KR20160039579A - 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- or anthracene-based sensitizer, (C4) hindered phenol antioxidant, a quinone antioxidant, an amine antioxidant, a sulfur-based antioxidant, an antioxidant, an antioxidant, a photopolymerization initiator, (C) at least one kind of (C) additive selected from a compound containing a thiol group, and (D) a photopolymerizable compound. .

Description

[0001] PHOTOSENSITIVE-RESIN COMPOSITION [0002]

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 comprising the permanent mask resistor.

In the field of manufacturing printed wiring boards, it has been practiced to form permanent mask resistors on printed wiring boards. The permanent mask resist has a role of preventing the corrosion of the conductor layer or maintaining electrical insulation between the conductor layers when using the printed wiring board. In recent years, the permanent mask resist has been used as a solder resist for preventing solder from adhering to an unnecessary portion of a conductor layer of a printed wiring board in the process of flip chip mounting, wire bonding mounting, etc. through a solder on a printed wiring board. I also had a role as a film.

Conventionally, a permanent mask resistor in the production of a printed wiring board is manufactured by a screen printing method using a thermosetting resin composition, or a photographic method using a photosensitive resin composition. For example, in a flexible wiring board using a mounting method called FC (Flip Chip), TAB (Tape Automated Bonding) and COF (Chip On Film), an IC chip, an electronic component, a liquid crystal display The thermosetting resin paste is screen printed and thermally cured to form a permanent mask resistor (for example, Patent Document 1).

In addition, in a semiconductor package substrate such as a BGA (ball grid array) or a CSP (chip size package) mounted on an electronic component, (1) in order to flip-chip 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 junction. For this reason, in order to form the permanent mask resist, a photolithography method is used in which a photosensitive resin composition is selectively applied and cured by irradiating actinic rays such as ultraviolet rays after drying, and only the unexposed portions are removed with a developer to form an image . The photographic method is suitable for mass production because of its good workability, and is widely used in image forming of a photosensitive resin composition in the electronic material industry (for example, Patent Documents 2 to 4).

Patent Document 1: Japanese Patent Application Laid-Open No. 2003-198105 Patent Document 2: JP-A-11-240930 Patent Document 3: JP-A-2010-235739 Patent Document 4: Japanese Unexamined Patent Application Publication No. 2011-133851

However, when a photosensitive resin composition containing pigments, fillers and the like as described in Patent Documents 2 to 4 is used, pigments, fillers, etc. interfere with transmission of ultraviolet rays or absorb ultraviolet rays, , There is a case that the photosensitive resin composition of the bottom portion is not sufficiently cured, and as a result, an undercut may be generated in which the bottom portion is cut off after the development.

When the exposure dose of ultraviolet light is increased in order to improve the photocurability of the bottom portion, the light diffraction and halation become large, and the intermediate portion (center portion) and the deepest portion (deepest portion (Bottom part) of the resist film (bottom part) becomes large, the resist shape deteriorates or the resolution is degraded. In addition, there is also a problem that the upper part of the resist is lost and the resist shape is deteriorated due to lack of photo-curing in the region from the surface to about 3 mu m in the depth direction of the resist due to oxygen inhibition. Therefore, when the permanent mask resist, which is a thick film having a thickness of 20 to 40 μm or more, is formed, there is no photosensitive resin composition having good photo-curability at the bottom and excellent resolution.

In addition, with the recent miniaturization and high performance of electronic devices, the size of the hole diameter of the permanent mask resistors and the interval pitch of the holes tend to become finer. For example, a high-precision pattern is used in which the size of the hole diameter is 100 mu m, the pitch of the spacing between the holes is 100 mu m, or the size of the hole diameter is 80 mu m, and the spacing between the holes is 80 mu m. For this reason, for example, in flip chip packaging, a permanent mask resistor having an improved stability in resist shape from the viewpoint of improvement in resolution and solder filling property is required.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a method for manufacturing a semiconductor device, which is excellent in curing property of a bottom portion of a via opening portion, The line width of the intermediate portion (central portion) and the deepest portion (bottom portion) of the pattern section does not become larger than the line width of the surface portion, that is, the linearity of the pattern outline is good, the resist shape is excellent, And a printed wiring board comprising the photosensitive element, the photosensitive element using the photosensitive resin composition, the permanent mask resist, and the permanent mask resist.

Further, by using the photosensitive resin composition of the present invention, it is possible to use a photosensitive element capable of forming a pattern, which is excellent in the size of a fine hole diameter and the formation stability of spacing pitch between holes in accordance with recent miniaturization and high performance of electronic equipment, A resistor, and a permanent mask register thereof.

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, found that the following inventions can solve the problems. That is, the present invention provides the following photosensitive resin composition, photosensitive element, permanent mask resist, and printed wiring board.

(1) A photosensitive resin composition comprising (A) an epoxy resin containing an acid-modified vinyl group, (B) an acylphosphine oxide photopolymerization initiator, (C1) an alkylaminobenzene derivative, (C2) a pyrazoline- C3) at least one photopolymerization initiator selected from imidazole-based photopolymerization initiators, acridine-based photopolymerization initiators, and titanocene photopolymerization initiators; (C4) hindered phenol-based antioxidants, quinone-based antioxidants, (C) at least one kind of (C) additive selected from the group consisting of (C5) thiol group-containing compounds, and (D) a photopolymerizable compound .

[2] A photosensitive element comprising a support and a photosensitive layer formed on the support using the photosensitive resin composition according to [1].

[3] A permanent mask resistor formed by the photosensitive resin composition according to [1] above.

[4] A printed wiring board comprising the permanent mask resistor according to [3].

According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a pattern having good linearity of pattern outline, excellent resist shape and excellent resolution, without occurrence of undercut where the bottom portion is cut off, It is possible to obtain a photosensitive element, a permanent mask resistor, and a printed wiring board provided with the photosensitive element, which can form a pattern having a fine hole diameter and an excellent formation stability of spacing pitch between holes.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view of a resist formed using the photosensitive resin composition of the present invention.
2 is a diagram showing a pattern shape of a negative mask used in the embodiment.
3 is a diagram showing a pattern shape of a negative mask used in the embodiment.

