KR102570738B1 - Photosensitive-resin composition - Google Patents

Abstract

(A) an acid-modified vinyl group-containing epoxy resin, (B) an acylphosphine oxide-based photopolymerization initiator, (C1) an alkylaminobenzene derivative, (C2) a pyrazoline-based sensitizer or anthracene-based sensitizer, (C3) an already at least one photopolymerization initiator selected from a dazole-based photopolymerization initiator, an acridine-based photopolymerization initiator, and a titanocene-based photopolymerization initiator, (C4) a hindered phenol-based antioxidant, a quinone-based antioxidant, an amine-based antioxidant, a sulfur-based antioxidant, And at least one antioxidant selected from phosphorus antioxidants, and (C5) at least one additive selected from thiol group-containing compounds, and (D) a photopolymerizable compound. .

Description

Photosensitive resin composition {PHOTOSENSITIVE-RESIN COMPOSITION}

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

[0002] In the field of manufacturing printed wiring boards, it is practiced to form permanent mask resistors on printed wiring boards. The permanent mask resistor has a role of preventing corrosion of the conductor layer or maintaining electrical insulation between the conductor layers when the printed wiring board is used. In recent years, a permanent mask resistor has been developed to prevent solder from adhering to unnecessary portions of the conductor layer of a printed wiring board in a process of carrying out flip chip mounting, wire bonding mounting, etc. through soldering of a semiconductor element on a printed wiring board. It also had a role as a membrane.

Conventionally, permanent mask resistors in printed wiring board production are produced by screen printing using a thermosetting resin composition or by a photographic method using a photosensitive resin composition. For example, in flexible wiring boards using the mounting methods of FC (Flip-Chip), TAB (Tape-Automated-Bonding), and COF (Chip-On-Film), IC chips, electronic parts, LCD (Liquid, Crystal, Display) panels, and connections A permanent mask resistor is formed by screen printing and thermosetting a thermosetting resin paste except for the wiring pattern portion (for example, Patent Document 1).

In addition, in semiconductor package substrates such as BGA (Ball, Grid, Array) and CSP (Chip, Size, Package) mounted on electronic components, (1) in order to flip-chip mount a semiconductor element through solder on a semiconductor package substrate, ( 2) In order to wire-bond the semiconductor element and the semiconductor package substrate, or (3) to solder the semiconductor package substrate onto the main board substrate, it is necessary to remove the permanent mask resistor at the joint portion. Therefore, in the formation of this permanent mask resist, a photographic method is used in which a photosensitive resin composition is cured by selectively irradiating actinic rays such as ultraviolet rays after application and drying, and only the unirradiated portion is removed with a developer to form an image. . Since the photographic method is suitable for mass production in view of its workability, it is widely used in the image formation of photosensitive resin compositions in the electronic material industry (for example, Patent Documents 2 to 4).

Patent Document 1: Japanese Unexamined Patent Publication No. 2003-198105 Patent Document 2: Japanese Unexamined Patent Publication No. Hei 11-240930 Patent Document 3: Japanese Unexamined Patent Publication No. 2010-235739 Patent Document 4: Japanese Unexamined Patent Publication No. 2011-133851

However, when using the photosensitive resin composition to which pigments, fillers, etc. are added as described in Patent Literatures 2 to 4, the pigments, fillers, etc. prevent transmission of ultraviolet rays or absorb ultraviolet rays, so that the thickness is 20 to 40 μm or more. When attempting to form a permanent mask resistor, which is a thick film called, photocuring of the photosensitive resin composition at the bottom may not be sufficiently obtained, and as a result, an undercut in which the bottom is cut out after development may occur.

If the exposure amount of ultraviolet irradiation is increased in order to improve the photocurability of the bottom portion, light diffraction and halation increase, and the middle portion (center portion) and deepest portion of the pattern cross section with respect to the line width of the surface portion (upper portion) are increased. Since the line width of the part (bottom part) is increased, there is a problem that the resist shape is deteriorated or the resolution is lowered. In addition, there is also a problem that the upper portion of the resist is missing and the resist shape deteriorates due to insufficient photocuring in the region extending from the surface to about 3 μm in the depth direction of the resist due to oxygen inhibition. Therefore, in the case of forming a permanent mask resistor, which is a thick film of 20 to 40 μm or more, the photosensitive resin composition having good bottom photocurability and excellent resolution does not exist.

In addition, in recent years, along with the miniaturization and high performance of electronic devices, the size of the hole diameter of the permanent mask resistor and the pitch between the holes tend to be miniaturized. For example, a high-precision pattern is used in which the hole diameter is 100 μm and the interval pitch between the holes is 100 μm, or the hole diameter is 80 μm and the interval between the holes is 80 μm. For this reason, for example, in flip-chip mounting, a permanent mask resistor which is excellent in resist shape stability in terms of solder fillability as well as improvement in resolution is required.

An object of the present invention has been made in view of these problems, and since the hardenability of the bottom of the via opening is excellent, it is possible to increase the exposure amount of ultraviolet irradiation without occurrence of undercuts in which the bottom is cut out and chipping of the upper part of the resist. Therefore, 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, that is, a pattern having good linearity of the pattern outline, excellent resist shape, and excellent resolution can be formed. It is to provide a printed wiring board provided with a photosensitive resin composition, a photosensitive element using the photosensitive resin composition, a permanent mask resistor, and the permanent mask resistor.

In addition, by using the photosensitive resin composition of the present invention, a photosensitive element capable of forming a pattern and a permanent mask having excellent stability in formation of the size of the miniaturized hole diameter and the pitch between holes in accordance with the recent miniaturization and performance of electronic devices, and permanent mask It is to provide a printed wiring board provided with a resistor and its permanent mask resistor.

The inventors of the present invention, as a result of intensive research to solve the above problems, found that they can be solved by the following invention. That is, this invention provides the following photosensitive resin composition, photosensitive element, permanent mask resistor, and printed wiring board.

[1] (A) an acid-modified vinyl group-containing epoxy resin, (B) an acylphosphine oxide-based photopolymerization initiator, (C1) an alkylaminobenzene derivative, (C2) a pyrazoline-based sensitizer or anthracene-based sensitizer, ( C3) at least one photopolymerization initiator selected from imidazole-based photopolymerization initiators, acridine-based photopolymerization initiators, and titanocene-based photopolymerization initiators, (C4) hindered phenol-based antioxidants, quinone-based antioxidants, amine-based antioxidants, and sulfur-based photopolymerization initiators A photosensitive resin composition comprising at least one antioxidant selected from antioxidants and phosphorus antioxidants, (C5) at least one additive selected from thiol group-containing compounds, and (D) a photopolymerizable compound. .

[2] A photosensitive element comprising a support and a photosensitive layer made of the photosensitive resin composition according to [1] above on the support.

[3] A permanent mask resistor formed from the photosensitive resin composition described in [1] above.

[4] A printed wiring board provided with the permanent mask resistor described in [3] above.

According to the present invention, a photosensitive resin composition capable of forming a pattern with excellent linearity of pattern outline, excellent resist shape, and excellent resolution without occurrence of undercutting in which the bottom portion is hollowed out and missing of the upper portion of the resist, A photosensitive element and a permanent mask resistor capable of forming patterns with excellent formation stability of the miniaturized hole diameter and pitch between holes, and a printed wiring board including the same can be obtained.

1] It is a schematic diagram of the cross section of the resist formed using the photosensitive resin composition of this invention.
[Fig. 2] It is a figure showing the pattern shape of the negative mask used in the Example.
[Fig. 3] It is a figure showing the pattern shape of the negative mask used in the Example.

[Photosensitive Resin Composition]

The photosensitive resin composition according to the embodiment in the present invention (hereinafter also referred to simply as “this embodiment”) includes (A) an acid-modified vinyl group-containing epoxy resin (hereinafter also referred to as “component (A)”) and , (B) an acylphosphine oxide photopolymerization initiator (hereinafter also referred to as “(B) component”), (C1) an alkylaminobenzene derivative (hereinafter also referred to as “(C1) component”), (C2) pyrazoline At least one photopolymerization initiator selected from an imidazole-based photopolymerization initiator, an acridine-based photopolymerization initiator, and a titanocene-based photopolymerization initiator (hereinafter, also referred to as “component (C3)”), (C4) at least one antioxidant selected from hindered phenolic antioxidants, quinone antioxidants, amine antioxidants, sulfur antioxidants, and phosphorus antioxidants (hereinafter also referred to as “(C4) component”), and (C5) thiol group-containing compounds (hereinafter also referred to as “(C5) component”) at least one (C) additive (hereinafter referred to as “(C) component”) ) component") and (D) a photopolymerizable compound (hereinafter, also referred to as "(D) component") is a photosensitive resin composition.

Hereinafter, each component is demonstrated.

<(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 (A) component.

(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, and an epoxy resin obtained by reacting an epoxy resin (a) with a vinyl group-containing monocarboxylic acid (b) ( a') is preferable, and the epoxy resin (a'') obtained by reacting the epoxy resin (a') with a saturated or unsaturated group-containing polybasic acid anhydride (c) is more preferable.

As an epoxy resin (a), it is preferable that it is at least 1 sort(s) chosen from the epoxy resin which has structural units represented by the following general formula (I) - (V). Epoxy resins having structural units represented by each general formula will be described.

[Novolak-type epoxy resin having a structural unit represented by general formula (I)]

First, as the epoxy resin (a), a novolak-type epoxy resin having a structural unit represented by the following general formula (I) is preferably used. As an epoxy resin having such a structural unit, for example, the following general formula ( A novolak-type epoxy resin represented by I') is preferably used.

In general formula (I), R ¹¹ represents a hydrogen atom or a methyl group, and Y ¹ represents a glycidyl group.

Among the novolac-type epoxy resins 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, still more preferably It is 95 mass % or more.

In 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 between the hydrogen atom and the glycidyl group is preferably 0. :100 to 30:70, more preferably 0:100 to 10:90, still more preferably 0:100. As can be seen from the molar ratio between hydrogen atoms and glycidyl groups, at least one Y ¹ ' represents a glycidyl group. In general formula (I'), n1 represents an integer greater than or equal to 1. In addition, a plurality of R ¹¹ ′ may be the same or different, respectively, and a plurality of Y ¹ ′ may be the same or different.

n1 is an integer greater than or equal to 1 as mentioned above, Preferably it is 10-200, More preferably, it is 30-150, More preferably, it is 30-100. When n1 is within the above range, a resist pattern with a better balance of resist shape, resolution, heat resistance, adhesion, and electrical insulation tends to be obtained.

As a novolac-type epoxy resin represented by general formula (I'), a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, etc. are mentioned preferably, for example. These novolac-type epoxy resins can be obtained, for example, by a known method by reacting a phenol resin such as a phenol novolac resin or a cresol novolac resin with an epihalohydrin such as epichlorohydrin.

Examples of the novolak-type epoxy resin represented by general formula (I') include YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, YDPN-602 (above, new Nippon Seitetsu Sumiking Chemical Co., Ltd., trade name), DEN-431, DEN-439 (above, Dow Chemical Co., Ltd., trade name), EOCN-120, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027, BREN (above, manufactured by Nippon Kayaku Co., Ltd., trade names), EPN-1138, EPN-1235, EPN-1299 (above, manufactured by BASF Japan Co., Ltd., trade names) , N-730, N-770, N-865, N-665, N-673, VH-4150, VH-4240 (above, manufactured by DIC Corporation, trade names) 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, and examples of the epoxy resin having such a structural unit are represented by the following general formula (II'). A bisphenol A-type epoxy resin and a bisphenol F-type epoxy resin are mentioned preferably.

In general formula (II), R ¹² represents a hydrogen atom or a methyl group, and Y ² represents a glycidyl group.

Among the epoxy resins having structural units represented by general formula (II), the content of structural units represented by general formula (II) is preferably 70% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more. mass % or more.

In 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 between the hydrogen atom and the glycidyl group is preferably 0. :100 to 30:70, more preferably 0:100 to 10:90, still more preferably 0:100. As can be seen from the molar ratio between hydrogen atoms and glycidyl groups, at least one Y ² ' represents a glycidyl group. In general formula (II'), n2 represents an integer greater than or equal to 1. In addition, a plurality of R ¹² ' may be the same or different, and when n2 is 2 or more, a plurality of Y ² ' may be the same or different.

n2 is an integer greater than or equal to 1 as mentioned above, Preferably it is 10-100, More preferably, it is 10-80, More preferably, it is 15-60. When n2 is within the above range, a resist pattern with a better balance of resist shape, resolution, adhesion, heat resistance, and electrical insulation tends to be obtained.

The bisphenol A-type epoxy resin or bisphenol F-type epoxy resin in which Y ² ' is a glycidyl group represented by the general formula (II') is, for example, the bisphenol A-type epoxy resin or bisphenol F represented by the following general formula (VII) It can obtain by making the hydroxyl group of a mold epoxy resin and epihalohydrin, such as epichlorohydrin, react.

In Formula (VII), R ¹² and n2 are the same as above.

The amount of epihalohydrin used is represented by the general formula (VII), considering that a resist pattern having a better balance of resist shape, resolution, film strength, heat resistance, insulation reliability, thermal shock resistance, and resolution can be obtained. It is preferable to set it as 2-10 mol with respect to 1 mol of hydroxyl groups in an epoxy resin.

