Metal Industry Co., Ltd., trade name: RMA SR-209) was applied to a test piece prepared under the same conditions as the test piece used in the evaluation of the resist shape. After being immersed in a solder bath set to 10 seconds, it was taken out from the solder layer. The immersion and removal were taken as one cycle, and after 10 cycles were repeated, the coating film appearance of the removed test piece was visually observed and evaluated according to the following criteria.
A: The appearance change of the resist coating film was not confirmed.
B: Slight peeling of the resist coating film was confirmed, but there was no practical problem.
C: Swelling or peeling of the resist coating was confirmed.

(8) Evaluation of crack resistance (4) A step of holding a test piece prepared under the same conditions as the test piece used in the evaluation of the resist shape at -65 ° C for 30 minutes and then holding at 150 ° C for 30 minutes. After repeating 1000 cycles as 1 cycle, the coating film appearance of the test piece was visually observed and evaluated according to the following criteria.
A (excellent): Appearance change was not confirmed within the range of the coating film 30 cm × 30 cm.
B (good): Within 1 to 5 cm of the coating film, 1 to 5 coating films were found to have swells or blisters.
C (defect): Six or more coatings were found to be in the range of 30 cm × 30 cm.

(9) Evaluation of adhesion The copper-clad laminated substrate (Hitachi Chemical Co., Ltd.) having a thickness of 0.6 mm obtained by buffing (roughening 5 μm in the depth direction) the copper surface of the photosensitive resin composition of each Example and Comparative Example. Co., Ltd., trade name: MCL-E-67) and chemical polishing (roughened by 0.5 μm in the depth direction using abrasive CZ8101 manufactured by MEC Co., Ltd.) A substrate (made by Hitachi Chemical Co., Ltd., trade name: MCL-E-67) was coated by screen printing so that the film thickness after drying was 35 μm to form a coating film, and then at 80 ° C. for 20 minutes. It dried using the hot air circulation type dryer.
Next, each negative mask having the pattern shown in FIG. 2 was brought into close contact with the coating film, and exposed using an ultraviolet exposure device (trade name: HTE-5102S, manufactured by Hitec Co., Ltd.) at an exposure amount of 600 mJ / cm ² . Thereafter, spray development was performed with a 1% by mass aqueous sodium carbonate solution for 60 seconds at a pressure of 0.18 MPa (1.8 kgf / cm ² ), and the unexposed area was dissolved and developed. Next, using a UV exposure device (trade name: conveyor type UV irradiation device, manufactured by GS Yuasa Lighting Co., Ltd.), the sample was exposed at an exposure amount of 1000 mJ / cm ² and heated at 150 ° C. for 1 hour to obtain a test piece. Was made.
About the obtained test piece, according to JIS K5600, after producing 100 1-mm banquets and attaching cellophane tape (product name: cello tape (registered trademark)) manufactured by Nichiban Co., Ltd., 90 degrees A peel test was conducted to forcibly peel the cellophane tape in the direction of. The state of peeling of the goblet was observed and evaluated according to the following criteria.
A (excellent): 90/100 or more and no peeling.
B (good): 50/100 or more and less than 90/100, no peeling.
C (defect): 0/100 or more and less than 50/100, no peeling.

(10) Solvent resistance The test piece prepared under the same conditions as the test piece used in the evaluation of the above (4) resist shape was immersed in isopropyl alcohol at room temperature for 30 minutes, and visually checked for abnormal appearance. Next, the cellophane tape (made by Nichiban Co., Ltd., trade name: cellotape (registered trademark)) is applied to the coating film of the test specimen after immersion, and then the cellophane tape is forcibly peeled in the direction of 90 degrees. A test was conducted, and the presence or absence of peeling of the coating film was visually confirmed and evaluated according to the following criteria.
A (excellent): No abnormality was observed in the appearance of the coating film, and there was no peeling.
B (defect): Abnormality was confirmed in the appearance of the coating film or peeled off.

(11) Acid resistance The test piece prepared under the same conditions as the test piece used in the above (4) evaluation of the resist shape was immersed in a 10% by mass hydrochloric acid aqueous solution for 30 minutes at room temperature, and visually checked for any abnormal appearance. did. Next, the cellophane tape (made by Nichiban Co., Ltd., trade name: cellotape (registered trademark)) is applied to the coating film of the test specimen after immersion, and then the cellophane tape is forcibly peeled in the direction of 90 degrees. A test was conducted, and the presence or absence of peeling of the coating film was visually confirmed and evaluated according to the following criteria.
A (excellent): Abnormality was not confirmed in the coating film appearance, and there was no peeling.
B (defect): Abnormality was confirmed in the coating film appearance or peeled off.

(12) Alkali resistance (4) A test piece prepared under the same conditions as the test piece used in the evaluation of the resist shape is immersed in a 5% by mass aqueous sodium hydroxide solution at room temperature for 30 minutes to determine whether the appearance is normal Visual confirmation was made. Next, the cellophane tape (made by Nichiban Co., Ltd., trade name: cellotape (registered trademark)) is applied to the coating film of the test specimen after immersion, and then the cellophane tape is forcibly peeled in the direction of 90 degrees. A test was conducted, and the presence or absence of peeling of the coating film was visually confirmed and evaluated according to the following criteria.
A (excellent): Abnormality was not confirmed in the coating film appearance, and there was no peeling.
B (defect): Abnormality was confirmed in the coating film appearance or peeled off.