[Photosensitive resin composition]

The photosensitive resin composition according to the embodiment of the present invention (hereinafter simply referred to as "the present embodiment") is a photosensitive resin composition containing an acid-modified vinyl group-containing epoxy resin (hereinafter also referred to as "component (A)") , (B) acylphosphine oxide photopolymerization initiator (hereinafter also referred to as "component (B)"), (C1) alkylaminobenzene derivative (hereinafter also referred to as "component (C1) (C3) an at least one photopolymerization initiator selected from imidazole-based photopolymerization initiators, acridine-based photopolymerization initiators, and titanocene-based photopolymerization initiators (hereinafter also referred to as " (Hereinafter also referred to as "component (C3)"), (C4) at least one antioxidant selected from hindered phenol antioxidants, quinone antioxidants, amine antioxidants, (Hereinafter also referred to as "component (C4)"), and (C5) thiol group (Hereinafter, also referred to as "(D) "), (D) at least one kind of additive (hereinafter also referred to as" ) Component "). ≪ / RTI >

Hereinafter, each component will be described.

<(A) Acid-Modified Vinyl Group-Containing Epoxy Resin>

The photosensitive resin composition of the present embodiment contains an acid-modified vinyl group-containing epoxy resin as the component (A).

The epoxy resin containing an acid-modified vinyl group (A) is not particularly limited as long as the epoxy resin is modified with an organic acid containing a vinyl group, and an epoxy resin obtained by reacting an epoxy resin (a) and a vinyl group- containing monocarboxylic acid (b) more preferably an epoxy resin (a '') obtained by reacting the epoxy resin (a ') with a saturated group or an unsaturated group-containing polybasic acid anhydride (c).

The epoxy resin (a) is preferably at least one selected from epoxy resins having the structural units represented by the following general formulas (I) to (V). An epoxy resin having a constituent unit represented by each general formula will be described.

[A novolak type epoxy resin having a structural unit represented by the general formula (I)

The epoxy resin (a) is preferably a novolak type epoxy resin having a structural unit represented by the following general formula (I). As the epoxy resin having such a structural unit, for example, I '). &Lt; / RTI &gt;

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

In the novolak type epoxy resin having a constituent unit represented by the general formula (I), the content of the constituent unit represented by the general formula (I) is preferably 70% by mass or more, more preferably 90% by mass or more, By mass is 95% by mass or more.

In the general formula (I '), R ¹¹ ' represents a hydrogen atom or a methyl group, Y ¹ 'represents a hydrogen atom or a glycidyl group, and the molar ratio of the hydrogen atom to the glycidyl group is preferably 0 : 100 to 30: 70, more preferably 0: 100 to 10: 90, and still more preferably 0: 100. As can be seen from the molar ratio of the hydrogen atom to the glycidyl group, at least one of Y ¹ 'represents a glycidyl group. In the general formula (I '), n1 represents an integer of 1 or more. The plural R ¹¹ 's may be the same or different from each other, and plural Y ¹ ' s may be the same or different.

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

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

Examples of the novolac epoxy resin represented by the general formula (I ') include YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, YDPN- EOCN-102S, EOCN-103S, EOCN-104S, and DEN-439 (trade names, manufactured by Daou Chemical Co., Ltd.) EOCN-1012, EOCN-1025, EOCN-1027 and BREN (trade names, manufactured by Nippon Kayaku Co., Ltd.), EPN-1138, EPN- , N-730, N-770, N-865, N-665, N-673, VH-4150 and VH-4240 (trade names, manufactured by DIC Corporation).

[Epoxy resin having a constituent unit represented by the general formula (II)] [

As the epoxy resin (a), an epoxy resin having a constituent unit represented by the following general formula (II) is preferably exemplified. As the epoxy resin having such a constituent unit, for example, an epoxy resin represented by the following general formula A bisphenol A type epoxy resin, and a bisphenol F type epoxy resin.

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

The content of the structural unit represented by the general formula (II) in the epoxy resin having the structural unit represented by the general formula (II) is preferably 70% by mass or more, more preferably 90% by mass or more, still more preferably 95% Mass% or more.

In the general formula (II '), R ¹² ' represents a hydrogen atom or a methyl group, Y ² 'represents a hydrogen atom or a glycidyl group, and the molar ratio of the hydrogen atom to the glycidyl group is preferably 0 : 100 to 30: 70, more preferably 0: 100 to 10: 90, and still more preferably 0: 100. As can be seen from the molar ratio of the hydrogen atom to the glycidyl group, at least one of Y ² 'represents a glycidyl group. In the general formula (II '), n2 represents an integer of 1 or more. The plurality of R ¹² 'may be the same or different from each other. When n 2 is 2 or more, a plurality of Y ² ' may be the same or different.

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

The bisphenol A type epoxy resin or bisphenol F type epoxy resin represented by the general formula (II ') wherein Y ² ' is a glycidyl group is, for example, bisphenol A type epoxy resin or bisphenol F type epoxy resin represented by the following general formula (VII) Type epoxy resin with an epihalohydrin such as epichlorohydrin.

In the general formula (VII), R ¹² and n 2 are the same as described above.

Considering that the amount of epihalohydrin to be used is a resist pattern which is more excellent in balance of resist shape, resolution, film strength, heat resistance, insulation reliability, thermal shock resistance and resolution, It is preferably 2 to 10 mol based on 1 mol of the hydroxyl group in the epoxy resin.

From the same viewpoint, it is preferable to use a basic catalyst in the reaction of the epoxy resin represented by the general formula (VII) with epihalohydrin. Preferable examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates and alkali metal hydroxides, and alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide are more preferable in terms of catalytic activity . The amount of the epoxy resin to be used is preferably 0.9 to 2 moles per mole of the hydroxyl group in the epoxy resin represented by the general formula (VII).