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. Examples of the basic catalyst include preferably alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides, etc., and alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide are more preferable from the viewpoint of catalytic activity. . Moreover, it is preferable that the usage-amount is 0.9-2 mol with respect to 1 mol of hydroxyl groups in the epoxy resin represented by General formula (VII).

In the reaction between the epoxy resin represented by the general formula (VII) and 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; ethers such as tetrahydrofuran and dioxane; It is preferable to use polar organic solvents, such as dimethylformamide, dimethylacetamide, and dimethyl sulfoxide. Among these, it can be used individually by 1 type or in combination of 2 or more types, and it is preferable to use 2 or more types in combination from a viewpoint of polarity adjustment.

Further, 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 less likely to be delayed and side reaction products are less likely to be generated.

After the above reaction, unreacted epihalohydrin, organic solvent, etc. are distilled off by distillation, preferably under heating and reduced pressure, to obtain an epoxy resin represented by general formula (II') .

In addition, from the viewpoint of obtaining a higher purity epoxy resin, the obtained epoxy resin can be redissolved in an organic solvent, and a basic catalyst such as the alkali metal hydroxide described above 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 an amount of 0.1 to 3% by mass relative to the epoxy resin. In this case, a high-purity epoxy resin can be obtained by removing a salt or the like produced after completion of the reaction by filtration, washing with water, or the like, and further distilling off the organic solvent or 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 Epicoat 807, 815, 825, 827, 828, 834, 1001, 1004, 1007 and 1009 (above, Mitsubishi Gagaku Co., Ltd., trade name), DER-330, DER-301, DER-361 (above, Dow Chemical Co., Ltd., trade name), YD-8125, YDF-170, YDF-175S, YDF-2001, YDF-2004, YDF-8170 (above, Nippon Seitetsu Sumiking Chemical Co., Ltd. product, trade name), etc. are commercially available.

[Epoxy resin having 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 used, and examples of the epoxy resin having such a structural unit are represented by the following general formula (III'). A triphenolmethane type epoxy resin is preferably used.

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

n3 is an integer greater than or equal to 1 as mentioned above, Preferably it is 10-100, More preferably, it is 15-80, More preferably, it is 15-70. When n3 is within the above range, a resist pattern having a more excellent balance of resist shape, resolution, heat resistance, adhesion, and electrical insulation can be obtained.

Among the epoxy resins 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, still more preferably 95% by mass or more. mass % or more.

As a triphenol methane type epoxy resin represented by general formula (III'), FAE-2500, EPPN-501H, EPPN-502H (above, Nippon Kayaku Co., Ltd. product, brand name) etc. are commercially available, for example. do.

[Bisphenol novolak-type epoxy resin having structural units represented by general formula (IV)]

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

In general formula (IV), R ¹³ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a sulfone group, or a trihalomethyl group, and 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 groups may be the same or different.

1-20 are preferable, as for carbon number of the alkyl group of R ^<13> , 1-12 are more preferable, and 1-3 are still more preferable. Further, 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 methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, sec-pentyl group, isopentyl group, and neopentyl group. These etc. are mentioned preferably, Among these, a methyl group is more preferable.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, anthryl group, and a phenanthryl group, preferably an aryl group having 6 to 20 ring carbon atoms, more preferably 6 ring carbon atoms. It is an aryl group of ~14. Further, 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. Further, 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.

Among the epoxy resins 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, still more preferably 95% by mass or more. mass % or more.

Within the above range, a resist pattern having a more excellent balance of resist shape, resolution, heat resistance, adhesion, and electrical insulation can be obtained.

[Bisphenol novolak-type epoxy resin having a structural unit represented by general formula (V)]

As the epoxy resin (a), a bisphenol novolak-type epoxy resin having a structural unit represented by the following general formula (V) is preferably exemplified.

In 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. In addition, as an alkyl group, an aryl group, and an aralkyl group of R ^<14> , the same thing as what was described for R ^<13> can be illustrated, and the preferable shape is also the same.

Among the epoxy resins 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, still more preferably 95% by mass or more. mass % or more. Within the above range, a resist pattern having a more excellent balance of resist shape, resolution, heat resistance, adhesion, and electrical insulation can be obtained.

In general formula (V), 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 and Y ⁵ is What is a glycidyl group is commercially available as EPON SU8 series (Mitsubishi Chemical Co., Ltd. product, brand name).

The bisphenol novolak-type epoxy resin having structural units represented by general formulas (IV) and (V) is, for example, the hydroxyl group and epichlorohydride of bisphenol novolak resins represented by the following general formulas (VIII) and (IX), respectively. It can be obtained by reacting epihalohydrins such as drin.

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

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

Here, the bisphenol compound is not particularly limited as long as it is a compound having two hydroxyphenyl groups, and examples thereof include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, and bisphenol G , bisphenol M, bisphenol S, bisphenol P, bisphenol TMC, bisphenol Z, etc. are mentioned preferably, and bisphenol A and bisphenol F are more preferable.

As the aldehyde compound to be reacted with the bisphenol compound, formaldehyde, acetaldehyde, benzaldehyde, 4-methylbenzaldehyde, 3,4-dimethylbenzaldehyde, biphenylaldehyde, naphthylaldehyde, etc. are preferably mentioned. As the ketone compound, Benzophenone, fluorenone, indanone, etc. are mentioned preferably. Among these, formaldehyde is preferable.

Examples of sulfonic acids having an alkyl group having 1 to 4 carbon atoms in the molecular structure include alkanesulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid and butanesulfonic acid, and perfluoroalkanesulfonic acids having a fluorine atom in the alkane moiety. .

The bisphenol novolak-type epoxy resin having structural units represented by general formulas (IV) and (V) can be more specifically, preferably obtained as follows.

The above bisphenol compound and aldehyde compound or ketone compound are placed in a reaction vessel, and sulfonic acid is continuously or intermittently added thereto to maintain a temperature in the range of 20 to 200° C. while stirring under an inert gas atmosphere to obtain a bisphenol compound and an aldehyde compound or ketone compound is reacted to obtain a crude bisphenol novolak 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 to neutralize, and further, the water-insoluble organic solvent is distilled off to obtain a bisphenol novolak-type epoxy resin can be obtained.

Here, the water-insoluble organic solvent preferably has a boiling point of 100 to 130°C from the viewpoint of improving the working efficiency of extraction, washing with water, and neutralization. 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 A butyl ketone is more preferable, and a methyl isobutyl ketone is still more preferable.

The above water washing is performed until the crude bisphenol novolak resin solution reaches pH 3 to 7, more preferably pH 5 to 7, and, if necessary, basic substances such as sodium hydroxide, sodium carbonate, ammonia, and triethylenetetramine are added. You can use it to neutralize it.

The above distillation is preferably carried out by heating and vacuum distillation under the conditions of, for example, a temperature of 170 to 200 ° C. and a pressure of 3 kPa or less.

As the epoxy resin (a), from the viewpoint of being excellent in process induction and improving solvent resistance, a novolac-type epoxy resin having a structural unit represented by general formula (I), general formula (II) An epoxy resin having a structural unit represented by , and a bisphenol novolac-type epoxy resin having a structural unit represented by general formula (IV) are preferred, and a novolac-type epoxy resin represented by general formula (I'), general formula (II' A bisphenol A-type epoxy resin or bisphenol F-type epoxy resin represented by ), and a bisphenol novolac A-type epoxy resin or bisphenol F-type epoxy resin having a structural unit represented by general formula (IV) are more preferred.

In addition, from the viewpoint of being able to further reduce the warpage of the thin film substrate and further improving the thermal shock resistance, an epoxy resin having a structural unit represented by general formula (IV) and a structural unit represented by general formula (V) It is preferable to use an epoxy resin together.

(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-furfuryl acrylic acid, β-styryl acrylic acid, cinnamic acid, acrylic acid derivatives such as crotonic acid and α-cyanocinnamic acid; A half-ester compound that is a reaction product of a hydroxyl group-containing acrylate and a dibasic acid anhydride, a half-ester compound that is a reaction product of a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester and a dibasic acid anhydride, etc. may be preferred.

The half-ester compound can be 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 individually by 1 type or in combination of 2 or more types.

Examples of the hydroxyl group-containing acrylate, vinyl group-containing monoglycidyl ether, and vinyl group-containing monoglycidyl ester used in the synthesis of the above half-ester compound, which is an example of the vinyl group-containing monocarboxylic acid (b), include hydroxyl Roxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, ditrimethylolpropanedi(meth)acrylate, pentaerythritol tri( meth) acrylate, dipentaerythritol penta (meth) acrylate, vinyl glycidyl ether, glycidyl (meth) acrylate and the like are preferred.

As dibasic acid anhydrides used in the synthesis of the above half ester compounds, those containing a saturated group and those 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, and ethylhexahydrophthalic anhydride. , itaconic acid anhydride, etc. are mentioned preferably.

In the above reaction between the epoxy resin (a) and the monocarboxylic acid (b) containing a vinyl group, the proportion of the monocarboxylic acid (b) containing a vinyl group is 0.6 to 1.05 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin (a). It is preferable to make it react with, it is more preferable to make it react in the ratio which becomes 0.8-1.0 equivalent, and it is more preferable to make it react in the ratio which becomes 0.9-1.0 equivalent. By reacting in such a ratio, photopolymerization property improves and photosensitivity becomes a thing more excellent.

The reaction between the epoxy resin (a) and the monocarboxylic acid (b) containing a vinyl group can be carried out by dissolving the epoxy resin (a) and the monocarboxylic acid (b) containing a vinyl group 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; glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, 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 hydrocarbons such as octane and decane; Petroleum solvents, such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha, etc. are mentioned preferably.

Furthermore, it is preferable to use a catalyst to promote the reaction. Preferable 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 relative to 100 parts by mass in total of the epoxy resin (a) and the monocarboxylic acid containing a vinyl group (b). The above usage amount is preferable because the reaction between the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) is accelerated.

For the purpose of preventing polymerization during the reaction, it is preferable to use a polymerization inhibitor. As a polymerization inhibitor, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol etc. are mentioned preferably, for example. The usage amount of the polymerization inhibitor is preferably 0.01 to 1 part by mass relative to 100 parts by mass in total of the epoxy resin (a) and the monocarboxylic acid containing a vinyl group (b). The above amount is preferable because the storage stability (self-life) of the composition is improved. In addition, the reaction temperature is preferably 60 to 150°C, more preferably 80 to 120°C.

Further, if necessary, a monocarboxylic acid (b) containing a vinyl group, a phenolic compound such as p-hydroxyphenethyl alcohol, trimellitic acid anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, and biphenyltetracarboxylic acid anhydride Polybasic acid anhydrides such as these can be used together.

It is estimated that the epoxy resin (a') obtained in this way has a hydroxyl group formed by an addition reaction between the epoxy group of the epoxy resin (a) and the carboxyl group of the monocarboxylic acid (b) containing a vinyl group.

(polybasic acid anhydride (c))

(A) As the acid-modified vinyl group-containing epoxy resin, an epoxy resin (a") obtained by reacting the above-described epoxy resin (a') with a polybasic acid anhydride (c) is also preferably included. Epoxy resin (a") In this case, it is presumed that the hydroxyl group of the epoxy resin (a') (including the hydroxyl group originally present in the epoxy resin (a)) and the acid anhydride group of the polybasic acid anhydride (c) are half-esterified.

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, ethyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and ethylhexahydro Phthalic anhydride, itaconic anhydride, etc. are mentioned preferably.

In the reaction between the epoxy resin (a') and the polybasic acid anhydride (c), 0.1 to 1.0 equivalent of the polybasic acid anhydride (c) is reacted with respect to 1 equivalent of the hydroxyl group in the epoxy resin (a'), thereby acid-modified vinyl group-containing epoxy. The acid value of 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, still more 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 less likely to decrease, and when it is 150 mgKOH/g or less, the electrical properties of the cured film are less likely to decrease.

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

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

(A) The weight average molecular weight of the acid-modified vinyl group-containing epoxy resin is preferably from 3000 to 30000, more preferably from 4000 to 25000, still more preferably from 5000 to 18000. When the weight average molecular weight of component (A) is within the above range, a pattern having a more excellent balance of resist shape, resolution, heat resistance, adhesiveness, and electrical insulation properties can be obtained. Here, the weight average molecular weight is a weight average molecular weight in terms of polyethylene measured by a gel permeation chromatography (GPC) method using tetrahydrofuran as a solvent. More specifically, for example, it is measured under the following GPC measuring device and measurement conditions, and the value converted using a calibration curve of standard polystyrene can be used as the weight average molecular weight. In addition, the preparation of a calibration curve uses 5 sample sets (“PStQuick MP-H” and “PStQuick B”, manufactured by Tosoh Corporation) as standard polystyrene.

(GPC measuring device)

GPC device: high-speed GPC device "HLC-8320GPC", detector is a differential refractometer, manufactured by Tosoh Co., Ltd.