(13) Evaluation of flux corrosion resistance The above (4) resist shape, except that in the above (4) resist shape evaluation, the pattern shown in FIG. 2 is a 1 mm square lattice pattern shown in FIG. A test piece was obtained in the same manner as in the evaluation. Next, a highly active water-soluble flux (manufactured by Alpha Metals Co., Ltd., trade name: K-183) was applied to the entire surface of the obtained test piece and left to stand for 3 minutes to remove excess flux. . Next, the test piece was preheated at 130 ° C. for 1 minute, then immersed in a solder bath at 280 ° C. for 20 seconds, and then removed from the solder bath. After standing to cool at room temperature for 1 minute, it was washed with water, and when the water droplets were wiped off, the appearance was visually observed. Also, a 24 mm wide cellophane tape (manufactured by Nichiban Co., Ltd., trade name: cellotape (registered trademark)) is attached to the test piece with the minimum circuit width, and the cellophane tape is forcibly peeled in the direction of 90 degrees. The appearance of the test piece after peeling was visually observed and evaluated according to the following criteria.
5: No peeling of the portion where the resist was present was confirmed even after the peeling test.
4: After the peeling test, peeling of 20% or less of the portion where the resist was present was confirmed.
3: Slight whitening was confirmed in the portion where the resist was present before the peeling test, and peeling of 20% or less of the portion where the resist was present was confirmed after the peeling test, but there was no problem in practical use.
2: Whitening was confirmed in the portion where the resist was present before the peeling test, and peeling of 20% or more of the portion where the resist was present was confirmed after the peeling test.
1: Remarkable whitening was confirmed in the portion where the resist was present before the peel test, and significant peel was confirmed after the peel test.

(14) Electroless plating resistance The test piece prepared under the same conditions as the test piece used in the above (4) evaluation of the resist shape was made of nickel using a commercially available electroless nickel plating bath and electroless gold plating bath. Plating was performed under conditions of 5 μm and gold of 0.05 μm. After plating, the presence or absence of plating soaking was visually confirmed. Next, the cellophane tape (made by Nichiban Co., Ltd., trade name: cellotape (registered trademark)) is applied to the coating film of the test specimen after immersion, and then the cellophane tape is forcibly peeled in the direction of 90 degrees. A test was conducted, and the presence or absence of peeling of the coating film was visually confirmed and evaluated according to the following criteria.
A: No soaking and peeling were observed.
B: Although soaking was seen after plating, peeling was not seen.
C: Peeling was observed after plating.

(Synthesis Example 1: Synthesis of acid-modified vinyl group-containing epoxy resin (I))
Cresol novolac type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name: YDCN704, in general formula (I), Y ¹ = glycidyl group, R ¹¹ = methyl group) 220 parts by mass, acrylic acid 72 parts by mass, hydroquinone 1 0.0 parts by mass and 180 parts by mass of carbitol acetate were mixed and heated to 90 ° C. and stirred to dissolve the reaction mixture. Next, the mixture was cooled to 60 ° C., mixed with 1 part by mass of benzyltrimethylammonium chloride, heated to 100 ° C., and reacted until the solid content acid value reached 1 mgKOH / g. Next, 152 parts by mass of tetrahydrophthalic anhydride and 100 parts by mass of carbitol acetate were mixed, heated to 80 ° C., and stirred for 6 hours. After cooling to room temperature, the solution containing the acid-modified vinyl group-containing epoxy resin (I) was obtained by diluting with carbitol acetate so that the solid content concentration was 60% by mass.
In addition, the solid content acid value in an Example was measured by the neutralization titration method. Specifically, 30 g of acetone is added to 1 g of a solution containing an epoxy resin containing an acid-modified vinyl and further uniformly dissolved, and then a phenolphthalein as an indicator is added to the solution containing the epoxy resin containing the acid-modified vinyl. It was measured by adding an appropriate amount to and titrating with a 0.1N potassium hydroxide aqueous solution.

(Synthesis Example 2; Synthesis of acid-modified vinyl group-containing epoxy resin (II) -a)
Bisphenol F type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name: YDF2001, Y ² = glycidyl group, R ¹² = H in general formula (II)) 475 parts by mass, acrylic acid 72 parts by mass, hydroquinone 0. 5 parts by mass and 120 parts by mass of carbitol acetate were mixed and heated to 90 ° C. and stirred to dissolve the reaction mixture. Subsequently, it cooled to 60 degreeC, 2 mass parts of benzyltrimethylammonium chloride was mixed, it heated to 100 degreeC, and it was made to react until a solid content acid value became 1 mgKOH / g. Next, 230 parts by mass of tetrahydrophthalic anhydride and 85 parts by mass of carbitol acetate were mixed, heated to 80 ° C., and stirred for 6 hours. After cooling to room temperature, the solution was diluted with carbitol acetate so that the solid content concentration was 60% by mass to obtain a solution containing the acid-modified vinyl group-containing epoxy resin (II) -a.