As the organic solvent, alcohols such as methanol and ethanol may be used as the organic solvent in view of increasing the reaction rate in the reaction of the epoxy resin represented by the general formula (VII) with epihalohydrin. Cellosolve such as methylcellosolve, ethylcellosolve; Ethers such as tetrahydrofuran and dioxane; Polar organic solvents such as dimethylformamide, dimethylacetamide and dimethylsulfoxide are preferably used. Of these, one type may be used alone, or two or more types may be used in combination. From the viewpoint of polarity adjustment, it is preferable to use two or more types in combination.

The reaction temperature is preferably 20 to 120 ° C, more preferably 50 to 120 ° C, and the reaction time is preferably 0.5 to 10 hours. If the reaction temperature and the reaction time are within the above range, the reaction is hardly delayed and side reaction products are hardly generated.

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

From the viewpoint of obtaining a higher purity epoxy resin, the obtained epoxy resin can be redissolved in an organic solvent and reacted with a basic catalyst such as an alkali metal hydroxide as described above. At this time, it is preferable to use an interphase transfer catalyst such as quaternary ammonium salt and crown ether in an amount of 0.1 to 3% by mass based on the epoxy resin, from the viewpoint of increasing the reaction rate. In this case, the salt or the like produced after completion of the reaction is removed by filtration, washing with water or the like, and the organic solvent or the like is distilled off under heating and reduced pressure, whereby a high-purity epoxy resin can be obtained.

Examples of the bisphenol A type epoxy resin or bisphenol F type epoxy resin represented by the general formula (II ') include Epikote 807, 815, 825, 827, 828, 834, 1001, 1004, 1007 and 1009 DER-330, DER-301, DER-361 (trade names, manufactured by Dow Chemical Co., Ltd.), YD-8125, YDF-170, YDF-175S, YDF-2001, YDF-2004 and YDF-8170 (all trade names, manufactured by Shin-Nippon Seisakusho Co., Ltd.) are commercially available.

[Epoxy resin having a structural unit represented by the general formula (III)

As the epoxy resin (a), an epoxy resin having a constituent unit represented by the following general formula (III) is preferably exemplified. As the epoxy resin having such a constituent unit, for example, And triphenol methane type epoxy resins.

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

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

The content of the structural unit represented by the general formula (III) in the epoxy resin having 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% Mass% or more.

Examples of the triphenolmethane type epoxy resin represented by the general formula (III ') include commercially available products such as FAE-2500, EPPN-501H and EPPN-502H (manufactured by Nippon Kayaku Co., Do.

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

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

In the 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 s} may be the same or different.

The alkyl group of R ¹³ preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 3 carbon atoms. The alkyl group may be linear or 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.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a sec-pentyl group, an isopentyl group, Etc. Among these, a methyl group is more preferable.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group and the like, preferably an aryl group having a ring forming (ring forming) carbon number of 6 to 20, &Lt; / RTI &gt; 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 above aryl group. Examples thereof include a benzyl group, a phenylethyl group, a phenylpropyl group, and a naphthylmethyl group. 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.

The content of the structural unit represented by the general formula (IV) in the epoxy resin having 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% Mass% or more.

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

[Bisphenol novolak type epoxy resin having a constituent unit represented by the 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 used.

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

The content of the structural unit represented by the general formula (V) in the epoxy resin having 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% Mass% or more. Within the above range, a resist pattern having better balance of resist shape, resolution, heat resistance, adhesion, and electrical insulation can be obtained.

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

The bisphenol novolak type epoxy resin having the constitutional units represented by the general formulas (IV) and (V) can be produced, for example, by reacting the hydroxyl groups of the bisphenol-novolac resins represented by the following general formulas (VIII) and (IX) Or an epihalohydrin such as borane or borane.

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

The bisphenol novolak resin having the constitutional units represented by the general formulas (VIII) and (IX) is preferably obtained by copolymerizing a bisphenol compound and an aldehyde compound or a ketone compound with an alkyl group having 1 to 4 carbon atoms in a molecular structure Can be obtained by the reaction in the presence of a sulfonic acid.

Examples of the bisphenol compound 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, and the like. Bisphenol A and bisphenol F are more preferable.

Examples of the aldehyde compound to be reacted with the bisphenol compound include formaldehyde, acetaldehyde, benzaldehyde, 4-methylbenzaldehyde, 3,4-dimethylbenzaldehyde, biphenylaldehyde and naphthylaldehyde. Benzophenone, fluorenone, indanone, and the like. Of these, formaldehyde is preferred.

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

More specifically, the bisphenol novolak type epoxy resin having the constitutional units represented by the general formulas (IV) and (V) can be preferably obtained as follows.

The bisphenol compound and the aldehyde compound or the ketone compound are placed in a reaction vessel and the mixture is continuously or intermittently added with a sulfonic acid so as to maintain the temperature within a range of 20 to 200 ° C while stirring in an inert gas atmosphere, To obtain a crude bisphenol novolak resin. Subsequently, the crude bisphenol novolac resin is extracted with a water-insoluble organic solvent to prepare a bisphenol novolak resin solution, which is then washed with water and neutralized, and further the water-insoluble organic solvent is removed therefrom to obtain a bisphenol novolac epoxy A resin can be obtained.

The non-aqueous organic solvent preferably has a boiling point of 100 to 130 캜 from the viewpoint of improving the working efficiency of extraction, washing and neutralization. Examples of the water-insoluble organic solvent include butanol, pentyl alcohol, methoxy ethanol, ethoxy ethanol, diethylene glycol, methyl isobutyl ketone and the like. Of these, butanol, methoxy ethanol, Butyl ketone is more preferable, and methyl isobutyl ketone is more preferable.