Column: Column TSKgel "SuperMultipore" HZ-H (column length: 15 cm, column inner diameter: 4.6 mm), manufactured by Tosoh Corporation

(Measuring conditions)

Solvent: Tetrahydrofuran (THF)

Measurement temperature: 40℃

Flow rate: 0.35ml/min

Sample concentration: 10mg/THF5ml

Injection volume: 20 μl

(A) As the 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, preferably, a bisphenol A type epoxy resin and a bisphenol F type epoxy resin represented by general formula (II'), and an epoxy resin obtained by reacting a vinyl group-containing monocarboxylic acid (b) ( a'), and an epoxy resin (a'') obtained by reacting the epoxy resin (a') with a saturated or unsaturated group-containing polybasic acid anhydride (c) is preferable, and an epoxy resin (a'') is more preferable. .

These epoxy resins (a') and (a'') can be used individually by 1 type or in combination of 2 or more types, and it is preferable to use them in combination of multiple types. 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 F type epoxy represented by the general formula (II') A combination of two types of an epoxy resin (a') or (a'') obtained from a resin is preferable, and an epoxy resin (a'') obtained from a novolac-type epoxy resin represented by the general formula (I'), and a general A combination of the two with an epoxy resin (a″) obtained from the bisphenol A type epoxy resin represented by the formula (II′) and the bisphenol F type epoxy resin is more preferable.

Epoxy resin (a') or (a″) obtained from a novolac-type epoxy resin represented by general formula (I'), and bisphenol A-type epoxy resin and bisphenol F-type epoxy resin represented by general formula (II') obtained from The mass mixing ratio with the epoxy resin (a') or (a'') is preferably 95:5 to 30:70, more preferably 90:10 to 40:60, and still more preferably 80:20 to 45:55. desirable.

Further, when a (C5) thiol group-containing compound described later is used as component (C), an epoxy resin (a') or (a') obtained from a bisphenol novolak-type epoxy resin having a structural unit represented by general formula (IV) '), and a combination of two types of 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') is preferable, and the general formula ( Epoxy resin (a″) obtained from a bisphenol novolac A-type epoxy resin or bisphenol F-type epoxy resin having a structural unit represented by IV), bisphenol A-type epoxy resin and bisphenol F-type epoxy represented by general formula (II’) A combination of the two with an epoxy resin (a'') obtained from the resin is more preferable.

Epoxy resin (a') or (a'') obtained from a bisphenol novolac-type epoxy resin having a structural unit represented by formula (IV) and bisphenol A-type epoxy resin and bisphenol F-type epoxy represented by formula (II') The mass mixing ratio with the epoxy resin (a') or (a'') obtained from the resin is preferably 90:10 to 30:70, more preferably 80:20 to 40:60, and 70:30 to 50: 50 is more preferable.

20-80 mass parts is preferable, as for content of (A) component which makes the total solid content in the photosensitive resin composition 100 mass parts, 30-75 mass parts is more preferable, and 40-75 mass parts is still more preferable. When the content of component (A) is within the above range, a coating film superior in heat resistance, electrical properties and chemical resistance can be obtained. Here, the solid content total amount in this embodiment is the total amount of solid content contained in (A)-(F) components. For example, when the photosensitive resin composition of this embodiment contains (A)-(D) component, the total amount of solid content contained in (A)-(D) component, and also the photosensitive resin composition of this embodiment When the components (A) to (E) are included, the total amount of solids contained in the components (A) to (E), and the photosensitive resin composition of the present embodiment also includes the components (A) to (F). In the case of doing so, the total amount of solid content contained in (A) to (F) components is the total amount of solid content.

<(B) Acylphosphine oxide photopolymerization initiator>

The photosensitive resin composition of this embodiment contains an acylphosphine oxide type photoinitiator as (B) component.

(B) the 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), for example, (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-dihydroxyphenyl)diphenylphosphine oxide, (p-hydroxyphenyl) diphenylphosphine oxide, bis (p-hydroxyphenyl) phenylphosphine oxide, tris (p-hydroxyphenyl) phosphine oxide, etc. are preferably mentioned, and one type alone Or it can use in combination of 2 or more types.

The content of the (B) acylphosphine oxide photopolymerization initiator, which makes the total solid content in the photosensitive resin composition 100 parts by mass, is preferably 0.2 to 15 parts by mass. When it is 0.2 parts by mass or more, the exposed portion becomes difficult to elute during development, and when it is 15 parts by mass or less, the heat resistance becomes difficult to decrease. For the same reasons, the content of the (B) photopolymerization initiator is more preferably 0.2 to 10 parts by mass, still more preferably 0.2 to 5 parts by mass, particularly preferably 0.5 to 5 parts by mass, and extremely preferably 0.5 to 3 parts by mass. .

In addition, photopolymerization initiators such as tertiary amines such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine It can be used individually by 1 type or in combination of 2 or more types.

<(C) Additives>

The photosensitive resin composition of the present embodiment, as component (C), (C1) an alkylaminobenzene derivative, (C2) a pyrazoline-based sensitizer or anthracene-based sensitizer, (C3) an imidazole-based photopolymerization initiator, an acridine-based photopolymerization Initiator, and at least one photopolymerization initiator selected from titanocene-based photopolymerization initiators, (C4) at least one selected from hindered phenol-based antioxidants, quinone-based antioxidants, amine-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants It contains at least 1 sort(s) chosen from a kind antioxidant, and (C5) thiol group containing compound. By using these additives in combination with (B) an acylphosphine oxide-based photopolymerization initiator, a photosensitive resin composition capable of forming patterns with excellent linearity of pattern outline, excellent resist shape, and excellent resolution can be obtained.

[(C1) Alkylaminobenzene Derivative]

The (C1) alkylaminobenzene derivative is not particularly limited as long as it has an alkylamino group on the benzene ring, and functions effectively as a hydrogen donor, and can further improve the photosensitivity and aging stability of the photosensitive resin composition. Here, the hydrogen donor means a compound capable of donating a hydrogen atom to radicals generated by exposure treatment of the photopolymerization initiator. In the present embodiment, the combination of the above (B) acylphosphine oxide-based photopolymerization initiator and the (C1) alkylaminobenzene derivative as a hydrogen donor provides particularly good linearity of the pattern outline and excellent resist shape. , it is effective in forming a pattern with excellent resolution.

(C1) As an alkylaminobenzene derivative, a phenylglycine derivative, aminobenzoic acid derivative, aminobenzoic acid ester derivative etc. are mentioned preferably, for example.

Preferred examples of the phenylglycine derivative include N-phenylglycine, N,N-diphenylglycine, and N-naphthylglycine.

As an aminobenzoic acid derivative, 2-methylaminobenzoic acid, 2-ethylaminobenzoic acid, etc. are mentioned preferably. Further, examples of aminobenzoic acid ester derivatives include ethyl N,N-dimethylaminobenzoate, ethyl N,N-diethylaminobenzoate, isoamyl N,N-dimethylaminobenzoate, and isoamyl N,N-diethylaminobenzoate. may be preferred.

In this embodiment, you may use the aromatic amine compound which has an alkylamino group. Specific examples include, for example, dialkyldiphenylamine having 8 to 14 carbon atoms in the alkyl group, octylated diphenylamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, and 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 mentioned preferably.

Among these (C1) alkylaminobenzene derivatives, N-phenylglycine, 2-methylaminobenzoic acid, and N,N-diethylaminobenzoate ethyl are preferred.

These (C1) alkylaminobenzene derivatives can be used individually by 1 type or in combination of 2 or more types. Moreover, you may use an aliphatic amine compound simultaneously with said alkylaminobenzene derivative. As a specific example, triethanolamine, triethylamine, etc. are mentioned preferably, for example.

The content of the (C1) alkylaminobenzene derivative, which makes the total solid content in the photosensitive resin composition 100 parts by mass, is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, still more preferably 0.2 to 1.5 parts by mass, and 0.2 to 5 parts by mass. 1.0 part by mass is particularly preferred. When this content is 0.1 parts by mass or more, it is difficult for the solution of the photosensitive resin composition to gel, and when it is 5 parts by mass or less, the photosensitivity is difficult to decrease, which is preferable.

[(C2) pyrazoline sensitizer or anthracene sensitizer]

(C2) Component is a pyrazoline-type sensitizer or an anthracene-type sensitizer. (C2) By adding a pyrazoline-based sensitizer, even in digital exposure, the occurrence of undercuts in which the bottom part is dug out and the absence of the upper part of the resist do not occur, and the linearity of the pattern outline is excellent, the resist shape is excellent, and the resolution is good. A photosensitive resin composition capable of forming excellent patterns can be obtained.

(C2) The pyrazoline-based sensitizer is not particularly limited as long as it is a sensitizer having a pyrazole ring, but a pyrazoline-based 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 represent an integer of 0 to 2, and the sum of a, b and c is 1 to 6. When the total of a, b, and c is 2 to 6, plural R's 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. As R, an alkyl group having 4, 8, and 12 carbon atoms is preferable, and more specifically, an n-butyl group, a tert-butyl group, a tert-octyl group, and an n-dodecyl group are preferable, and the same or It is preferable to be different.

As such a pyrazoline sensitizer, 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)-pyra Zoline, 1,5-bis-(4-tert-octyl-phenyl)-3-(4-tert-octyl-styryl)-pyrazoline, 1-(4-dodecyl-phenyl)-3-styryl- 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) syl-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 are preferred.

The content of the (C2) pyrazoline-based sensitizer, which makes the total solid content in the photosensitive resin composition 100 parts by mass, is preferably 0.01 to 10.0 parts by mass, more preferably 0.01 to 5 parts by mass, still more preferably 0.02 to 1 part by mass, and 0.03 parts by mass. - 0.5 parts by mass is particularly preferred, and 0.03 - 0.2 parts by mass is extremely preferred. (C2) When the content of the pyrazoline-based sensitizer is 0.01 part by mass or more, it becomes difficult to elute during development in the exposed portion, and when it is 10 parts by mass or less, the heat resistance can be suppressed.

It is preferable to add the (C2) anthracene type sensitizer to the photosensitive resin composition of this embodiment.

The (C2) anthracene-based sensitizer used in the photosensitive resin composition of the present embodiment is capable of forming a pattern with excellent resist shape and excellent resolution by improving photocurability.

(C2) As an anthracene type sensitizer, the compound represented by the following general formula (XI) is mentioned preferably, for example.

In Formula (XI), I ₁₁ is an integer of 1 to 10, and R ³ is 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 hetero group. Represents an aryl group or -N(R ⁴ ) ₂ group, and two or more R ³ groups may be bonded to each other to form a cyclic structure, the cyclic structure may contain a hetero atom, and the alkyl group and alkenyl group may be linear. It may be branched or 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 addition, 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, -SC(=O)-group, -O-SO ₂ -group , or -S-SO ₂ - group. However, X is a single bond and R ³ is a combination of hydrogen atoms (ie, unsubstituted anthracene). In addition, a plurality of X's 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, and R ⁴ are bonded to each other to form a cyclic structure may be formed, and the cyclic structure may include a hetero atom, and the alkyl group and alkenyl group may be linear or branched, and may also be a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amide group, an alkoxy group, etc. may be substituted by

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, as well as a norbornyl group, a tricyclodecanyl group, and a tetracyclo group. and bridged alicyclic hydrocarbon groups having 6 to 20 carbon atoms such as dodecyl group, adamantyl group, methyl adamantyl group, ethyl adamantyl group, and butyl adamantyl group.

As the aryl group, those exemplified as the aryl group for R ¹³ are preferable, and as the heteroaryl group, one or more of the arbitrary reducing atoms constituting these aryl groups is a hetero atom such as a sulfur atom, an oxygen atom, a nitrogen atom, and the like. What is obtained by substitution is preferable.

Examples of R ³ and R ⁴ as described above include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group. Preferable examples include a sil group, n-heptyl group, n-octyl group, cyclopentyl group, cyclohexyl group, comporoyl group, norbornyl group, p-tolyl group, benzyl group, phenyl group, and 1-naphthyl group.

In addition, as the (C2) anthracene-based sensitizer represented by the above general formula (XI), for example, 1-methylanthracene, 2-methylanthracene, 2-ethylanthracene, 2-t-butylanthracene, 9-methyl Alkylanthracenes such as anthracene; dialkyl anthracenes such as 9,10-dimethylanthracene, 9,10-dipropylanthracene, and 9,10-dibutylanthracene; hydroxyalkyl anthracenes such as 9-(hydroxymethyl)anthracene and 9-(2-hydroxyethyl)anthracene; dialkoxyanthracenes such as 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-di(2-ethylhexyloxy)anthracene; alkenylanthracenes such as 9-vinylanthracene and 9-allylanthracene; aminoanthracenes such as 1-aminoanthracene, 2-aminoanthracene, and 9-(methylaminomethyl)anthracene; Anthraaldehyde, such as 9-anthraaldehyde and 10-methyl-9-anthraaldehyde; In addition, 9-phenylanthracene, 9-acetylanthracene, 9,10-diphenylanthracene, 1,2-benzanthracene, 1,8,9-triacetoxyanthracene, 1,4,9,10-tetrahydroxy Anthracene etc. are mentioned preferably, These anthracene type sensitizers can be used individually by 1 type or in combination of 2 or more types.