(Synthesis Example 3; Synthesis of acid-modified vinyl group-containing epoxy resin (IV) -a)
A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was charged with 272 parts by mass of bis (4-hydroxyphenyl) methane dissolved at 80 ° C., and stirring was started at 80 ° C. To this was added 3 parts by mass of methanephosphonic acid, and 16.3 parts by mass of a paraformaldehyde aqueous solution (concentration: 92% by mass) was added dropwise over 1 hour so as to maintain the liquid temperature in the range of 80 to 90 ° C. After completion of dropping, the mixture was heated to 110 ° C. and stirred for 2 hours. Next, 1000 parts by mass of methyl isobutyl ketone was further added, transferred to a separatory funnel and washed with water. After continuing washing with water until the washing water shows neutrality, the solvent and unreacted bis (4-hydroxyphenyl) methane are removed from the organic layer under heating and reduced pressure (temperature: 220 ° C., pressure: 66.7 Pa), As a result, 164 parts by mass of a bisphenol novolac resin as a brown solid was obtained. The obtained bisphenol novolac resin had a softening point of 74 ° C. and a hydroxyl group equivalent of 154 g / eq.

Next, 154 parts by mass of the bisphenol-based novolak resin obtained above, 463 parts by mass of epichlorohydrin, and 139 parts by mass of n-butanol while purging nitrogen gas into a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer And 2 parts by mass of tetraethylbenzylammonium chloride were mixed and dissolved. Next, this was heated to 65 ° C., and the pressure was reduced to an azeotropic pressure, and then 90 parts by mass of an aqueous sodium hydroxide solution (concentration: 49% by mass) was added dropwise at a constant rate over 5 hours, followed by stirring for 30 minutes. . During this time, the distillate distilled by azeotropic distillation was separated by a Dean-Stark trap, the aqueous layer was removed, and the reaction was carried out while returning the oil layer to the flask (reaction system). Thereafter, 590 parts by mass of methyl isobutyl ketone and 177 parts by mass of n-butanol were added to the crude epoxy resin obtained by distilling off unreacted epichlorohydrin by distillation under reduced pressure (temperature: 22 ° C., pressure: 1.87 kPa). Dissolved. After adding 10 parts by mass of an aqueous sodium hydroxide solution (concentration: 10% by mass) to this solution and reacting at 80 ° C. for 2 hours, washing with 150 parts by mass of water was repeated three times until the pH of the washing solution became neutral. It was. It was confirmed that the pH of the cleaning liquid used for the third water washing was neutral. Next, the inside of the flask (reaction system) was dehydrated by azeotropic distillation and subjected to microfiltration, and then the solvent was distilled off under reduced pressure (pressure: 1.87 kPa) to obtain a brown viscous liquid. A bisphenol novolak type epoxy resin (epoxy resin (a) having a constitutional unit of Y ⁴ = glycidyl group and R ¹³ = H in the general formula (IV)) used in the invention was obtained. The epoxy resin had a hydroxyl group equivalent of 233 g / eq.

To 450 parts by mass of the epoxy resin (a) obtained above, 124 parts by mass of acrylic acid, 1.5 parts by mass of hydroquinone, and 250 parts by mass of carbitol acetate are mixed, heated to 90 ° C. and stirred to obtain a reaction mixture. Dissolved. Subsequently, after cooling to 60 ° C., 2 parts by mass of benzyltrimethylammonium chloride was mixed, heated to 100 ° C., and reacted until the acid value reached 1 mgKOH / g. Next, 230 parts by mass of tetrahydrophthalic anhydride and 180 parts by mass of carbitol acetate were mixed with the reactants, heated to 80 ° C., and reacted for 6 hours. Next, the mixture was cooled to room temperature and diluted with carbitol acetate so that the solid content concentration was 60% by mass to obtain a solution containing the acid-modified vinyl group-containing epoxy resin (IV) -a.
The softening point of the resin was measured in accordance with the ring and ball method defined in JIS-K7234: 1986 (heating rate: 5 ° C./min).

Synthesis Example 4 Synthesis of Acid-Modified Vinyl Group-Containing Epoxy Resin (IV) -b
A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was charged with 272 parts by mass of 2,2-bis (4-hydroxyphenyl) propane dissolved at 80 ° C., and stirring was started at 80 ° C. To this, 3 parts by mass of methanephosphonic acid was added, and 16.3 parts by mass of paraformaldehyde (92% by mass) was added dropwise over 1 hour so that the liquid temperature was maintained in the range of 80 to 90 ° C. After completion of dropping, the mixture was heated to 110 ° C. and stirred for 2 hours. Next, 1000 parts by mass of methyl isobutyl ketone was further added, transferred to a separatory funnel and washed with water. After washing with water until the washing water shows neutrality, the solvent and unreacted 2,2- (4-hydroxyphenyl) propane are heated from the organic layer under reduced pressure (temperature: 240 ° C., pressure: 26.7 Pa). This was removed to obtain 164 parts by mass of a bisphenol novolac resin as a brown solid. The obtained bisphenol novolac resin had a softening point of 87 ° C. and a hydroxyl group equivalent of 174 g / eq.