The washing with water is carried out until the crude bisphenol novolak resin solution has a pH of 3 to 7, more preferably, a pH of 5 to 7, and if necessary, a basic substance such as sodium hydroxide, sodium carbonate, ammonia or triethylenetetramine .

It is preferable to carry out the distillation under reduced pressure distillation under the conditions of, for example, a temperature of 170 to 200 DEG C and a pressure of 3 kPa or less. By carrying out the distillation under these conditions, a bisphenol novolak resin having high purity can be obtained.

As the epoxy resin (a), a novolak type epoxy resin having a structural unit represented by the general formula (I), a structural unit represented by the general formula (II) And a bisphenol novolak type epoxy resin having a structural unit represented by the general formula (IV) are preferable, and a novolak type epoxy resin represented by the general formula (I '), a bisphenol novolak type epoxy resin represented by the general formula (II' ), Bisphenol A type epoxy resin or bisphenol F type epoxy resin having a structural unit represented by the general formula (IV), or a bisphenol F type epoxy resin having a structural unit represented by the general formula (IV) are more preferable.

From the viewpoint of further reducing warpage of the thin film substrate and further improving thermal shock resistance, an epoxy resin having a structural unit represented by the general formula (IV) and a structural unit represented by the general formula (V) It is preferable to use an epoxy resin in combination.

(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, dimer of acrylic acid, methacrylic acid,? -Furfuryl acrylic acid,? -Styryl acrylic acid, Acrylic acid derivatives such as crotonic acid and? -Cyano cinnamic acid; A semi-ester compound which is a reaction product of a hydroxyl group-containing acrylate and a dibasic acid anhydride, a half ester compound which is a reaction product of a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester and a dibasic acid anhydride Can be preferably used.

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 at an equivalent molar ratio. These vinyl group-containing monocarboxylic acids (b) may be used singly or in combination of two or more.

Examples of the hydroxyl group-containing acrylates, vinyl group-containing monoglycidyl ethers and vinyl group-containing monoglycidyl esters used in the synthesis of the above-mentioned half ester compounds, which are examples of the vinyl group-containing monocarboxylic acids (b) (Meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, ditrimethylolpropane di (meth) acrylate, pentaerythritol tri (Meth) acrylate, dipentaerythritol penta (meth) acrylate, vinyl glycidyl ether, and glycidyl (meth) acrylate.

As the dibasic acid anhydride used in the synthesis of the above-mentioned half ester compounds, those containing a saturated group and those containing an unsaturated group can be used. Specific examples of dibasic acid anhydrides include maleic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride , Itaconic anhydride, and the like.

In the reaction of the above-mentioned epoxy resin (a) with the vinyl group-containing monocarboxylic acid (b), the ratio of the equivalent of the vinyl group-containing monocarboxylic acid (b) to 0.6 to 1.05 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin (a) , More preferably 0.8 to 1.0 equivalent, and still more preferably 0.9 to 1.0 equivalent. By reacting at such a ratio, the photopolymerization is improved and the photosensitivity is more excellent.

The reaction between the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) can be carried out by dissolving the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) in an organic solvent.

Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; 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 ether such as petroleum ether, petroleum naphtha, hydrogenated naphtha and solvent naphtha.

Further, it is preferable to use a catalyst to promote the reaction. As the catalyst, for example, triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide, triphenylphosphine and the like are preferably used . The amount of the catalyst to be used is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). When the amount is used, the reaction between the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) is promoted, which is preferable.

It is preferable to use a polymerization inhibitor for the purpose of preventing polymerization during the reaction. As the polymerization inhibitor, for example, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like are preferably used. The amount of the polymerization inhibitor to be used is preferably 0.01 to 1 part by mass based on 100 parts by mass of the total amount of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). The above-mentioned amount is preferable because the storage stability (self-life) of the composition is improved. The reaction temperature is preferably 60 to 150 占 폚, more preferably 80 to 120 占 폚.

If necessary, the vinyl group-containing monocarboxylic acid (b) and a phenol-based compound such as p-hydroxyphenethyl alcohol, anhydrous trimellitic acid, anhydrous pyromellitic acid, benzophenonetetracarboxylic acid anhydride, biphenyltetracarboxylic acid anhydride May be used in combination with the polybasic acid anhydride.

The epoxy resin (a ') thus obtained is presumed to have a hydroxyl group formed by the addition reaction of the epoxy group of the epoxy resin (a) with the carboxyl group of the vinyl group-containing monocarboxylic acid (b).

(Polybasic acid anhydride (c))

As the epoxy resin containing an acid-modified vinyl group (A), an epoxy resin (a ") obtained by reacting the above-mentioned epoxy resin (a ') with a polybasic acid anhydride (c) It is presumed that the acid anhydride groups of the epoxy group (a ') in the hydroxyl group (including the hydroxyl group originally present in the epoxy resin (a)) and 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, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Phthalic anhydride, itaconic anhydride, and the like.

(C) in an amount of 0.1 to 1.0 equivalent per one equivalent of hydroxyl groups in the epoxy resin (a ') in the reaction of the epoxy resin (a') with the polybasic acid anhydride (c) The acid value of the resin can be adjusted.

The acid value of the acid-modified vinyl group-containing epoxy resin (A) is preferably 30 to 150 mgKOH / g, more preferably 40 to 120 mgKOH / g, and 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 the diluted alkali solution is not lowered, and when the acid value is 150 mgKOH / g or less, the electrical characteristics of the cured film are hardly lowered.

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

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

The weight average molecular weight of the acid-modified vinyl group-containing epoxy resin (A) is preferably from 3,000 to 30,000, more preferably from 4,000 to 25,000, and still more preferably from 5,000 to 18,000. When the weight average molecular weight of the component (A) is within the above range, a pattern having a better balance of resist shape, resolution, heat resistance, adhesion, and electrical insulation can be obtained. Here, the weight average molecular weight is a weight average molecular weight in terms of polyethylene measured by a gel permeation chromatograph (GPC) method using tetrahydrofuran as a solvent. More specifically, for example, the weight average molecular weight may be determined by measuring the GPC measurement apparatus and measurement conditions described below, and converting the value obtained by using the calibration curve of standard polystyrene. The calibration curve was prepared using 5 sample sets ("PStQuick MP-H" and "PStQuick B ", manufactured by Tosoh Corporation) as standard polystyrene.