Among these, diphenylanthracene, dialkylanthracene, and dialkoxyanthracene are preferred, and 9,10-dimethylanthracene, 9,10-diphenylanthracene, 9,10-diethoxyanthracene, and 9,10-dipropoxyanthracene. , 9,10-dibutoxyanthracene, and 9,10-di(2-ethylhexyloxy)anthracene are more preferred, and 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10- Dibutoxyanthracene and 9,10-dialkoxyanthracene such as 9,10-di(2-ethylhexyloxy)anthracene are more preferred. In the present embodiment, when these anthracene-based sensitizers are used, a photosensitive resin composition having photosensitivity to radiation with a wavelength of 300 to 450 nm can be obtained, and photocurability can be improved, so that the resist shape is excellent and resolution A pattern with excellent properties can be formed.

The content of the (C2) anthracene-based sensitizer, which makes the total solid content in the photosensitive resin composition 100 parts by mass, is preferably 0.001 to 10 parts by mass. (C2) When the content of the anthracene-based sensitizer is within the above range, since photocurability can be improved, a pattern with excellent resist shape and excellent resolution can be formed. For the same reason, the content of the (C2) anthracene-based sensitizer is more preferably 0.01 to 5 parts by mass, still more preferably 0.03 to 3 parts by mass, and particularly preferably 0.1 to 1.5 parts by mass.

Further, the content of (C2) anthracene-based sensitizer relative 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, and 0.03 to 3 parts by mass. more preferable

[(C3) at least one photopolymerization initiator selected from imidazole-based photopolymerization initiators, acridine-based photopolymerization initiators, and titanocene-based photopolymerization initiators]

Component (C3) is at least one type of photopolymerization initiator selected from imidazole-based photopolymerization initiators, acridine-based photopolymerization initiators, and titanocene-based photopolymerization initiators.

In the present embodiment, the combination of the above-mentioned (B) acylphosphine oxide-based photopolymerization initiator and the component (C3) provides, in particular, a pattern with excellent linearity of pattern outline, excellent resist shape, and excellent resolution. effective in terms of forming

The imidazole-based 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- 2,4,5-triaryls such as dimethoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methylmercaptophenyl)-4,5-diphenylimidazole dimer Imidazole dimer etc. are mentioned preferably.

In the 2,4,5-triarylimidazole dimer, the two 2,4,5-triarylimidazoles constituting the dimer may have the same structure or different structures. . That is, the types of triaryl groups in the 2,4,5-triarylimidazole dimer may be the same or different.

As such a 2,4,5-triarylimidazole dimer, for example, 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 -Chloro p-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 body, 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-methylmercapto Phenyl) -4,5-diphenylimidazole 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-iodophenyl)imidazole dimer, 2,2'-bis(m-bromophenyl)-4,4',5,5'-tetraphenylimidazole A dimer, 2,2'-bis(m,p-dibromophenyl)-4,4',5,5'-tetraphenylimidazole dimer, etc. are mentioned preferably.

In these 2,4,5-triarylimidazole dimers, the aryl group is further divided into a halogen atom, an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, an aryl group of 6 to 14 carbon atoms, an amino group, and a carbon atom of 1 ~10 alkylamino group, nitro group, cyano group, mercapto group, C1-10 alkylmercapto group, C2-20 dialkylamino group, allyl group, C1-20 hydroxyalkyl group, carbon number of alkyl group It may be substituted with a carboxyalkyl group of 1 to 10, an acyl group of 1 to 10 carbon atoms, an alkoxyl group of 1 to 20 carbon atoms, or a group containing a heterocyclic ring.

The acridine-based 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-xylenebis[ β-(acridin-9-yl)acrylate], triethylene glycol bis[β-(acridin-9-yl)acrylate, 9-phenylacridine, 1,7-bis(9,9 '-Acridinyl)heptane etc. are mentioned preferably.

The titanocene-based 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-(1H- Pyrrol-1-yl)phenyl)titanium, bis(2,4-cyclopentadienyl)-bis(2,6-difluoro-3-(1-pyryl)phenyl)titanium, etc. are mentioned preferably. These photoinitiators can be used individually by 1 type or in combination of 2 or more types.

The content of the (C3) photopolymerization initiator, which makes the total solid content in the photosensitive resin composition 100 parts by mass, is preferably 0.01 to 15 parts by mass, more preferably 0.01 to 5 parts by mass, still more preferably 0.01 to 3.5 parts by mass, and 0.02 to 1.0 parts by mass. Addition is particularly preferred. When this content is 0.01 parts by mass or more, it is difficult for the solution of the photosensitive resin composition to gel, and when it is 15 parts by mass or less, the photosensitivity is difficult to decrease, so it is preferable.

The total content of the (B) acylphosphine oxide photopolymerization initiator and the (C3) photopolymerization initiator, which makes the total solid content in the photosensitive resin composition 100 parts by mass, is preferably 0.2 to 15 parts by mass. When it is 0.2 parts by mass or more, it becomes difficult for the exposed portion to elute during development, and when it is 15 parts by mass or less, it becomes difficult to lower the heat resistance. For the same reason, the total content of (B) photopolymerization initiator and (C3) photopolymerization initiator is more preferably 0.2 to 10 parts by mass, still more preferably 0.2 to 5 parts by mass, particularly preferably 0.5 to 5 parts by mass, 0.5 to 3 parts by mass is extremely preferred.

The mass ratio of the above (B) acylphosphine oxide-based photopolymerization initiator and (C3) photopolymerization initiator is preferably 100:0.5 to 100:8, more preferably 100:1 to 100:6, and 100:1 ~100:5 is more preferred. When the mass ratio is within the above range, the resist shape is excellent, and the bottom hardenability and via hole diameter tend to be improved, so it is preferable.

[(C4) at least one antioxidant selected from hindered phenol-based antioxidants, quinone-based antioxidants, amine-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants]

Component (C4) is at least one antioxidant selected from hindered phenol-based antioxidants, quinone-based antioxidants, amine-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants.

By using component (C4), it is possible to obtain a photosensitive resin composition capable of forming a pattern having excellent resist shape and excellent resolution, and having excellent solder heat resistance and flux corrosion resistance.

As the hindered phenolic antioxidant, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF Japan Co., Ltd., Irganox 1010 (trade name) )), thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (BASF Japan Co., Ltd. product, Irganox 1035 (trade name)), octadecyl [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF Japan Co., Ltd., Irganox 1076 (trade name)), octyl 1-3,5-di- t-Butyl-4-hydroxy-hydrocinnamic acid (manufactured by BASF Japan Co., Ltd., Irganox 1135 (trade name)), and 4,6-bis(octylthiomethyl-o-cresol) (manufactured by BASF Japan Co., Ltd.) , Irganox 1520L), 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-t-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-(methylene3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionatemethane, 3,9-bis(2-(3- (3-t-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)prepionylhexamethylenediamine, 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-sali Siloyl-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 etc. are mentioned preferably, These can be used individually by 1 type or in combination of 2 or more types. Further, as the quinone-based antioxidant, quinone-based antioxidants such as hydroquinone, 2-t-butylhydroquinone, hydroquinone monomethyl ether, metaquinone, and benzoquinone are preferably exemplified, and these may be used alone or in combination of two or more. can be used in combination. Antioxidants having these phenolic hydroxyl groups can be expected to trap peroxy radicals (ROO·), alkyl radicals (R·), and the like.

As the amine antioxidant, phenyl naphthylamine, 4,4'-dimethoxydiphenylamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, di-t-butyldiphenylamine, N ,N'-di(octylphenyl)amine, 4-isopropoxydiphenylamine, N,N'-di(2-naphthyl)-p-phenylenediamine, bis(2,2,6,6-tetra Methyl-4-piperidyl)-sebacate, phenothiadine, etc. are preferable, and these can be used individually by 1 type or in combination of 2 or more types. Amine-based antioxidants can be expected to trap peroxy radicals (ROO·).

As the sulfur-based antioxidant, didodecyl-3,3'-thiodipropionate, ditetradecyl-3,3'-thiodipropionate, dioctadecyl-3,3'-thiodipropionate, Tridecyl-3,3'-thiodipropionate, pentaerythyltetrakis (3-dodecylthiopropionate), pentaerythyltetrakis (3-tettadecylthiopropionate), pentaerythyl Tetrakis(3-tridecylthiopropionate), dilauryl-3,3-thiodipropionate, dimyristyl-3,3-thiodipropionate, distearyl-3,3-thiodipropionate Zinc salt of propionate, pentaerythyltetrakis (3-laurylthiodipropionate, 2-mercaptobenzoimidazole, laurylsteallylthiodipropionate, 2-mercaptomethylbenzimidazole, Zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc dibutylthiocarbamate, etc. are mentioned preferably, and these can be used individually by 1 type or in combination of 2 or more types.

As the phosphorus antioxidant, triphenyl phosphite, tris (methylphenyl) phosphite, triisooctyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tris (nonylphenyl) phosphite, tris (octylphenyl) ) phosphite, tris [decyl poly (oxyethylene) phosphite, tris (cyclohexylphenyl) phosphite, tricyclohexyl phosphite, tri (decyl) thiophosphite, triisodecyl thiophosphite, phenyl-bis (2 -Ethylhexyl)phosphite, phenyl-diisodecylphosphite, tetradecylpoly(oxyethylene)-bis(ethylphenyl)phosphite, phenyl-dicyclohexylphosphite, phenyl-diisooctylphosphite, phenyl-di (tridecyl) phosphite, diphenyl-cyclohexyl phosphite, diphenyl-isooctyl phosphite, diphenyl-2-ethylhexyl phosphite, diphenyl-isodecyl phosphite, diphenyl-cyclohexylphenyl phosphite, Diphenyl-(tridecyl)thiophosphite etc. are mentioned preferably, These can be used individually by 1 type or in combination of 2 or more types.

As the sulfur-based antioxidant and the phosphorus-based antioxidant, an effect of decomposing peroxide can be expected. Commercially available sulfur-based antioxidants and phosphorus-based antioxidants include, for example, Adekastave TPP (product name, manufactured by Adeka Co., Ltd.), Mark AO-412S (product name, manufactured by Adecase Co., Ltd.), and Sumi Rider TPS (product name, manufactured by Sumitomo Commercial items, such as Kagaku Co., Ltd. product, brand name), are mentioned.

Further, in the present embodiment, as the (C4) antioxidant, using a hindered phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, and the like in combination results in a good resist shape and excellent solder heat resistance and flux corrosion resistance It is particularly preferable in terms of obtaining

The content of the (C4) antioxidant, which makes the total solid content in the photosensitive resin composition 100 parts by mass, is preferably 0.2 to 15 parts by mass. When it is 0.2 parts by mass or more, the exposed portion becomes difficult to elute during development, and when it is 15 parts by mass or less, the heat resistance is difficult to decrease. For the same reasons, the content of the (C4) antioxidant is more preferably 0.2 to 10 parts by mass, still more preferably 0.5 to 5 parts by mass, and particularly preferably 0.5 to 3 parts by mass.

[(C5) thiol group-containing compound]

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.

(C5) Examples of the thiol group-containing compound include mercaptobenzoxazole, mercaptobenzothiazole, mercaptobenzoimidazole, ethanethiol, benzenethiol, mercaptophenol, mercaptotoluene, 2-mercaptoethyl Amine, mercaptoethyl alcohol, mercaptoxylene, thioxylenol, 2-mercaptochinoline, mercaptoacetic acid, α-mercaptopropionic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thiosalicylic acid, mercaptocyclohexane , α-mercaptodiphenylmethane, C-mercaptotetrazole, mercaptonaphthalin, mercaptonaphthol, 4-mercaptobiphenyl, mercaptohypoxanthine, mercaptopyridine, 2-mercaptopyrimidine, mercaptopurine, Thiocumazone, thiocumothiazone, butane-2,3-dithiol, thiocyanuric acid, 2,4,6-trimercapto-s-triadine, 2-dibutylamino-4,6-dimercapto -s-triadine, 2-anilino-4,6-dimercapto-s-triadine, etc. are mentioned.

These (C5) thiol group-containing compounds can be used individually by 1 type or in combination of 2 or more types. Among these, from the viewpoint of effectively functioning as a hydrogen donor and further improving the sensitivity and aging stability of the photosensitive resin composition, mercaptobenzoxazole, mercaptobenzothiazole, and mercaptobenzoimidazole are preferred. Preferably it is mercaptobenzoimidazole.

The content of the (C5) thiol group-containing compound in the photosensitive resin composition is preferably 0.01 to 5 parts by mass based on the total solid content of the photosensitive resin composition from the viewpoint of obtaining a photosensitive resin composition capable of forming a pattern with excellent resolution. , 0.1 to 3 parts by mass is more preferable, and 0.2 to 1.5 parts by mass is still more preferable. (C5) When 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 when it is 5 parts by mass or less, a decrease in sensitivity can be suppressed.

<(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 is a compound having a photopolymerizable functional group, and examples thereof include a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, and a maleimide group. , a nadiimide group, a compound having an ethylenically oxide-type unsaturated group such as a (meth)acryloyl group is preferable, and a compound having a (meth)acryloyl group is more preferable 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; mono- or di(meth)acrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, and polyethylene glycol; (meth)acrylamides such as N,N-dimethyl (meth)acrylamide and N-methylol (meth)acrylamide; aminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate; Polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and tris-hydroxyethyl isocyanurate, or polyhydric (meth)acrylates of ethylene oxide or propylene oxide adducts thereof ; (meth)acrylates of ethylene oxide or propylene oxide adducts of phenols, such as phenoxyethyl (meth)acrylate and polyethoxydi(meth)acrylate of bisphenol A; (meth)acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; Melamine (meth)acrylate etc. are mentioned preferably. These (D) photopolymerizable compounds can be used individually by 1 type or in combination of 2 or more types.