Next, 154 parts by mass of the bisphenol-based novolak resin obtained above, 463 parts by mass of epichlorohydrin, and 139 parts by mass of n-butanol while purging nitrogen gas into a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer And 2 parts by mass of tetraethylbenzylammonium chloride were mixed and dissolved. Next, this was heated to 65 ° C., and the pressure was reduced to an azeotropic pressure, and then 90 parts by mass of an aqueous sodium hydroxide solution (concentration: 49% by mass) was added dropwise at a constant rate over 5 hours, followed by stirring for 30 minutes. . During this time, the distillate distilled by azeotropic distillation was separated by a Dean-Stark trap, the aqueous layer was removed, and the reaction was carried out while returning the oil layer to the flask (reaction system). Thereafter, 590 parts by mass of methyl isobutyl ketone and 177 parts by mass of n-butanol were added to the crude epoxy resin obtained by distilling off unreacted epichlorohydrin by distillation under reduced pressure (temperature: 22 ° C., pressure: 1.87 kPa). Dissolved. After adding 10 parts by mass of an aqueous sodium hydroxide solution (concentration: 10% by mass) to this solution and reacting at 80 ° C. for 2 hours, washing with water was repeated 3 times with 150 parts by mass of water until the pH of the washing solution became neutral. It was. It was confirmed that the pH of the cleaning liquid used in the third water washing was neutral. Next, the inside of the flask (reaction system) was dehydrated by azeotropic distillation and subjected to microfiltration, and then the solvent was distilled off under reduced pressure (pressure: 1.87 kPa) to obtain a brown viscous liquid. A bisphenol novolac type epoxy resin (epoxy resin (a) having a constitutional unit of Y ⁴ = glycidyl group and R ¹³ = methyl group in the general formula (IV)) used in the invention was obtained. The epoxy resin had a hydroxyl group equivalent of 233 g / eq.

To 450 parts by mass of the epoxy resin (a) obtained above, 124 parts by mass of acrylic acid, 1.5 parts by mass of hydroquinone, and 250 parts by mass of carbitol acetate are mixed, heated to 90 ° C. and stirred to obtain a reaction mixture. Dissolved. Next, the mixture was cooled to 60 ° C., mixed with 2 parts by mass of benzyltrimethylammonium chloride, heated to 100 ° C., and reacted until the acid value reached 1 mgKOH / g. Next, 230 parts by mass of tetrahydrophthalic anhydride and 180 parts by mass of carbitol acetate were mixed with the reactants, heated to 80 ° C., and reacted for 6 hours. Next, the mixture was cooled to room temperature and diluted with carbitol acetate so that the solid content concentration was 60% by mass to obtain a solution containing acid-modified vinyl group-containing epoxy resin (IV) -b.

(Synthesis Example 5: Synthesis of acid-modified vinyl group-containing epoxy resin (IV) -c)
Thermometer, dropping funnel, a cooling tube, and a flask provided with a stirrer, a bisphenol F novolac type epoxy resin (DIC (trade name) manufactured by: EXA-7376, in the general formula (IV), Y ⁴ and Y ⁵ = Glycidyl group, R ¹³ = hydrogen atom) 350 parts by mass, acrylic acid 70 parts by mass, methylhydroquinone 0.5 parts by mass, carbitol acetate 120 parts by mass, reacted by heating to 90 ° C. and stirring. The mixture was completely dissolved. Next, the obtained solution was cooled to 60 ° C., 2 parts by mass of triphenylphosphine was added, and the mixture was heated to 100 ° C. until the acid value of the solution reached 1 mgKOH / g. To the solution after the reaction, 98 parts by mass of tetrahydrophthalic anhydride (THPAC) and 85 parts by mass of carbitol acetate were added, heated to 80 ° C., and reacted for 6 hours. Thereafter, the solution was cooled to room temperature to obtain a solution containing acid-modified vinyl group-containing epoxy resin (IV) -c having a solid content of 73% by mass.

(Synthesis Example 6: Synthesis of acid-modified vinyl group-containing epoxy resin (II) -b)
In a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer, a bisphenol F-type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: 4004, epoxy equivalent: 526 g / eq, in the general formula (II), Y ² = hydrogen atom, R ¹² = hydrogen atom) 1,052 parts by mass, 144 parts by mass of acrylic acid (b), 1 part by mass of methylhydroquinone, 850 parts by mass of carbitol acetate and 100 parts by mass of solvent naphtha were mixed. The mixture was dissolved by heating and stirring at 0 ° C. Next, the solution was cooled to 50 ° C., 2 parts by mass of triphenylphosphine and 75 parts by mass of solvent naphtha were mixed, heated to 100 ° C., and reacted until the solid content acid value became 1 mgKOH / g or less. Next, the obtained solution was cooled to 50 ° C., 745 parts by mass of tetrahydrophthalic anhydride (THPAC), 75 parts by mass of carbitol acetate and 75 parts by mass of solvent naphtha were mixed and heated to 80 ° C. for 6 hours. Reacted. Thereafter, the mixture was cooled to room temperature to obtain a solution containing an acid-modified vinyl group-containing epoxy resin (II) -b having a solid content acid value of 80 mgKOH / g and a solid content of 62% by mass.