(GPC measuring device)

GPC apparatus: a high-speed GPC apparatus "HLC-8320GPC", a detector was a differential refractometer, manufactured by Tosoh Corporation

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)

Measuring temperature: 40 ° C

Flow rate: 0.35 ml / min

Sample concentration: 10 mg / THF 5 ml

Injection amount: 20 μl

Examples of the acid-modified vinyl group-containing epoxy resin (A) include a novolak type epoxy resin having a structural unit represented by the general formula (I), a novolak type epoxy resin represented by the general formula (I '), An epoxy resin obtained by reacting an epoxy resin having a constituent unit represented by the formula (II), preferably a bisphenol A type epoxy resin and a bisphenol F type epoxy resin represented by the formula (II ') with a vinyl group-containing monocarboxylic acid (b) is preferably an epoxy resin (a '') obtained by reacting an epoxy resin (a ') and an epoxy resin (a') with a saturated or unsaturated polybasic acid anhydride (c) .

These epoxy resins (a ') and (a ") may be used singly or in combination of two or more kinds, and it is preferable to use a plurality of kinds of epoxy resins in combination. Examples of the combination include an epoxy resin (a ') or (a' ') obtained from the novolak type epoxy resin represented by the general formula (I') and a bisphenol A type epoxy resin represented by the general formula (II ' Is preferably a combination of two kinds of epoxy resin (a ') or (a' ') obtained from a resin and is preferably a combination of an epoxy resin (a' ') obtained from a novolak type epoxy resin represented by the general formula (I' And a combination of two kinds of epoxy resin (a '') obtained from a bisphenol A type epoxy resin represented by the formula (II ') and a bisphenol F type epoxy resin.

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

When the (C5) thiol group-containing compound described later is used as the component (C), the epoxy resin (a ') or (a') obtained from the bisphenol novolak type epoxy resin having the structural unit represented by the general formula (IV) ) And an epoxy resin (a ') or (a ") obtained from a bisphenol A type epoxy resin and a bisphenol F type epoxy resin represented by the general formula (II'), (A ") obtained from a bisphenol novolak A type epoxy resin or a bisphenol F type epoxy resin having a constituent unit represented by the following formula (IV), a bisphenol A type epoxy resin represented by the formula (II ') and a bisphenol F type epoxy And an epoxy resin (a '') obtained from a resin are more preferable.

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

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

&Lt; (B) Acylphosphine oxide photopolymerization initiator &gt;

The photosensitive resin composition of the present embodiment contains an acylphosphine oxide-based photopolymerization initiator as the component (B).

The (B) acylphosphine oxide-based photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator having an acylphosphine oxide group (= P (= O) -C (= O) - group) Dimethoxybenzoyl) -2,4,6-trimethylbenzoyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, (2,5-dihydroxyphenyl) diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphinate, (p-hydroxyphenyl) diphenylphosphine oxide, bis (p-hydroxyphenyl) phenylphosphine oxide, and tris (p-hydroxyphenyl) phosphine oxide. Or two or more of them may be used in combination.

The content of the acylphosphine oxide-based photopolymerization initiator (B) in which the total solid content in the photosensitive resin composition is 100 parts by mass is preferably 0.2 to 15 parts by mass. When the amount is 0.2 parts by mass or more, the exposed portion is difficult to elute during development, and when it is 15 parts by mass or less, the heat resistance is less likely to deteriorate. For the same reason, the content of the photopolymerization initiator (B) is more preferably from 0.2 to 10 parts by mass, more preferably from 0.2 to 5 parts by mass, particularly preferably from 0.5 to 5 parts by mass, and particularly preferably from 0.5 to 3 parts by mass .

In addition, a photopolymerization initiator such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine and triethanolamine, They may be used alone or in combination of two or more.

<(C) Additive>

The photosensitive resin composition of the present embodiment is characterized by comprising, as the component (C), (C1) an alkylaminobenzene derivative, (C2) a pyrazoline-based sensitizer or an anthracene-based sensitizer, (C3) an imidazole-based photopolymerization initiator, At least one photopolymerization initiator selected from a photopolymerization initiator, an initiator, and a titanocene photopolymerization initiator; (C4) at least one photopolymerization initiator selected from a hindered phenol antioxidant, a quinone antioxidant, an amine antioxidant, An antioxidant of the species, and (C5) a thiol group-containing compound. By using these additives in combination with the (B) acylphosphine oxide-based photopolymerization initiator, a photosensitive resin composition capable of forming a pattern having good 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 in the benzene ring and can function effectively as a hydrogen donor, thereby improving the photosensitivity and light stability of the photosensitive resin composition. Here, the hydrogen donor means a compound capable of donating a hydrogen atom to a radical generated by the exposure treatment of the photopolymerization initiator. In the present embodiment, the combination of the acylphosphine oxide-based photopolymerization initiator (B) and the alkylaminobenzene derivative (C1) as the hydrogen donor is particularly preferable because the linearity of the outline of the pattern is good and the resist shape is excellent , And is effective in forming a pattern having excellent resolution.

(C1) alkylaminobenzene derivatives include, for example, phenylglycine derivatives, aminobenzoic acid derivatives, and aminobenzoic acid ester derivatives.

As the phenylglycine derivative, N-phenylglycine, N, N-diphenylglycine, N-naphthylglycine and the like are preferably exemplified.

Examples of the aminobenzoic acid derivative include 2-methylaminobenzoic acid and 2-ethylaminobenzoic acid. Examples of aminobenzoic acid ester derivatives include N, N-dimethylaminobenzoate, N, N-diethylaminobenzoate, N, N-dimethylaminobenzoic acid isoamyl, N, N-diethylaminobenzoic acid, Can be preferably used.