The content of the (D) photopolymerizable compound, which makes the total solid content in the photosensitive resin composition 100 parts by mass, is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, still more preferably 1 to 15 parts by mass, Especially preferably, it is 1.5-10 mass parts. When it is 0.1 parts by mass or more, the exposed portion is difficult to elute during development, and the sensitivity and resolution of the photosensitive resin composition tend to be improved. When it is 30 parts by mass or less, heat resistance tends to be improved.

<(E) inorganic filler>

It is preferable that the photosensitive resin composition of this embodiment contains an inorganic filler as (E) component.

(E) The inorganic filler is preferably used for the purpose of improving various properties such as adhesiveness, heat resistance, and coating film hardness of the photosensitive resin composition. (E) Examples of inorganic fillers 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), 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 4Al ₂ O ₃ H ₂ O), aluminum titanate (TiO ₂ Al ₂ O ₃ ), yttria-containing zirconia (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, etc. may be preferred. These (E) inorganic fillers can be used individually by 1 type or in combination of 2 or more types.

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

(E) Among inorganic fillers, silica is preferable from the viewpoint of improving heat resistance, and can improve solder heat resistance, crack resistance (thermal shock resistance), and adhesive strength between the underfill material and the cured film after PCT test. From the point of view, barium sulfate is preferable. From the viewpoint of improving the aggregation prevention effect, the barium sulfate is preferably surface-treated with at least one selected from alumina and organosilane-based compounds.

The elemental composition of aluminum on the surface of barium sulfate surface-treated with at least one selected from alumina and organosilane-based compounds is preferably 0.5 to 10 atomic %, more preferably 1 to 5 atomic %, and 1.5 atomic %. ~3.5 atomic % is more preferred. 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 still more 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%, still more 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-based compounds, NanoFine BFN40DC (manufactured by Nippon Sorbay Co., Ltd., trade name) is commercially available, for example.

(E) When containing an inorganic filler, content of the (E) inorganic filler which makes the total solid content in the photosensitive resin composition 100 mass parts is 15-80 mass parts is preferable, 15-70 mass parts are more preferable, and 20-70 mass parts Part by mass is more preferable, 20 to 50 parts by mass is particularly preferable, and 20 to 45 parts by mass is extremely preferable. (E) When the content of the inorganic filler is within the above range, the film strength, heat resistance, insulation reliability, thermal shock resistance, resolution and the like of the photosensitive resin composition can be further improved.

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

<(F) pigment>

It is preferable that the photosensitive resin composition of this embodiment contains a pigment as (F) component.

(F) The pigment is preferably used depending on the desired color when concealing the wiring pattern or the like. (F) As the pigment, a colorant capable of developing a desired color may be appropriately selected and used. As the colorant, for example, known colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, and crystal violet are preferred. can hear

(F) When containing a pigment, content of the (F) pigment which makes the total solid content in the photosensitive resin composition 100 mass parts is 0.1-5 mass parts is preferable, and 0.1-3 mass parts is more preferable. (F) If the content of the pigment is within the above range, it is preferable from the viewpoint of concealing the wiring pattern.

<other ingredients>

The photosensitive resin composition of this embodiment can use a diluent in order to adjust a viscosity as needed. As a diluent, an organic solvent, a photopolymerizable monomer, etc. are mentioned preferably, for example. The organic solvent can be appropriately selected and used from solvents exemplified as organic solvents that can be used in the reaction between the above-described 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 used of the diluent is preferably 50 to 90% by mass, more preferably 60 to 80% by mass, and still more preferably 65 to 75% by mass for the total solid content in the photosensitive resin composition. That is, 10-50 mass % is preferable, as for content of the diluent in the photosensitive resin composition in the case of using a diluent, 20-40 mass % is more preferable, and its 25-35 mass % is still more preferable. 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 more highly precise pattern becomes possible.

The photosensitive resin composition of this embodiment may contain a hardening|curing agent. As the curing agent, a compound that itself is cured by heat, ultraviolet rays, or the like, or a carboxyl group or hydroxyl group of the (A) acid-modified vinyl group-containing epoxy resin, which is the photocurable resin component in the composition of the present embodiment, is cured by heat, ultraviolet rays, or the like. compounds are preferred. By using a curing agent, the heat resistance, adhesiveness, chemical resistance, etc. of the final cured film can be improved.

As a hardening|curing agent, an epoxy compound, a melamine compound, a urea compound, an oxazoline compound etc. are mentioned preferably as a thermosetting compound, for example. Examples of the epoxy compound include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, and bisphenol S type epoxy resin; novolak-type epoxy resins; Biphenyl type epoxy resin; Heterocyclic epoxy resins, such as triglycidyl isocyanurate; Non-ylenol-type epoxy resins and the like are preferred. As a melamine compound, triaminotriadine, hexamethoxymelamine, hexabutoxylated melamine etc. are mentioned preferably, for example. As a urea compound, dimethylol urea etc. are mentioned preferably.

As the curing agent, from the viewpoint of further improving the heat resistance of the cured film, it is preferable to include at least one selected from epoxy compounds (epoxy resins) and block type isocyanates, and it is more preferable to use an epoxy compound and block type isocyanate together. do.

As the blocked isocyanate, an addition reaction product of a polyisocyanate compound and an isocyanate blocking agent is used. As this polyisocyanate compound, for example, tolylene diisocyanate, xylene diisocyanate, phenylene diisocyanate, naphthylene diisocyanate, bis(isocyanate methyl)cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethyl Preferable examples thereof include polyisocyanate compounds such as hexamethylene diisocyanate and isophorone diisocyanate, and adducts, biurets and isocyanurates thereof.

Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; lactam-based blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; active methylene-based 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, alcohol-based blocking agents such as butyl glycolate, diacetone alcohol, methyl lactate, and ethyl lactate; oxime-based blocking agents such as formaldehyde, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexane oxime; mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol, and ethylthiophenol; acid amide blocking agents such as acetic acid amide and benzamide; imide-based blocking agents such as succinic acid imide and maleic acid imide; amine-based blocking agents such as xylidine, aniline, butylamine, and dibutylamine; imidazole-based blocking agents such as imidazole and 2-ethylimidazole; Imine type blocking agents, such as methyleneimine and propyleneimine, etc. are mentioned preferably.

A hardening|curing agent is used individually by 1 type or in combination of 2 or more types. In the case of using a curing agent, the content thereof is preferably 2 to 50 parts by mass, more preferably 2 to 40 parts by mass, still more preferably 3 to 30 parts by mass, and preferably 5 to 50 parts by mass, relative to 100 parts by mass of the total solid content in the photosensitive resin composition. 20 parts by mass is particularly preferred. By setting the content of the curing agent within the above range, the heat resistance of the cured film to be formed can be further improved while maintaining good developability.

An epoxy resin curing agent can be used in combination with the photosensitive resin composition of the present embodiment 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, and 2-methylimidazole. imidazoles such as phenyl-4-methyl-5-hydroxymethylimidazole; guanamines such as acetoguanamine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, and polybasic hydrazide; at least one selected from organic acid salts and epoxy adducts thereof; amine complexes of boron trifluoride; triadine derivatives such as ethyldiamino-S-triadine, 2,4-diamino-S-triadine, and 2,4-diamino-6-xylyl-S-triadine; Trimethylamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa(N-methyl)melamine, 2,4,6-tris(dimethylaminophenol), tetramethylguanidine, tertiary amines such as m-aminophenol; polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac, and alkylphenol novolac; organic phosphines such as tributylphosphine, triphenylphosphine, and tris-2-cyanoethylphosphine; phosphonium salts such as tri-n-butyl(2,5-dihydroxyphenyl)phosphonium bromide and hexadecyltributylphosnium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; the above polybasic acid anhydrides; diphenyliodonium tetrafluoroborate; triphenylsulfonium hexafluoroantimonate; 2,4,6-triphenylthiopyrylium hexafluorophosphate etc. are mentioned preferably.

An epoxy resin curing agent is used individually by 1 type or in combination of 2 or more types, In the photosensitive resin composition, Preferably it is 0.01-20 mass %, More preferably, it is 0.1-10 mass %.

The photosensitive resin composition of this embodiment is polymerization inhibitors, such as hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol, as needed; thickeners such as bentone and montmorillonite; Antifoaming agents, such as a silicone type, a fluorine type, and a vinyl resin type; Known and usual various additives, such as a silane coupling agent, can be used.

Furthermore, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus-based phosphate compounds, aromatic condensed phosphoric acid esters, and halogen-containing condensed phosphoric acid esters may be used.

(elastomer)

The photosensitive resin composition of this embodiment may contain an elastomer. An elastomer is especially preferably used when using the photosensitive resin composition of this embodiment for manufacture of a semiconductor package board|substrate. By adding an elastomer to the photosensitive resin composition of the present embodiment, the curing reaction proceeds by ultraviolet light, heat, or the like, and is attributed to (A) distortion (internal stress) inside the resin due to curing shrinkage of the acid-modified vinyl group-containing epoxy resin. As long as, it is possible to suppress deterioration of flexibility and adhesiveness.

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

In addition to the above elastomers, rubber-modified epoxy resins can be used. The rubber-modified epoxy resin is, for example, part or all of the above-mentioned 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 is obtained by modifying the epoxy group with a carboxylic acid-modified butadiene-acrylonitrile rubber at both terminals, an amino-modified silicone rubber at the terminals, or the like. Among these elastomers, from the viewpoint of shear adhesiveness, both terminal carboxyl group-modified butadiene-acrylonitrile copolymers and Espel (Hitachi Chisei Co., Ltd., Espel 1612, 1620 (trade name)) which are polyester elastomers having hydroxyl groups ) is preferred.

The blending amount of the elastomer is preferably 2 to 30 parts by mass, more preferably 4 to 20 parts by mass, still more preferably 10 to 20 parts by mass, based on 100 parts by mass of the (A) acid-modified vinyl group-containing epoxy resin. . When 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 when it is 30 parts by mass or less, the unexposed portion tends to elute from the developing solution.

The photosensitive resin composition of this embodiment can be obtained by uniformly kneading and mixing the various components used as desired, including the components (A) to (F), by a roll mill, a bead mill, or the like.

Moreover, it is preferable that the photosensitive resin composition of this embodiment is in liquid form. By using a liquid form, a permanent mask resistor can be easily formed by various coating methods described later.

[Photosensitive element, permanent mask resistor and printed wiring board]

The photosensitive resin composition of this embodiment is suitably used for formation of a photosensitive element and a permanent mask resistor, and the photosensitive element and permanent mask resistor of this embodiment are formed using the photosensitive resin composition of this embodiment. .

The photosensitive element of the present embodiment includes a support and a photosensitive layer made of the photosensitive resin composition of the present embodiment on the support. Examples of the support include preferably resin films having heat resistance and solvent resistance, such as polyester resin films such as polyethylene terephthalate and polyolefin resin films such as polyethylene and polypropylene. From the viewpoint of transparency, polyethylene terephthalate It is preferable to use a phthalate film. Further, the thickness of the support is preferably 1 to 100 μm, more preferably 1 to 50 μm, still more preferably 1 to 30 μm, in consideration of obtaining mechanical strength and good resolution.

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

The permanent mask resistor of this embodiment and the printed wiring board equipped with the permanent mask resistor are image-formed 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, etc.), the photosensitivity of the present embodiment is applied by a method such as a screen printing method, a spray method, a roll coating method, a curtain coating method, and an electrostatic coating method. The resin composition is applied to a film thickness (after drying: 10 to 200 μm) according to the purpose to form a coating film, and the coating film is dried at 60 to 110 ° C. In place of the coating film, the photosensitive layer of the photosensitive element may be transferred (laminated) onto a base material on which the resist is to be formed. In this case, the dried coating film on the support is applied onto the substrate using an atmospheric laminator or a vacuum laminator as needed.

After the photosensitive layer (coating film) is formed on the substrate, a negative film is directly contacted or through a transparent film, active rays such as ultraviolet rays are preferably irradiated with an energy amount of 10 to 1,000 mJ/cm ² , and the resin When a film is affixed, the resin film is peeled off, and the unexposed area is dissolved and removed (developed) with a diluted alkaline aqueous solution.

Next, the exposed portion is sufficiently cured by post-exposure (ultraviolet ray exposure), post-heating, or post-exposure and post-heating to obtain a cured film. Post-exposure is preferably 1 to 5 J/cm ² , for example, and post-heating is preferably 30 minutes to 12 hours at 100 to 200°C.

In the permanent mask resist obtained in this way, undercutting in which the bottom part is cut out is difficult to occur, and chipping of the upper part of the resist is difficult to occur. Since it does not increase with respect to the surface, the linearity of the pattern outline is good, the resist shape is excellent, and the pattern with excellent resolution is obtained. In addition, this permanent mask resistor has a pattern that is excellent in the formation stability of the size of the hole diameter and the pitch between the holes, which have been reduced due to the miniaturization and high performance of electronic devices in recent years.

Example

Below, the present invention will be described more specifically by examples, but the present invention is not limited by these examples in any way.