Examples 1 to 32 and Comparative Examples 1 to 32
Compositions were blended according to the blending compositions shown in Tables 1 to 6 and kneaded by a three roll mill to prepare a photosensitive resin composition. Carbitol acetate was added so that the solid content concentration was 70% by mass to obtain a photosensitive resin composition. It evaluated based on said evaluation method using the obtained photosensitive resin composition. The evaluation results are shown in Tables 1-6. In addition, the unit of the compounding quantity of each component in a table | surface is a mass part, and the compounding quantity of (A) component in a table | surface means the compounding quantity as a solution containing the epoxy resin obtained by each synthesis example.

Examples 33 and 34 and Comparative Examples 33 and 34
A photosensitive resin composition was prepared in the same manner as in Example 1 according to the formulation shown in Table 6. Each obtained photosensitive resin composition was diluted with methyl ethyl ketone, coated on a PET film, and then dried at 90 ° C. for 10 minutes to form a photosensitive layer made of a photosensitive resin composition having a thickness of 25 μm. Further, a polyethylene film (protective layer) was laminated thereon to produce a photosensitive element.
The protective layer was peeled off from the photosensitive element obtained above, and the photosensitive element was heat-laminated on a solid copper foil substrate. Next, a negative mask having a pattern with a hole diameter of 100 μm and a pitch between holes of 100 μm, or a pattern with a hole diameter of 80 μm and a pitch between holes shown in FIG. And exposed to a predetermined exposure amount shown in Table 6 using an ultraviolet exposure apparatus (trade name: HTE-5102S, manufactured by Hitec Corporation). Thereafter, spray development was performed with a 1% by mass aqueous sodium carbonate solution for 60 seconds at a pressure of 0.18 MPa (1.8 kgf / cm ² ), and the unexposed area was dissolved and developed. Next, after exposing with an exposure amount of 1000 mJ / cm ² using an ultraviolet exposure device (trade name: conveyor type UV irradiation device, manufactured by GS Yuasa Lighting Co., Ltd.), the test piece was heated at 150 ° C. for 1 hour. Was made. Evaluation similar to Example 31 was performed using the obtained test piece. The evaluation results are shown in Table 6.

I) Details of each material in Table 1 are as follows.
・ Irgacure 819: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (trade name, manufactured by BASF Japan Ltd.)
・ Darocur TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name, manufactured by BASF Japan Ltd.)
Irgacure 907: 2-methyl- [4- (methylthio) phenyl] morpholino-1-propanone (trade name, manufactured by BASF Japan Ltd.)
・ Irgacure OXE01: (1,2-octanedione, 1- [4- (phenylthio)-, 2- (o-benzoyloxime)] (BASF Japan Ltd., trade name)
・ Kayarad DPHA: Dipentaerythritol pentaacrylate (Nippon Kayaku Co., Ltd., trade name)
- BaSO _4: Sakai Chemical Industry Co., Ltd., SiO ₂ :( Ltd.) Tatsumori Ltd. - EPIKOTE 828: bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd., trade name)

From the results shown in Table 1, in the photosensitive resin compositions of the present invention of Examples 1 to 6, the pattern of the permanent mask resist (solder resist) has a hole diameter of 100 μm and an interval pitch between holes of 100 μm. Or a high-definition pattern with a hole diameter of 80 μm and an interval pitch between holes of 80 μm, it maintains excellent surface curability and bottom curability, and has an excellent via shape in resist shape. As a result, it was confirmed that the thickness around the pattern could be reduced and the via diameter accuracy was excellent. Moreover, it was confirmed that not only the excellent resist shape but also other properties such as solder heat resistance are excellent. This is considered to be an effect obtained by a combination of the photosensitive resin composition of the present invention, in particular, (B) an acylphosphine oxide photopolymerization initiator and (C1) an alkylaminobenzene derivative as a hydrogen donor. .
On the other hand, in Comparative Examples 1 to 4, the problems of bottom curability and resist shape were not solved, and the thickness around the pattern of the permanent mask resist (solder resist) was generated, resulting in an insufficient result. .