In the present embodiment, an aromatic amine compound having an alkylamino group may be used. Specific examples thereof include dialkyldiphenylamines having 8-14 carbon atoms in the alkyl group, octyldiphenylamine, 4,4'-bis (?,? - dimethylbenzyl) diphenylamine, N-phenyl-N Phenyl-N '- (3-methacryloyloxy-phenyl) -isopropyl-p-phenylenediamine, 2-hydroxypropyl) -p-phenylenediamine, and the like.

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

These (C1) alkylaminobenzene derivatives may be used singly or in combination of two or more. Also, an aliphatic amine compound may be used at the same time as the above alkylaminobenzene derivative. As specific examples, triethanolamine, triethylamine and the like are preferably exemplified.

The content of the (C1) alkylaminobenzene derivative in which the total solid content in the photosensitive resin composition is 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, 1.0 part by mass is particularly preferable. When the content is 0.1 part by mass or more, the solution of the photosensitive resin composition becomes difficult to gel, and when it is 5 parts by mass or less, photosensitivity is not easily deteriorated.

[(C2) pyrazoline-based sensitizer or anthracene-based sensitizer]

(C2) is a pyrazoline-based sensitizer, or an anthracene-based sensitizer. (C2) pyrazoline-type sensitizer, it is possible to provide a resist composition which is excellent in linearity of a pattern contour, excellent in resist shape, and has excellent resolution even without digital exposure, A photosensitive resin composition capable of forming an excellent pattern can be obtained.

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

In 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 sum of a, b, and c is 2 to 6, a plurality of Rs in the same molecule may be the same or different. The alkyl group of R may be linear or 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. As R, an alkyl group having 4, 8 and 12 carbon atoms is preferable, and more specifically, n-butyl group, tert-butyl group, tert-octyl group and n-dodecyl group are preferable, It is preferable that the other is different.

Examples of such pyrazoline sensitizers include 1- (4-tert-butylphenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl- - (4-tert-butyl-phenyl) -pyrazolene, l- (4-tert- phenyl-3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) (4-tert-octyl-phenyl) -3-styryl-pyrazoline, 5- (4-dodecyl-phenyl) -pyrazoline, 1- (4-dodecyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, - (4-tert-butyl-phenyl) -pyrazoline, 1- (4-tert-butyl- (4-tert-butyl-styryl) -5- (4-tert- butylphenyl) - pyrazoline, 1- (4-dodecyl- Butyl-phenyl) -3- (4-dodecyl- (4-tert-octyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, (4-tert-octyl-phenyl) -pyrazoline, 1- (4-tert- Phenyl-3- (3,5-di-tert-butyl-phenyl) butyl-styryl) -5- (3,5-di-tert-butyl-phenyl) (2,5-di-tert-butyl-styryl) -5- (2,5-di-tert-butyl) (2,6-di-n-butyl-phenyl) -pyrazoline, 1- ( Phenyl-3-styryl-5-phenyl-pyrazoline, 1- (3,5-di-tert- (3,5-di-tert-butyl-phenyl) - pyrazoline, 1- (4-tert- (3,5-di-tert-butyl-phenyl) -3- (3,5-di-tert- butylstyryl) And the like can be referred to sleepy preferred.

The content of the (C2) pyrazoline type sensitizer in the total amount of the solid content in the photosensitive resin composition 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, even more preferably 0.03 to 1 part by mass To 0.5 parts by mass is particularly preferable, and 0.03 to 0.2 parts by mass is extremely preferable. When the content of the (C2) pyrazoline type sensitizer is 0.01 parts by mass or more, the exposed portion is difficult to elute during development, and when it is 10 parts by mass or less, deterioration of heat resistance can be suppressed.

In the photosensitive resin composition of the present embodiment, it is preferable to add (C2) anthracene-based sensitizer.

The (C2) anthracene type sensitizer used in the photosensitive resin composition of the present embodiment makes it possible to form a pattern having excellent resist shape and excellent resolution by improving the photocurability.

As the (C2) anthracene-based sensitizer, for example, compounds represented by the following general formula (XI) are preferably exemplified.

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 an -N (R ⁴ ) ₂ group, two or more of R ³ 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 straight- 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. The plurality of R ³ and R ⁴ may be the same or different.

X represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, -N (R ') - group, -C (= O) SO ₂ -O- group, -S- -SO _{2 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 (i.e., unsubstituted anthracene). The plural Xs may be the same or different.

Here, R ⁴ is, represents a hydrogen atom, an alicyclic group having 1 to 8 carbon atoms an alkyl group, having 3 to 20 carbon atoms, the alkenyl group, an aryl group having a carbon number of 2-8, or a heteroaryl group, R ⁴ together are bonded to each other cyclic structure An alkyl group, an aryl group, an aralkyl group, an amino group, an amide group, an alkoxy group, etc., may be added to the cyclic structure, May be substituted.

Examples of the alicyclic group having 3 to 20 carbon atoms in R ³ and R ⁴ include a cyclic group such as a norbornyl group, a tricyclodecanyl group, a tetracyclo-cyclohexyl group, a tricyclodecanyl group, And bridged alicyclic hydrocarbon groups having 6 to 20 carbon atoms such as a dodecyl group, an adamantyl group, a methyladamantyl group, an ethyladamantyl group, and a butyladamantyl group.

The aryl group is preferably those exemplified as the aryl group of R &lt; ¹³ & gt ^{;. As} the heteroaryl group, at least one of the optional reducing groups constituting the aryl group may be substituted with a hetero atom such as a sulfur atom, And the like.