(Assessment Methods)

(1) Evaluation of surface hardenability

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 to form a coating film. Subsequently, it was dried using a hot air circulating 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: Thermo Fisher Scientific Co., Ltd., product name: Nicolet iS50R

・Number of accumulated times: 128 times

Next, it was exposed with an exposure amount of 600 mJ/cm ² using an ultraviolet exposure apparatus (trade name: HTE-5102S, manufactured by Hi-Tech Co., Ltd.). The infrared absorption spectrum (ATR method) of the surface of the coated film after exposure was measured under the same conditions as above, and the rate of change of the carbon-carbon double bond appearing at 1470 cm ^-1 before and after exposure was obtained from the following formula, and the average of three accumulated times was obtained It was set as surface hardenability (%).

Double bond change rate (%) = 100 - (amount of carbon-carbon double bonds after exposure / amount of carbon-carbon double bonds before exposure × 100)

(2) Evaluation of photosensitivity

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 to form a coating film. Subsequently, it was dried using a hot air circulating dryer at 80°C for 20 minutes. Next, 41 steps of step tablets (manufactured by Hitachi Chemical Co., Ltd.) were adhered to the coating film, and ultraviolet rays ("LI9200 (model number)", manufactured by Dainippon Screen Manufacturing Co., Ltd.) were applied with a predetermined cumulative exposure amount. The entire surface was irradiated with 50 mJ/cm ² . Subsequently, after developing for 60 seconds with a 1% by mass aqueous solution of sodium carbonate, the number of stages of the coating film remaining without development was confirmed. By number, it was evaluated according to the following criteria.

A (Excellent): 10 steps or more

B (good): 　 6-9 steps

C (poor): 5 steps or less

(3) Evaluation of bottom 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 to form a coating film. Subsequently, it was dried using a hot air circulating 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: Thermo Fisher Scientific Co., Ltd., product name: Nicolet iS50R

・Accumulated times: 128 times

Next, it was exposed with an exposure amount of 600 mJ/cm ² using an ultraviolet exposure apparatus (trade name: HTE-5102S, manufactured by Hi-Tech Co., Ltd.). After that, the exposed coating film was peeled off from the PET film, and the infrared absorption spectrum (ATR method) of the coating film on the surface side of the PET film after exposure was measured under the same conditions as above. The rate of change of the carbon-carbon double bond appearing at 1470 cm ⁻¹ before and after exposure was obtained from the following formula, and the average value of 3 accumulated times was taken as the coating film bottom curing property (%).

Double bond change rate (%) = 100 - (amount of carbon-carbon double bonds after exposure / amount of carbon-carbon double bonds before exposure × 100)

(4) Evaluation of resist shape

The photosensitive resin composition of each Example and Comparative Example was applied to a 0.6 mm thick copper clad laminated board (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-67) in a size of 50 cm × 50 cm, and the film thickness after drying was 35 After forming a coating film by screen printing so as to be ㎛, it was dried using a hot air circulation type dryer at 80 ℃ for 20 minutes.

Subsequently, a negative mask having a pattern with a hole diameter of 100 μm and a pitch between holes of 100 μm and a pattern with a hole diameter of 80 μm and a pitch between holes of 80 μm shown in FIG. 2 are respectively coated. was adhered to, and exposed at a predetermined exposure amount shown in Tables 1 to 6 using an ultraviolet exposure device (manufactured by Hi-Tech Co., Ltd., trade name: HTE-5102S).

Thereafter, spray development was carried out with a 1% by mass aqueous solution of sodium carbonate for 60 seconds at a pressure of 0.18 MPa (1.8 kgf/cm ² ) to dissolve and develop the unexposed portion. Next, using an ultraviolet exposure device (manufactured by GS Yuasa Lighting Co., Ltd., trade name: conveyor type UV irradiation device), exposure was performed at an exposure amount of 1000 mJ/cm ² , followed by heating at 150° C. for 1 hour to prepare a test piece.

The test piece on which the pattern was formed was molded with an epoxy resin (Epicoat 828 (trade name), manufactured by Mitsubishi Chemical Corporation) and a thermosetting resin using triethylenetetramine as a curing agent, and after sufficiently cured, a polishing machine (manufactured by Refinetec Co., Ltd.) , Trade name: Refine Polisher), the cross section of the pattern was shaved, and the resist shape was observed with a metallographic microscope and evaluated according to the following criteria. Fig. 1 schematically shows the cross-sectional shape of a resist.

A (good): The resist shape was rectangular or trapezoidal, and the linearity of the pattern outline was good.

B (poor): The resist shape was confirmed to be undercut, lower width pulled, or thickened, or the linearity of the pattern outline was poor.

(5) Evaluation of Via Diameter Accuracy

The photosensitive resin composition of each Example and Comparative Example was applied to a 0.6 mm thick copper clad laminated board (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-67) in a size of 50 cm × 50 cm, and the film thickness after drying was 35 After forming a coating film by screen printing so as to be ㎛, it was dried using a hot air circulation type dryer at 80 ℃ for 20 minutes.

Subsequently, negative masks having patterns shown in FIG. 2 were brought into close contact with the respective coating films, and exposed to light at an exposure amount of 600 mJ/cm ² using an ultraviolet ray exposure device (trade name: HTE-5102S, manufactured by Hi-Tech Co., Ltd.). Thereafter, spray development was carried out with a 1% by mass aqueous solution of sodium carbonate 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 (good): 80% of the patterns of 100 μm and 80 μm were reproduced.

B (defective): Only less than 80% of the patterns of 100 μm and 80 μm were reproduced.

Here, using a microscope, magnify 700 times to observe the patterns of 100 μm and 80 μm, and in the case of the 100 μm pattern, the bottom of the pattern is formed in a size of 80 μm or more (80% or more of the pattern diameter) A case in which there was a pattern was considered to be reproduced. In the case of the pattern of 80 μm, the case where the bottom portion of the pattern was formed in a size of 64 μm or more was regarded as reproducing the pattern. In addition, in judgment of "A" and "B", the case where the total number of patterns formed 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)

Water-soluble flux (manufactured by Alpha Metals Co., Ltd., trade name: K-183) was applied to a test piece prepared under the same conditions as the test piece used in the above (4) evaluation of resist shape, and immersed in a solder bath at 265 ° C. for 10 seconds. After that, it was taken out of the solder layer. After making immersion and taking-out 1 cycle and repeating 6 cycles, the external appearance of the coating film was visually observed and evaluated according to the following criteria.

A (good): No change in appearance was observed within the range of the coating film 30 cm x 30 cm.

B (Good): Within the range of 30 cm × 30 cm of the coating film, 1 to 5 coating films were lifted or parts were confirmed.

C (defective): Within the range of 30 cm × 30 cm of the coating film, 6 or more coating films were lifted or parts were confirmed.

(7) Evaluation of solder heat resistance (ii)

On a test piece produced under the same conditions as the test piece used in the above (4) evaluation of the resist shape, a no-clean flux (manufactured by Senju Kinzoku Kogyo Co., Ltd., trade name: RMA SR-209) was applied, and solder set at 280 ° C. After being immersed in the bath for 10 seconds, it was taken out from the solder layer. After repeating 10 cycles by making the immersion and taking out one cycle, the external appearance of the coating film of the taken out test piece was visually observed and evaluated according to the following criteria.

A: No change in the appearance of the resist coating was observed.

B: It was confirmed that the coating film of the resist was peeled off a little, but it was not a problem in practical use.

C: Part or peeling of the coating film of the resist was confirmed.

(8) Evaluation of crack resistance

The test piece produced under the same conditions as the test piece used in the above (4) evaluation of the resist shape was kept at -65°C for 30 minutes, and then held at 150°C for 30 minutes. , The appearance of the coating film of the test piece was visually observed and evaluated according to the following criteria.

A (good): No change in appearance was observed within the range of the coating film 30 cm x 30 cm.

B (Good): Lifting or parts of 1 to 5 coating films were confirmed within the range of the coating film 30 cm x 30 cm.

C (defective): Within the range of 30 cm × 30 cm of the coating film, 6 or more coating films were lifted or parts were confirmed.

(9) Evaluation of adhesion

A 0.6 mm-thick copper-clad laminated board (trade name: MCL-E manufactured by Hitachi Chemical Co., Ltd.) obtained by buffing the copper surface of the photosensitive resin composition of each Example and Comparative Example (roughening 5 μm in the depth direction). -67) and chemical polishing (0.5 μm roughening in the depth direction using abrasive CZ8101 manufactured by Mack Co., Ltd.), 0.6 mm thick copper-clad laminated board (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-67) Then, a coating film was formed by screen printing so that the film thickness after drying was 35 μm, and then dried using a hot air circulation dryer at 80° C. for 20 minutes.

Next, negative masks having patterns shown in FIG. 2 were brought into close contact with the respective coating films, and exposed to light at an exposure amount of 600 mJ/cm ² using an ultraviolet ray exposure device (trade name: HTE-5102S, manufactured by Hi-Tech Co., Ltd.). Thereafter, spray development was carried out with a 1% by mass aqueous solution of sodium carbonate for 60 seconds at a pressure of 0.18 MPa (1.8 kgf/cm ² ) to dissolve and develop the unexposed portion. Next, it was exposed at an exposure amount of 1000 mJ/cm ² using an ultraviolet exposure device (manufactured by GS Yuasa Lighting Co., Ltd., trade name: conveyor type UV irradiation device), and heated at 150° C. for 1 hour to prepare a test piece.

On the obtained test piece, 100 checkerboard grids of 1 mm were prepared in accordance with JIS K5600, cellophane tape (Nichiban Co., Ltd. product, trade name: Cellotape (registered trademark)) was applied, and then the cellophane tape was applied in a direction of 90 degrees. The peeling test which peels forcibly was implemented. The peeling state of the checkerboard grid was observed and evaluated according to the following criteria.

A (excellent): 90/100 or more, and there was no peeling.

B (good): 50/100 or more and less than 90/100, and there was no peeling.

C (defect): 0/100 or more and less than 50/100, and there was no peeling.

(10) Solvent resistance

A test piece prepared under the same conditions as the test piece used in the above (4) evaluation of the resist shape was immersed in isopropyl alcohol at room temperature for 30 minutes, and it was visually confirmed that there was no abnormality in appearance. Next, cellophane tape (trade name: cellophane (registered trademark), manufactured by Nichiban Co., Ltd.) was applied to the coating film of the test piece after immersion, and then a peeling test was conducted in which the cellophane tape was forcibly peeled off in a direction of 90 degrees, and the coating film The presence or absence of peeling was visually confirmed and evaluated according to the following criteria.

A (good): 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 peeling occurred.

(11) Acid resistance

A test piece prepared under the same conditions as the test piece used in the above (4) evaluation of resist shape was immersed in a 10% by mass aqueous hydrochloric acid solution at room temperature for 30 minutes, and it was visually confirmed that there was no abnormality in appearance. Next, cellophane tape (trade name: cellophane (registered trademark), manufactured by Nichiban Co., Ltd.) was applied to the coating film of the test piece after immersion, and then a peeling test was conducted in which the cellophane tape was forcibly peeled off in a direction of 90 degrees, and the coating film The presence or absence of peeling was visually confirmed and evaluated according to the following criteria.

A (good): 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 peeling occurred.

(12) Alkali resistance

A test piece prepared under the same conditions as the test piece used in the above (4) resist shape evaluation was immersed in a 5% by mass aqueous solution of sodium hydroxide at room temperature for 30 minutes, and visually confirmed that there was no abnormality in appearance. Next, cellophane tape (trade name: cellophane (registered trademark), manufactured by Nichiban Co., Ltd.) was applied to the coating film of the test piece after immersion, and then a peeling test was conducted in which the cellophane tape was forcibly peeled off in a direction of 90 degrees, and the coating film The presence or absence of peeling was visually confirmed and evaluated according to the following criteria.

A (good): 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 peeling occurred.

(13) Evaluation of flux corrosion resistance

In the above (4) evaluation of the resist shape, a test piece was obtained in the same manner as in the above (4) evaluation of the resist shape, except that the pattern shown in FIG. 2 was changed to the 1 mm square grid pattern shown in FIG. 3. Next, 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 standing for 3 minutes to remove excess flux. Next, the test piece was preheated at 130°C for 1 minute, then immersed in a 280°C solder bath for 20 seconds, and then taken out of the solder bath. After cooling at room temperature for 1 minute, it was washed with water and the appearance was visually observed in a state where water droplets were wiped off. In addition, a 24 mm wide cellophane tape (manufactured by Nichiban Co., Ltd., trade name: Cellophane (registered trademark)) was attached to the portion of the minimum circuit width of the test piece, and a peel test was conducted in which the cellophane tape was forcibly peeled in a direction of 90 degrees. , The external appearance of the test piece after peeling was visually observed and evaluated according to the following criteria.

5: Even after the peeling test, no peeling of the portion where the resist was present was confirmed.

4: After the peeling test, peeling of 20% or less of the portion where the resist was present was confirmed.

3: A little whitening was observed 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: Significant whitening was observed in the portion where the resist was present before the peeling test, and significant peeling was observed after the peeling test.