I) Details of each material in Table 2 are as follows.
・ Irgacure 819: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (trade name, manufactured by BASF Japan Ltd.)
・ Darocur TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name, manufactured by BASF Japan Ltd.)
Irgacure 907: 2-methyl- [4- (methylthio) phenyl] morpholino-1-propanone (trade name, manufactured by BASF Japan Ltd.)
・ Irgacure 369: 2-benzoyl-2-dimethylamino-1- (4-morpholino-phenyl) butanone-1 (trade name, manufactured by BASF Japan Ltd.)
・ Pyrazoline sensitizer: 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline ・ EAB: 4,4′-diethylaminobenzophenone (Hodogaya Chemical ( Made by Co., Ltd.)
DETX-S: 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd.)
・ Kayarad DPHA: Dipentaerythritol pentaacrylate (Nippon Kayaku Co., Ltd., trade name)
- BaSO _4: Sakai Chemical Industry Co., Ltd., SiO ₂ :( Ltd.) Tatsumori Ltd. - EPIKOTE 828: bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd., trade name)

From the results shown in Table 2, the photosensitive resin compositions of Examples 7 to 12 of the present invention were excellent in photosensitivity, maintained bottom curability and excellent in resist shape even in digital exposure. A via shape was obtained. Further, the pattern of the permanent mask resist (solder resist film) is a pattern in which the hole diameter is 100 μm and the interval pitch between holes is 100 μm, or the hole diameter is 80 μm and the interval pitch between holes is as high as 80 μm. Even with a fine pattern, it was confirmed that the surrounding thickness could be reduced and the via diameter accuracy was excellent. Moreover, it was confirmed that not only the excellent resist shape but also other properties such as solder heat resistance are excellent. This is considered to be an effect obtained by the combination of the photosensitive resin composition of the present invention, in particular, (B) an acylphosphine oxide photopolymerization initiator and (C2) a pyrazoline sensitizer.
On the other hand, in Comparative Examples 5 to 12, the problems of bottom curability and resist shape are not solved, and the pattern of permanent mask resist (solder resist) (the hole diameter is 100 μm and the pitch between holes is 100 μm). Or a pattern in which the hole diameter is 80 μm and the interval between holes is 80 μm) is also insufficient.

I) Details of each material in Table 3 are as follows.
・ Irgacure 819: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (trade name, manufactured by BASF Japan Ltd.)
・ Darocur TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name, manufactured by BASF Japan Ltd.)
・ Irgacure 907: 2-methyl- [4- (methylthio) phenyl] morpholino-1-propanone (trade name, manufactured by BASF Japan Ltd.)
Anthracene sensitizer 1: 9,10-dibutoxyanthracene Anthracene sensitizer 2: 9,10-diethoxyanthracene Anthracene sensitizer 3: 9,10-dipropoxyanthracene EAB: 4, 4'-diethylaminobenzophenone (Hodogaya Chemical Co., Ltd.)
DETX-S: 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd.)
・ Kayarad DPHA: Dipentaerythritol pentaacrylate (Nippon Kayaku Co., Ltd., trade name)
- BaSO _4: Sakai Chemical Industry Co., Ltd., SiO ₂ :( Ltd.) Tatsumori Ltd. - EPIKOTE 828: bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd., trade name)

From the results shown in Table 3, the photosensitive resin compositions of the present invention of Examples 13 to 18 have excellent photocurability, and the pattern of the permanent mask resist (solder resist) has a large hole diameter. Even if it is a high-definition pattern with a length of 100 μm and a spacing pitch between holes of 100 μm, or a high-definition pattern with a hole diameter of 80 μm and a spacing pitch between holes of 80 μm, it has excellent bottom curability. It was confirmed that an excellent resist shape was obtained and that the via diameter accuracy was excellent without undercut, skirting, or thickening being confirmed, or the linearity of the pattern contour being poor. In addition to having excellent solder heat resistance and flux corrosion resistance, it was also confirmed that it has excellent performance such as adhesion, solvent resistance, and chemical resistance (acid resistance, alkali resistance). .
On the other hand, in Comparative Examples 13 to 20, the photocurability and the bottom curability were low, the resist shape exhibited an undercut, and the resist shape was poor.

I) Details of each material in Table 4 are as follows.
・ Irgacure 819: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (trade name, manufactured by BASF Japan Ltd.)
・ Darocur TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name, manufactured by BASF Japan Ltd.)
Irgacure 907: 2-methyl- [4- (methylthio) phenyl] morpholino-1-propanone (trade name, manufactured by BASF Japan Ltd.)
• Imidazole: 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer • Acridine: 1,7-bis (9,9′-acridinyl) heptane • Titanocene: bis (η ⁵ -cyclopentadienyl) -Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium Irgacure OXE01: (1,2-octanedione, 1- [4- (phenylthio)-, 2- (o- Benzoyl oxime)] (BASF Japan Ltd., trade name)
・ Kayarad DPHA: Dipentaerythritol pentaacrylate (Nippon Kayaku Co., Ltd., trade name)
- BaSO _4: Sakai Chemical Industry Co., Ltd., SiO ₂ :( Ltd.) Tatsumori Ltd. - EPIKOTE 828: bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd., trade name)

From the results shown in Table 4, the photosensitive resin compositions of Examples 19 to 24 of the present invention maintain the bottom curability and stably obtain a via shape excellent in the resist shape. Even if the pattern of the resist is a pattern with a hole diameter of 100 μm and an interval pitch between holes of 100 μm, or a high-definition pattern with a hole diameter of 80 μm and an interval pitch between holes of 80 μm, It was confirmed that the surrounding thickness could be reduced and the via diameter accuracy was excellent. Moreover, it was confirmed that not only the excellent resist shape but also other properties such as solder heat resistance are excellent. This is considered to be an effect obtained by the combination of the photosensitive resin composition of the present invention, in particular, (B) an acylphosphine oxide photopolymerization initiator and (C3) a photopolymerization initiator.
On the other hand, in Comparative Examples 21 to 24, the problems of bottom curability and resist shape were not solved, and thickening around the pattern of the permanent mask resist occurred, which was an insufficient result.