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 naphthyl group, a p-tolyl group, a benzyl group, a phenyl group, a 1-naphthyl group and the like can be preferably exemplified as the naphthyl group, the naphthyl group, the naphthyl group,

Examples of the (C2) anthracene type sensitizer represented by the above general formula (XI) include 1-methyl anthracene, 2-methyl anthracene, 2-ethyl anthracene, 2- Alkylanthracene such as anthracene; Dialkyl anthracenes such as 9,10-dimethyl anthracene, 9,10-dipropylanthracene and 9,10-dibutyl anthracene; Hydroxyalkylanthracene such as 9- (hydroxymethyl) anthracene and 9- (2-hydroxyethyl) anthracene; Dialkoxyanthracene such as 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-di (2-ethylhexyloxy) anthracene; Alkenyl anthracene such as 9-vinyl anthracene and 9-allylanthracene; Aminoanthracene such as 1-aminoanthracene, 2-aminoanthracene and 9- (methylaminomethyl) anthracene; Anthraldehyde such as 9-anthraldehyde and 10-methyl-9-anthraldehyde; In addition, it is also possible to use 9-phenylanthracene, 9-acetylanthracene, 9,10-diphenylanthracene, 1,2-benzanthracene, 1,8,9-triacetoxyanthracene, 1,4,9,10-tetrahydroxy And anthracene. These anthracene sensitizers may be used singly or in combination of two or more.

Among these, diphenylanthracene, dialkyl anthracene, and dialkoxyanthracene are preferable, and 9,10-dimethylanthracene, 9,10-diphenylanthracene, 9,10-diethoxyanthracene, 9,10- , 9,10-dibutoxyanthracene and 9,10-di (2-ethylhexyloxy) anthracene are more preferable, and 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, And 9,10-dialkoxy anthracene such as dibutoxy anthracene and 9,10-di (2-ethylhexyloxy) anthracene are more preferable. In the present embodiment, by using these anthracene sensitizers, it is possible to obtain a photosensitive resin composition having photosensitivity particularly in the wavelength range of 300 to 450 nm, and the photocurability can be improved, It is possible to form an excellent pattern.

The content of (C2) anthracene-based sensitizer in 100 parts by mass of the total solid content in the photosensitive resin composition is preferably 0.001 to 10 parts by mass. When the content of the (C2) anthracene type sensitizer is within the above range, the photocurability can be improved, and a pattern excellent in resist shape and excellent in resolution can be formed. For the same reason, the content of (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.

The content of (C2) anthracene-based sensitizer in (A) 100 parts by mass of the 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, further preferably 0.03 to 3 parts by mass More preferable.

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

(C3) is at least one photopolymerization initiator selected from an imidazole-based photopolymerization initiator, an acridine-based photopolymerization initiator, and a titanocene photopolymerization initiator.

In the present embodiment, the combination of the above-mentioned (B) acylphosphine oxide-based photopolymerization initiator and the (C3) component is particularly preferable as the combination of the pattern Is effective.

The imidazole-based photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator having an imidazole ring in the molecule, and examples thereof include 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'- Imidazole 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) Dimethoxyphenyl) -4,5-diphenylimidazole dimer, and 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer, etc., 2,4,5-triaryl Imidazole dimer, and the like.

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

Examples of such 2,4,5-triarylimidazole dimer include 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl- -Imidazole, 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'- Tetra (p-fluorophenyl) imidazole dimer, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p (O, p-dichlorophenyl) imidazole dimer, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'- (O, p-dibromophenyl) imidazole dimer, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'- ) -4,4 ', 5,5'-tetra (p-chloronaphthyl) imidazole dimer, 2,2'-bis (m, p- Tetraphenylimidazole dimer, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5 (O, p-dichlorophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) imidazole dimer, 2,2'-bis - (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p- Phenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4 , 5-diphenylimidazole dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer, 2,2'-bis (p-bromophenyl) 4 ', 5,5'-tetraphenylimidazole dimer, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetra (o, Bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p-iodophenyl) imidazole dimer, 2,2'-bis Bis (m, p-dibromophenyl) -4,4 ', 5,5'-tetramethyldimodazole dimer, 2,2'- Phenyl imidazole dimer, and the like.

The aryl group of the 2,4,5-triarylimidazole dimer is further substituted by a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an amino group, An alkylamino group having 1 to 10 carbon atoms, a nitro group, a cyano group, a mercapto group, an alkylmercapto group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, an allyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, A carboxyalkyl group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms in the alkyl group, an alkoxyl group having 1 to 20 carbon atoms, or a group having 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-butylene bis- (acridine-9-yl) acrylate, p- acrylate], triethylene glycol bis [? - (acridine-9-yl) acrylate, 9-phenylacridine, 1,7-bis '-Acridinyl) heptane, and the like.

As the titanocene photopolymerization initiator, there is no particular limitation 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- (2,4-cyclopentadienyl) -bis (2,6-difluoro-3- (1-pyryl) phenyl) titanium and the like. These photopolymerization initiators may be used singly or in combination of two or more.

The content of the (C3) photopolymerization initiator in the total amount of the solid content in the photosensitive resin composition is preferably 0.01 to 15 parts by mass, more preferably 0.01 to 5 parts by mass, further preferably 0.01 to 3.5 parts by mass, more preferably 0.02 to 1.0 part by mass The addition is particularly preferred. When the content is 0.01 part by mass or more, the solution of the photosensitive resin composition becomes difficult to gel, and when it is less than 15 parts by mass, the photosensitivity is hardly lowered.

The total content of the acylphosphine oxide-based photopolymerization initiator (B) and the photopolymerization initiator (C3) in which the total solid content in the photosensitive resin composition is 100 parts by mass is preferably 0.2 to 15 parts by mass. When the amount is 0.2 parts by mass or more, the exposed portion is difficult to elute during development, and when it is 15 parts by mass or less, the heat resistance is less likely to deteriorate. For the same reason, the total content of the photopolymerization initiator (B) and the photopolymerization initiator (C3) is more preferably 0.2 to 10 parts by mass, 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 preferable.