(14) Non-electrolytic plating property

Test pieces prepared under the same conditions as the test pieces used in the above (4) evaluation of the resist shape were prepared using commercially available electroless nickel plating baths and electroless gold plating baths, with a nickel thickness of 5 µm and gold thickness of 0.05 µm. Plating was carried out under the following conditions. After plating, the presence or absence of penetration of the plating was visually confirmed. Next, cellophane tape (trade name: cellophane (registered trademark), manufactured by Nichiban Co., Ltd.) was applied to the coating film of the test piece after immersion, and then a peeling test was conducted in which the cellophane tape was forcibly peeled off in a direction of 90 degrees, and the coating film The presence or absence of peeling was visually confirmed and evaluated according to the following criteria.

A: Simmering and peeling were not observed.

B: Although smear was observed after plating, peeling was not observed.

C: Peeling was observed after plating.

(Synthesis Example 1; Synthesis of acid-modified vinyl group-containing epoxy resin (I))

220 parts by mass of cresol novolak-type epoxy resin (manufactured by Nippon Steel Sumikin Chemicals Co., Ltd., trade name: YDCN704, in general formula (I), Y ¹ = glycidyl group, R ¹¹ = methyl group), 72 parts by mass of acrylic acid, 1.0 mass part of hydroquinone and 180 mass parts of carbitol acetate were mixed, and it heated and stirred at 90 degreeC, and dissolved the reaction mixture. It was then cooled to 60°C, mixed with 1 part by mass of benzyltrimethylammonium chloride, heated to 100°C, and reacted until the solid dispersion value became 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, it was diluted with carbitol acetate so that the solid content concentration might be 60% by mass, and a solution containing acid-modified vinyl group-containing epoxy resin (I) was obtained.

In addition, the solid content acid value in the Example was measured according to the neutralization titration method. Specifically, 30 g of acetone was added to 1 g of the solution containing the acid-modified vinyl group-containing epoxy resin to further dissolve it uniformly, and then an appropriate amount of phenolphthalein as an indicator was added to the solution containing the acid-modified vinyl group-containing epoxy resin. It was measured by performing titration using a 0.1 N aqueous solution of potassium hydroxide.

(Synthesis Example 2; Synthesis of acid-modified vinyl group-containing epoxy resin (II)-a)

Bisphenol F-type epoxy resin (manufactured by Nippon Steel & Chemical Co., Ltd., trade name: YDF2001, in general formula (II), Y ² =glycidyl group, R ¹² =H) 475 parts by mass, acrylic acid 72 parts by mass, hydro 0.5 parts by mass of quinone and 120 parts by mass of carbitol acetate were mixed, heated and stirred at 90°C to dissolve the reaction mixture. Then, 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 of the solid content was 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, it was diluted with carbitol acetate so that the solid content concentration might be 60% by mass, and a solution containing acid-modified vinyl group-containing epoxy resin (II)-a was obtained.

(Synthesis Example 3; Synthesis of acid-modified vinyl group-containing epoxy resin (IV)-a)

272 parts by mass of bis(4-hydroxyphenyl)methane dissolved at 80°C was put into a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer, and stirring was started at 80°C. 3 parts by mass of methanephosphonic acid was added thereto, and 16.3 parts by mass of an aqueous solution of paraformaldehyde (concentration: 92% by mass) was added dropwise over 1 hour so that the temperature of the liquid was maintained in the range of 80 to 90°C. After completion of the dropping, it was heated to 110°C and stirred for 2 hours. Subsequently, 1000 parts by mass of methyl isobutyl ketone was further added, and the mixture was transferred to a separatory funnel and washed with water. After continued washing with water until the washing water was neutral, the solvent and unreacted bis(4-hydroxyphenyl)methane were removed from the organic layer under heating and reduced pressure (temperature: 220°C, pressure: 66.7 Pa) to obtain a brown solid 164 parts by mass of a phosphorus bisphenol-based novolac resin was obtained. The softening point of the obtained bisphenol-type novolac resin was 74 degreeC, and the hydroxyl equivalent was 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 were added to a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer while purging with nitrogen gas. part, and 2 parts by mass of tetraethylbenzylammonium chloride were mixed and dissolved. Next, this was heated to 65 ° C., and after reducing the pressure to an azeotropic pressure, 90 parts by mass of an aqueous sodium hydroxide solution (concentration: 49% by mass) was added dropwise over 5 hours at a constant speed, and stirred for 30 minutes. . In the meantime, the distillate distilled out by the azeotrope was separated with a Dean Stark trap, the water layer was removed, and the oil layer was allowed to react while being returned to the flask (reaction system). Thereafter, to a crude epoxy resin obtained by distilling unreacted epichlorohydrin by reduced pressure distillation (temperature: 22° C., pressure: 1.87 kPa), 590 parts by mass of methyl isobutyl ketone and 177 parts by mass of n-butanol Part was added to dissolve. 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 confirmed that the pH of the cleaning liquid used for the third water washing was neutral. Subsequently, the inside of the flask (inside the reaction system) was dehydrated by azeotropy, microfiltration was performed, and the solvent was distilled off under reduced pressure (pressure: 1.87 kPa) to obtain a brown viscous liquid in the bisphenol-based furnace used in the present invention. A rockfish-type epoxy resin (an epoxy resin (a) having structural units of Y ⁴ =glycidyl group and R ¹³ =H in general formula (IV)) was obtained. The hydroxyl equivalent of this epoxy resin was 233 g/eq.

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

In addition, the softening point of the resin was measured based on 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)

272 parts by mass of 2,2-bis(4-hydroxyphenyl)propane dissolved at 80°C was put into a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer, and stirring was started at 80°C. 3 parts by mass of methanephosphonic acid was added to this, and 16.3 parts by mass of paraformaldehyde (92% by mass) was added dropwise over 1 hour so that the temperature of the liquid was maintained in the range of 80 to 90°C. After completion of the dropping, the mixture was heated to 110°C and stirred for 2 hours. Subsequently, 1000 parts by mass of methyl isobutyl ketone was further added, and the mixture was transferred to a separation funnel and washed with water. After continued washing with water until the washing water was neutral, the solvent and unreacted 2,2-(4-hydroxyphenyl)propane were removed from the organic layer under heating and reduced pressure (temperature: 240°C, pressure: 26.7 Pa). , 164 parts by mass of a brown solid bisphenol-based novolak resin was obtained. The softening point of the obtained bisphenol-type novolac resin was 87°C, and the hydroxyl equivalent was 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 were added to a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer while purging with nitrogen gas. part and 2 parts by mass of tetraethylbenzyl ammonium chloride were mixed and dissolved. Next, after heating this to 65 degreeC and reducing pressure to the azeotropic pressure, 90 mass parts of sodium hydroxide aqueous solution (concentration: 49 mass %) was added dropwise over 5 hours at a constant speed, and it stirred for 30 minutes. In the meantime, the distillate distilled out by azeotrope was separated with a Dean Stark trap, the water layer was removed, and the oil layer was reacted while being returned to the flask (reaction system). Thereafter, to a crude epoxy resin obtained by distilling off unreacted epichlorohydrin by distillation under reduced pressure (temperature: 22° C., pressure: 1.87 kPa), 590 parts by mass of methyl isobutyl ketone and 177 parts by mass of n-butanol were added, 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 confirmed that the pH of the washing liquid used in the third water washing was neutral. Subsequently, the inside of the flask (inside the reaction system) was dehydrated by azeotropy, microfiltration was performed, and the solvent was distilled off under reduced pressure (pressure: 1.87 kPa) to obtain a brown viscous liquid in the bisphenol-based furnace used in the present invention. A rockfish-type epoxy resin (epoxy resin (a) having constituent units of Y ⁴ =glycidyl group and R ¹³ =methyl group in general formula (IV)) was obtained. The hydroxyl equivalent of this epoxy resin was 233 g/eq.

450 parts by mass of the epoxy resin (a) obtained above was mixed with 124 parts by mass of acrylic acid, 1.5 parts by mass of hydroquinone, and 250 parts by mass of carbitol acetate, heated to 90°C and stirred to dissolve the reaction mixture. Then, it was cooled to 60°C, mixed with 2 parts by mass of benzyltrimethylammonium chloride, heated to 100°C, and reacted until the acid value became 1 mgKOH/g. Next, 230 parts by mass of tetrahydrophthalic anhydride and 180 parts by mass of carbitol acetate were mixed with the reaction mixture, heated to 80°C, and reacted for 6 hours. Then, it 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)

In a flask equipped with a thermometer, a dropping funnel, a cooling pipe, and a stirrer, bisphenol F novolak-type epoxy resin (manufactured by DIC Corporation, trade name: EXA-7376, in general formula (IV), Y ⁴ and Y ⁵ = 350 parts by mass of glycidyl group, R ¹³ =hydrogen atom), 70 parts by mass of acrylic acid, 0.5 parts by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were mixed, heated to 90°C and reacted by stirring, and the mixture was completely dissolved. did Next, the obtained solution was cooled at 60°C, 2 parts by mass of triphenylphosphine was added, heated at 100°C, and reacted until the acid value of the solution became 1 mgKOH/g. 98 mass parts of tetrahydrophthalic anhydride (THPAC) and 85 mass parts of carbitol acetate were added to the solution after reaction, and it heated at 80 degreeC and made it react for 6 hours. After that, it was cooled to room temperature to obtain a solution containing acid-modified vinyl group-containing epoxy resin (IV)-c having a solid concentration 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 cooling pipe, and a stirrer, bisphenol F-type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: 4004, epoxy equivalent: 526 g/eq, in the general formula (II) is 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, and heated and stirred at 70°C. so that the mixture was dissolved. Next, the solution was cooled to 50°C, mixed with 2 parts by mass of triphenylphosphine and 75 parts by mass of solvent naphtha, 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, mixed with 745 parts by mass of tetrahydrophthalic anhydride (THPAC), 75 parts by mass of carbitol acetate, and 75 parts by mass of solvent naphtha, heated to 80°C, and reacted for 6 hours. Thereafter, it was cooled to room temperature to obtain a solution containing acid-modified vinyl group-containing epoxy resin (II)-b having a solid acid value of 80 mgKOH/g and a solid content of 62% by mass.

Examples 1 to 32, and Comparative Examples 1 to 32

According to the compounding composition shown in Tables 1-6, the composition was mix|blended and knead|mixed by the 3 roll mill, and the photosensitive resin composition was prepared. Carbitol acetate was added so that solid content concentration might be 70 mass %, and the photosensitive resin composition was obtained. It evaluated based on said evaluation method using the obtained photosensitive resin composition. An evaluation result is shown to 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, 34, and Comparative Examples 33, 34

According to the compounding composition shown in Table 6, the photosensitive resin composition was prepared by the method similar to Example 1. Each obtained photosensitive resin composition was diluted with methyl ethyl ketone, applied onto a PET film, and then dried at 90°C for 10 minutes to form a photosensitive layer composed of the photosensitive resin composition having a thickness of 25 µm. Furthermore, a polyethylene film (protective layer) was bonded thereon to fabricate a photosensitive element.

The protective layer was peeled off from the photosensitive element obtained above, and the photosensitive element was thermally laminated to a solid copper foil substrate. Subsequently, a negative mask having a pattern shown in FIG. 2 having a hole diameter of 100 μm and a pitch between holes of 100 μm or a pattern having a hole diameter of 80 μm and a pitch between holes of 80 μm is applied to the coating film It was brought into close contact with each other, and was exposed at a predetermined exposure amount shown in Table 6 using an ultraviolet exposure device (trade name: HTE-5102S, manufactured by Hi-Tech Co., Ltd.). Thereafter, spray development was carried out with a 1% by mass aqueous solution of sodium carbonate for 60 seconds at a pressure of 0.18 MPa (1.8 kgf/cm ² ) to dissolve and develop the unexposed portion. Next, using an ultraviolet exposure device (manufactured by GS Yuasa Lighting Co., Ltd., trade name: conveyor type UV irradiation device), exposure was performed at an exposure amount of 1000 mJ/cm ² , followed by heating at 150° C. for 1 hour to prepare a test piece. Evaluation similar to Example 31 was performed using the obtained test piece. Table 6 shows the evaluation results.

Note) Details of each material in Table 1 are as follows.

Irgacure 819: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by BASF Japan Co., Ltd., trade name)

Darocur TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF Japan Co., Ltd., trade name)

Irgacure 907: 2-methyl-[4-(methylthio)phenyl]morpholino-1-propanone (manufactured by BASF Japan Co., Ltd., trade name)

Irgacure OXE01: (1,2-octanedione, 1-[4-(phenylthio)-, 2-(o-benzoyloxime)] (BASF Japan Co., Ltd., trade name)

・Kayarad DPHA: dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name)

・BaSO ₄ : manufactured by Sakai Chemical Industry Co., Ltd.

SiO ₂ : manufactured by Tatsumori Co., Ltd.

Epicoat 828: bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name)

From the results shown in Table 1, the photosensitive resin composition of the present invention of Examples 1 to 6 shows that the pattern of the permanent mask resist (solder resist) has a hole diameter of 100 μm and a pitch between holes of 100 μm, Alternatively, even in a high-precision pattern with a hole diameter of 80 μm and an interval pitch between holes of 80 μm, excellent surface hardenability and bottom hardenability are maintained, a via shape with excellent resist shape can be obtained, and the thickness around the pattern is reduced. As a result, it was confirmed that the degree of via diameter was excellent. Moreover, it was confirmed that it was excellent not only in excellent resist shape but also in other properties such as solder heat resistance. This is considered to be an effect obtained by combining the photosensitive resin composition of the present invention, particularly (B) an acylphosphine oxide-based photopolymerization initiator, and a (C1) alkylaminobenzene derivative as a hydrogen donor.