I) Details of each material in Table 5 are as follows.
・ Irgacure 819: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (trade name, manufactured by BASF Japan Ltd.)
・ Darocur TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name, manufactured by BASF Japan Ltd.)
・ Irgacure 907: 2-methyl- [4- (methylthio) phenyl] morpholino-1-propanone (trade name, manufactured by BASF Japan Ltd.)
Irganox 1010: Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name, manufactured by BASF Japan Ltd.)
Irganox 1035: Thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name, manufactured by BASF Japan Ltd.)
Irganox 1076: Octadecyl [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name, manufactured by BASF Japan Ltd.)
・ Kayarad DPHA: Dipentaerythritol pentaacrylate (Nippon Kayaku Co., Ltd., trade name)
- BaSO _4: Sakai Chemical Industry Co., Ltd., SiO ₂ :( Ltd.) Tatsumori Ltd. - EPIKOTE 828: bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd., trade name)

From the results shown in Table 5, in the photosensitive resin compositions of Examples 25 to 30 of the present invention, the pattern of the permanent mask resist (solder resist) has a hole diameter of 100 μm and an interval pitch between holes of 100 μm. Even if it is a high-definition pattern with a hole diameter of 80 μm and an interval pitch between holes of 80 μm, excellent surface curability and bottom curability are maintained, undercut, skirting, or It was confirmed that an excellent resist shape was obtained without being thickened or the linearity of the pattern outline was poor, and that the via diameter accuracy was excellent. In addition to having excellent solder heat resistance and flux corrosion resistance, it was also confirmed that it has excellent performance such as adhesion, solvent resistance, and chemical resistance (acid resistance, alkali resistance). .
On the other hand, in Comparative Examples 25 to 30, the surface curability and the bottom curability are low, and the resist shape exhibits an undercut. In Comparative Examples 29 and 30, the irradiation dose during development is increased, so that the surface Although the curability and bottom curability were good, the halation increased and the line width of the middle part (center part) and deepest part (bottom part) increased with respect to the line width of the surface part (top part) of the pattern cross section. As a result, the resist shape deteriorated.

I) Details of each material in Table 6 are as follows.
・ Irgacure 819: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (trade name, manufactured by BASF Japan Ltd.)
Irgacure 907: 2-methyl- [4- (methylthio) phenyl] morpholino-1-propanone (trade name, manufactured by BASF Japan Ltd.)
DETX-S: 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd., trade name)
-MBI: Mercaptobenzimidazole-Phthalocyanine pigment: Sanyo dye Co., Ltd.-Aronix M402: Dipentaerystol hexaacrylate (trade name, manufactured by Toagosei Co., Ltd.)
・ BaSO ₄ : Sakai Chemical Industry Co., Ltd. ・ SiO ₂ : Tatsumori Co., Ltd. ・ YSLV-80XY: Tetramethylbisphenol F type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., trade name)
RE-306: Novolac type polyfunctional epoxy resin (product name) manufactured by Nippon Kayaku Co., Ltd.
PB-3600: Epoxidized polybutadiene (trade name, manufactured by Daicel Chemical Industries, Ltd.)
SP1108: Polyester resin (trade name, manufactured by Hitachi Chemical Co., Ltd.)
-DICY 7: Dicyandiamide

From the results shown in Table 6, in the photosensitive resin compositions of the present invention of Examples 31 to 34, the pattern of the photosensitive element and the permanent mask resist (solder resist) had a hole diameter of 100 μm and a space between the holes. Even if the pattern is 100 μm in spacing pitch, or a high-definition pattern with a hole diameter of 80 μm and spacing pitch between holes of 80 μm, undercut, skirting, or thickening is confirmed, or the pattern contour It was confirmed that an excellent resist shape could be obtained without the linearity being bad.
Moreover, it was confirmed that it was excellent also in various performances such as electroless plating resistance, solder heat resistance, crack resistance, adhesion, solvent resistance, and chemical resistance (acid resistance and alkali resistance).
In contrast, the photosensitive resin compositions of Comparative Examples 31 to 34 were inferior in resist shape and solder heat resistance and crack resistance.

According to the present invention, a photosensitive resin capable of forming a pattern having excellent linearity of the pattern outline, excellent resist shape, and excellent resolution without occurrence of undercut that causes the bottom portion to be removed and lack of the upper portion of the resist. It is possible to obtain a permanent mask resist capable of forming a pattern, which is excellent in the composition and the formation stability of the refined hole diameter and the pitch between the holes. The permanent mask resist is suitably used for a printed wiring board.

Claims (15)

(A) acid-modified vinyl group-containing epoxy resin, (B) acylphosphine oxide photopolymerization initiator, (C1) alkylaminobenzene derivative, (C2) pyrazoline sensitizer or anthracene sensitizer, (C3 ) At least one photopolymerization initiator selected from an imidazole photopolymerization initiator, an acridine photopolymerization initiator, and a titanocene photopolymerization initiator, (C4) a hindered phenol antioxidant, a quinone antioxidant, At least one antioxidant selected from amine-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants, and (C5) at least one (C) additive selected from thiol group-containing compounds; (D) The photosensitive resin composition containing a photopolymerizable compound. (A) An acid-modified vinyl group-containing epoxy resin is an epoxy resin having a structural unit represented by general formula (I), an epoxy resin having a structural unit represented by general formula (II), or represented by general formula (III) At least one epoxy selected from an epoxy resin having a structural unit, a bisphenol novolac epoxy resin having a structural unit represented by the general formula (IV), and a bisphenol novolac epoxy resin having a structural unit represented by the general formula (V) Obtained by reacting the resin (a ′) obtained by reacting the resin (a) with the vinyl group-containing monocarboxylic acid (b) and the saturated or unsaturated group-containing polybasic acid anhydride (c). The photosensitive resin composition of Claim 1 which is resin.

[In Formula (I), R ¹¹ represents a hydrogen atom or a methyl group, and Y ¹ represents a glycidyl group. ]

[In the formula (II), R ¹² represents a hydrogen atom or a methyl group, and Y ² represents a glycidyl group. A plurality of R ¹² may be the same or different. ]

[In Formula (III), Y ³ represents a hydrogen atom or a glycidyl group, at least one Y ³ represents a glycidyl group, and a plurality of Y ³ may be the same or different. ]

[In the formula (IV), R ¹³ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a sulfone group, or a trihalomethyl group, Y ⁴ represents a hydrogen atom or a glycidyl group, and at least one Y ⁴ represents glycidyl. And a plurality of R ¹³ may be the same or different. ]

[In the formula (V), R ¹⁴ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a sulfone group, or a trihalomethyl group, Y ⁵ represents a hydrogen atom or a glycidyl group, and at least one Y ⁵ represents glycidyl. A plurality of R ¹⁴ may be the same or different. ] (B) Acylphosphine oxide photopolymerization initiator is (2,6-dimethoxybenzoyl) -2,4,6-trimethylbenzoyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-2,4,6-trimethylbenzoylphenylphosphinate, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, (2,5-dihydroxy Phenyl) diphenylphosphine oxide, (p-hydroxyphenyl) diphenylphosphine oxide, bis (p-hydroxyphenyl) phenylphosphine oxide, and tris (p-hydroxyphenyl) phosphine oxide At least one is a photosensitive resin composition according to claim 1 or 2 which is. The additive according to any one of claims 1 to 3, wherein the additive (C) is at least one (C1) alkylaminobenzene derivative selected from phenylglycine derivatives, aminobenzoic acid derivatives, and aminobenzoic acid ester derivatives. Photosensitive resin composition. The photosensitive resin composition according to any one of claims 1 to 3, wherein the additive (C) is a (C2) pyrazoline sensitizer represented by the following general formula (VI).

[In the formula (VI), R represents an alkyl group having 4 to 12 carbon atoms, a, b and c each represents an integer of 0 to 2, and the sum of a, b and c is 1 to 6. When the sum of a, b and c is 2 to 6, a plurality of R in the same molecule may be the same or different. ] The photosensitive resin according to any one of claims 1 to 3, wherein the additive (C) is at least one (C2) anthracene sensitizer selected from dialkylanthracene, diphenylanthracene, and dialkoxyanthracene. Composition. (C) The additive is 2,4,5-triarylimidazole dimer, 1,7-bis (9,9′-acridinyl) heptane, bis (η ⁵ -cyclopentadienyl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium and bis (2,4-cyclopentadienyl) -bis (2,6-difluoro-3- (1-pyryl) phenyl) titanium The photosensitive resin composition according to any one of claims 1 to 3, which is at least one (C3) photopolymerization initiator selected from: The additive according to any one of claims 1 to 3, wherein the additive (C) is at least one (C4) antioxidant selected from a hindered phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant. 2. The photosensitive resin composition according to item 1. The photosensitive composition according to any one of claims 1 to 3, wherein the additive (C) is at least one (C5) thiol group-containing compound selected from mercaptobenzoxazole, mercaptobenzothiazole, and mercaptobenzimidazole. Resin composition. The photosensitive resin composition according to any one of claims 1 to 9, wherein the (D) photopolymerizable compound is a compound containing a (meth) acryloyl group. The photosensitive resin composition according to any one of claims 1 to 10, further comprising (E) an inorganic filler. 12. The photosensitive resin composition according to claim 1, which is used for forming a permanent mask resist. A photosensitive element comprising: a support; and a photosensitive layer formed using the photosensitive resin composition according to any one of claims 1 to 12 on the support. A permanent mask resist formed from the photosensitive resin composition according to any one of claims 1 to 12. A printed wiring board comprising the permanent mask resist according to claim 14.

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