On the other hand, in Comparative Examples 1 to 4, the problem of bottom curability and resist shape was not resolved, and the permanent mask resist (solder resist) pattern periphery also thickened, resulting in insufficient results.

Note) Details of each material in Table 2 are as follows.

Irgacure 819: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by BASF Japan Co., Ltd., trade name)

Darocur TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF Japan Co., Ltd., trade name)

Irgacure 907: 2-methyl-[4-(methylthio)phenyl]morpholino-1-propanone (manufactured by BASF Japan Co., Ltd., trade name)

Irgacure 369: 2-benzoyl-2-dimethylamino-1-(4-morpholino-phenyl)butanone-1 (BASF Japan Co., Ltd., trade name)

Pyrazoline sensitizer: 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline

EAB: 4,4'-diethylaminobenzophenone (manufactured by Hodogaya Chemical Co., Ltd.)

DETX-S: 2,4'-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.)

・Kayarad DPHA: dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name)

・BaSO ₄ : manufactured by Sakai Chemical Industry Co., Ltd.

SiO ₂ : manufactured by Tatsumori Co., Ltd.

Epicoat 828: bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, 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 and maintained bottom curability even in digital exposure, and were able to obtain via shapes with excellent resist shapes. In addition, the pattern of the permanent mask resist (solder resist film) is a pattern in which the hole diameter is 100 μm and the pitch between the holes is 100 μm, or the hole diameter is 80 μm and the pitch between the holes is 80 μm. Even with a high-precision pattern, it was confirmed that the thickness of the periphery could be reduced and the via diameter accuracy was excellent. In addition, it was confirmed that not only the resist shape was excellent, but also the other properties such as solder heat resistance were excellent. This is considered to be an effect obtained by combining the photosensitive resin composition of the present invention, particularly, (B) an acylphosphine oxide-based photopolymerization initiator and (C2) a pyrazoline-based sensitizer.

On the other hand, in Comparative Examples 5 to 12, the problem of bottom curability and resist shape was not resolved, and a permanent mask resist (solder resist) pattern (a pattern with a hole diameter of 100 μm and a spacing pitch between holes of 100 μm, Alternatively, a pattern in which the size of the hole diameter is 80 μm and the interval between the holes is 80 μm) also occurs, which is an insufficient result.

Note) Details of each material in Table 3 are as follows.

Irgacure 819: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by BASF Japan Co., Ltd., trade name)

Darocur TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF Japan Co., Ltd., trade name)

Irgacure 907: 2-methyl-[4-(methylthio)phenyl]morpholino-1-propanone (manufactured by BASF Japan Co., Ltd., trade name)

Anthracene-based sensitizer 1: 9,10-dibutoxyanthracene

Anthracene-based sensitizer 2: 9,10-diethoxyanthracene

Anthracene-based sensitizer 3: 9,10-dipropoxyanthracene

EAB: 4,4'-diethylaminobenzophenone (manufactured by Hodogaya Chemical Co., Ltd.)

DETX-S: 2,4'-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.)

・Kayarad DPHA: dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name)

・BaSO ₄ : manufactured by Sakai Chemical Industry Co., Ltd.

SiO ₂ : manufactured by Tatsumori Co., Ltd.

Epicoat 828: bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name)

From the results shown in Table 3, the photosensitive resin composition of the present invention of Examples 13 to 18 has excellent photocurability, and the pattern of the permanent mask resist (solder resist) has a hole diameter of 100 μm and a gap between the holes Even a pattern with a pitch of 100 μm or a high-precision pattern in which the size of the hole diameter is 80 μm and the pitch between the holes is 80 μm, it has excellent bottom hardenability, and undercut, bottom width pulling, or thickening is confirmed, or It was confirmed that an excellent resist shape could be obtained without poor linearity of the pattern outline, and the via diameter was excellent. In addition, it has been confirmed that it not only has excellent solder heat resistance and flux corrosion resistance, but also has excellent various performances such as adhesion, solvent resistance, and chemical resistance (acid resistance and alkali resistance).

On the other hand, in Comparative Examples 13 to 20, the photocurability and bottom curing properties were low, the resist shape showed an undercut, and the resist shape was poor.

Note) Details of each material in Table 4 are as follows.

Irgacure 819: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by BASF Japan Co., Ltd., trade name)

Darocur TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF Japan Co., Ltd., trade name)

Irgacure 907: 2-methyl-[4-(methylthio)phenyl]morpholino-1-propanone (manufactured by BASF Japan Co., Ltd., trade name)

Imidazole: 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer

Acridine: 1,7-bis (9,9'-acridinyl) pentane

Tinanocene: 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-benzoyloxime)] (BASF Japan Co., Ltd., trade name)

・Kayarad DPHA: dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name)

・BaSO ₄ : manufactured by Sakai Chemical Industry Co., Ltd.

SiO ₂ : manufactured by Tatsumori Co., Ltd.

Epicoat 828: bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name)

From the results shown in Table 4, the photosensitive resin compositions of Examples 19 to 24 of the present invention maintain bottom curability, can stably obtain a via shape with excellent resist shape, and a pattern of permanent mask resist (solder resist) , a pattern with a hole diameter of 100 μm and a pitch between holes of 100 μm, or a high-precision pattern with a hole diameter of 80 μm and a pitch between holes of 80 μm, the thickness of the surroundings can be reduced, , it was confirmed that the degree of via diameter was excellent. In addition, it was confirmed that not only the resist shape was excellent, but also the other properties such as solder heat resistance were excellent. This is considered to be an effect obtained by the combination of the photosensitive resin composition of the present invention, in particular, the (B) acylphosphine oxide-based photopolymerization initiator and the (C3) photopolymerization initiator.

On the other hand, in Comparative Examples 21 to 24, the problems of bottom curing properties and resist shape were not resolved, and also thickening around the pattern of the permanent mask resist occurred, resulting in insufficient results.

Note) Details of each material in Table 5 are as follows.

Irgacure 819: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by BASF Japan Co., Ltd., trade name)

Darocur TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF Japan Co., Ltd., trade name)

Irgacure 907: 2-methyl-[4-(methylthio)phenyl]morpholino-1-propanone (manufactured by BASF Japan Co., Ltd., trade name)

Irganox 1010: Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF Japan Co., Ltd., trade name)

Irganox 1035: Thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF Japan Co., Ltd., trade name)

Irganox 1076: Octadecyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF Japan Co., Ltd., trade name)

・Kayarad DPHA: dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name)

・BaSO ₄ : manufactured by Sakai Chemical Industry Co., Ltd.

SiO ₂ : manufactured by Tatsumori Co., Ltd.

Epicoat 828: bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name)

From the results shown in Table 5, the photosensitive resin composition of the present invention of Examples 25 to 30 has a permanent mask resist (solder resist) pattern having a hole diameter of 100 μm and a pitch between holes of 100 μm, Alternatively, even in a high-precision pattern in which the size of the hole diameter is 80 μm and the interval pitch between the holes is 80 μm, excellent surface hardenability and bottom hardenability are maintained, and undercut, bottom width pull, or thickening is confirmed, or a straight line of the pattern outline It was confirmed that an excellent resist shape could be obtained without poor properties, and that the degree of via diameter was excellent. In addition, it has been confirmed that it not only has excellent solder heat resistance and flux corrosion resistance, but also has excellent various performances such as adhesion, solvent resistance, and chemical resistance (acid resistance and alkali resistance).

On the other hand, in Comparative Examples 25 to 30, the surface curability and bottom curability were low, and the resist shape exhibited an undercut. In Comparative Examples 29 and 30, the irradiation dose during development was increased and the surface curability and bottom curability were good, but the As a result, the line width of the middle portion (center portion) and the deepest portion (bottom portion) of the pattern cross section became larger with respect to the line width of the surface portion (upper portion) of the pattern cross section, and the resist shape deteriorated.

Note) Details of each material in Table 6 are as follows.

Irgacure 819: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by BASF Japan Co., Ltd., trade name)

Irgacure 907: 2-methyl-[4-(methylthio)phenyl]morpholino-1-propanone (manufactured by BASF Japan Co., Ltd., trade name)

・DETX-S: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name)

MBI: mercaptobenzoimidazole

・Phthalocyanine pigment: manufactured by Sanyo Shikiso Co., Ltd.

・Alonics M402: dipentaerythritol hexaacrylate (Toagosei Co., Ltd., trade name)

・BaSO ₄ : manufactured by Sakai Chemical Industry Co., Ltd.

SiO ₂ : manufactured by Tatsumori Co., Ltd.

YSLV-80XY: tetramethylbisphenol F-type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., trade name)

RE-306: Novolak type multifunctional epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name)

・PB-3600: epoxidized polybutadiene (manufactured by Daisel Chemical Co., Ltd., trade name)

・SP1108: Polyester resin (manufactured by Hitachi Chemical Co., Ltd., trade name)

DICY 7: dicyandiamide

From the results shown in Table 6, the photosensitive resin composition of the present invention of Examples 31 to 34 has a photosensitive element and a permanent mask resist (solder resist) pattern having a hole diameter of 100 μm and a gap pitch between holes of 100 μm. Even in a pattern with a hole diameter of 80 μm and a high-precision pattern in which the pitch between holes is 80 μm, undercutting, pulling in the bottom width, or thickening are not confirmed, or the linearity of the pattern outline is not bad. It was confirmed that an excellent resist shape could be obtained.

In addition, it was confirmed that it was excellent 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 deteriorated in resist shape and were also inferior in solder heat resistance and crack resistance.

industrial usability

ADVANTAGE OF THE INVENTION According to the present invention, a photosensitive resin composition capable of forming a pattern with excellent linearity of pattern outline, excellent resist shape, and excellent resolution, without occurrence of undercutting in which the bottom part is cut out and missing of the upper part of the resist, and miniaturization It is possible to obtain a permanent mask resistor capable of forming a pattern with excellent formation stability of the size of one hole diameter and the spacing pitch between holes. A permanent mask resistor is suitably used for a printed wiring board.

Claims (15)

(A) an acid-modified vinyl group-containing epoxy resin;
(B) an acylphosphine oxide-based photopolymerization initiator;
(C1) including (C) an additive that is an alkylaminobenzene derivative and (D) a photopolymerizable compound;
(A) The 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 a structural unit represented by general formula (III) At least one type of epoxy resin selected from an epoxy resin having a constituent unit represented by general formula (IV), a bisphenol novolac-type epoxy resin having a constitutional unit represented by general formula (V), and a bisphenol novolac-type epoxy resin having a constitutional unit represented by formula (V) A resin obtained by reacting a) with a monocarboxylic acid (b) containing a vinyl group (a') obtained by reacting a polybasic acid anhydride containing a saturated group or an unsaturated group (c),
(B) the acylphosphine oxide photopolymerization initiator is at least one selected from the group consisting of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide including,
(C1) the alkylaminobenzene derivative is an aminobenzoic acid ester derivative;
A photosensitive resin composition that does not contain an acridine derivative represented by the following general formula (XII).

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

[In 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 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 represents a glycidyl group, and a plurality of R ¹³ may be the same or different.]

[In 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 is represents a glycidyl group, and a plurality of R ¹⁴ may be the same or different.]
^(XII)
[However, in Formula (XII), A represents any one of an oxygen atom, a sulfur atom, and NR ¹⁰ , R ¹ , R ² , Q ³ , Q ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^{8 ,} , R ⁹ , and R ¹⁰ each independently represent either a hydrogen atom or a monovalent substituent, and groups adjacent to each other may bond to form a ring. The monovalent substituent may further have a substituent.] delete According to claim 1,
(B) The photosensitive resin composition in which the acylphosphine oxide photopolymerization initiator contains bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide According to claim 1,
(B) The photosensitive resin composition in which the acylphosphine oxide-based photopolymerization initiator contains 2,4,6-trimethylbenzoyldiphenylphosphine oxide According to any one of claims 1, 3, 4,
The photosensitive resin composition in which the said (D) photopolymerizable compound is a compound containing a (meth)acryloyl group. According to claim 5,
(D) The photosensitive resin composition in which the photopolymerizable compound contains dipentaerythritol pentaacrylate. According to any one of claims 1, 3, 4,
(E) The photosensitive resin composition further containing an inorganic filler. According to claim 7,
(E) The photosensitive resin composition in which an inorganic filler contains barium sulfate. According to claim 7,
(E) The photosensitive resin composition in which an inorganic filler contains barium sulfate and a silica. According to any one of claims 1, 3, 4,
(F) The photosensitive resin composition further containing a pigment. According to claim 10,
(F) The photosensitive resin composition in which a pigment further contains at least 1 sort(s) selected from the group which consists of phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, and crystal violet. According to any one of claims 1, 3, 4,
A photosensitive resin composition used in the formation of permanent mask resistors. A photosensitive element comprising a support and a photosensitive layer made of the photosensitive resin composition according to any one of claims 1, 3 and 4 on the support. A permanent mask resistor formed of the photosensitive resin composition according to any one of claims 1, 3 and 4. A printed wiring board comprising the permanent mask resistor according to claim 14.