The mass ratio of the acylphosphine oxide-based photopolymerization initiator (B) to the photopolymerization initiator (C3) is preferably 100: 0.5 to 100: 8, more preferably 100: 1 to 100: 6, To 100: 5 is more preferable. When the mass ratio is within the above range, it is preferable because the resist shape is excellent and the bottom hardness and the viahole diameter accuracy (accuracy) tend to be improved.

At least one antioxidant selected from the group consisting of [(C4) hindered phenol antioxidants, quinone antioxidants, amine antioxidants, sulfur antioxidants, and phosphorus antioxidants]

(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 the component (C4), a photosensitive resin composition which can form a pattern having excellent resist shape and excellent in resolution and capable of forming a pattern having excellent solder heat resistance and flux corrosion resistance can be obtained.

Examples of the hindered phenol antioxidant include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (BASF Japan, Irganox 1010 (Manufactured by BASF Japan, Irganox 1035 (trade name)), octadecyl (meth) acrylate (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (BASF Japan, Irganox 1076 (trade name) (octylthiomethyl-o-cresol) (manufactured by BASF Japan Co., Ltd.), and 4,6-bis (octylthiomethyl-o-cresol) (3'5'-di-t-butyl-4'-hydroxyphenyl) -propionate, n-octadecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate, ) -Propionate, 1,6-hexanediol-bis- (3- (3,5-di-t- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), 1,4-butanediol- (Methylene) 3- (3 ', 5'-di-t-butyl-propyl) Hydroxyphenyl) propionate methane, 3,9-bis (2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) ) 2,4,8,10-tetraoxaspiro (5,5) undecane, N, N'-bis-3- (3'5'-di-t- butyl-4-hydroxyphenol) N, N'-bis- (3- (3'-methyl-5'-t- butylphenol) propionyldiamine, N, N'-tetramethylenebis (5-di-t-butyl-4-hydroxyphenol) propionyl) hydrazine, N-salicyloyl-N'-salicylidenehydrazine, 3- Triazole and N, N'-bis (2- (3- (3,5-di-butyl 4-hydroxyphenyl) propionyloxy) ethyl) oxyamide These can be used singly or in combination of two or more. Examples of the quinone antioxidant include quinone antioxidants such as hydroquinone, 2-t-butylhydroquinone, hydroquinone monomethyl ether, metaquinone, and benzoquinone. These antioxidants may be used alone or as a mixture of two or more Can be used in combination. These antioxidants having a phenolic hydroxyl group can be expected to have a trapping effect such as a peroxy radical (ROO), an alkyl radical (R), and the like.

Examples of the amine antioxidant include phenylnaphthylamine, 4,4'-dimethoxydiphenylamine, 4,4'-bis (?,? - dimethylbenzyl) diphenylamine, di- (N, N'-di (2-naphthyl) -phenylenediamine, bis (2,2,6,6-tetra Methyl-4-piperidyl) sebacate, phenothiazine and the like, and these may be used singly or in combination of two or more. The amine-based antioxidant can be expected to capture the peroxy radical (ROO).

As the sulfur-based antioxidant, there can be mentioned, for example, didodecyl-3,3'-thiodipropionate, ditetradecyl-3,3'-thiodipropionate, dioctadecyl-3,3'-thiodipropionate, (3-dodecylthiopropionate), pentaerythritol tetrakis (3-dodecylthiopropionate), pentaerythritol tetrakis (3-tetradecylthiopropionate), pentaerythritol Tetrakis (3-tridecylthiopropionate), dilauryl-3,3-thiodipropionate, dimyristyl-3,3-thiodipropionate, distearyl-3,3-thiodi Propionate, pentaerythritol tetrakis (3-lauryl thiodipropionate, 2-mercaptobenzoimidazole, lauryl stearyl thiodipropionate, zinc salt of 2-mercaptomethyl benzimidazole, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc dibutylthiocarbamate, and the like. These may be used singly or in combination of two or more.

Examples of the phosphorus antioxidant include triphenyl phosphite, tris (methylphenyl) phosphite, triisooctyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tris (nonylphenyl) phosphite, tris ), Bis (2-ethylhexyl) phosphite, tris [decyl poly (oxyethylene) phosphite, tris (cyclohexylphenyl) phosphite, tricyclohexyl phosphite, (Ethylhexyl) phosphite, phenyldiisodecylphosphite, tetradecylpoly (oxyethylene) -bis (ethylphenyl) phosphite, phenyl-dicyclohexylphosphite, phenyl-diisooctylphosphite, phenyldi (Tridecyl) phosphite, diphenyl-cyclohexylphosphite, diphenyl-isooctylphosphite, diphenyl-2-ethylhexylphosphite, diphenyl-isodecylphosphite, diphenyl-cyclohexylphenylphosphine , Diphenyl (tridecyl) may be preferably mentioned an alkylthio such as phosphate, may be used in these alone or in combination of two or more.

As a sulfur-based antioxidant and a phosphorus-based antioxidant, an effect of decomposing peroxides can be expected. Examples of commercially available products of the sulfur-based antioxidant and phosphorus-based antioxidant include Adekastab TPP (trade name, manufactured by Adeka Co., Ltd.), Mark AO-412S (trade name, manufactured by Adeka Corporation), Sumiridor TPS (Trade names, manufactured by Kagaku Co., Ltd.).

Further, in the present embodiment, it is preferable to use a combination of a hindered phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, and the like as the antioxidant (C4) in an excellent resist shape and excellent solder heat resistance and anti- Is particularly preferable.

The content of the antioxidant (C4) in which the total solid content in the photosensitive resin composition is 100 parts by mass is preferably 0.2 to 15 parts by mass. When the amount is 0.2 parts by mass or more, the exposed portions are difficult to elute during development, and when the amount is 15 parts by mass or less, heat resistance is less likely to deteriorate. For the same reason, the content of the (C4) antioxidant is more preferably from 0.2 to 10 parts by mass, still more preferably from 0.5 to 5 parts by mass, and particularly preferably from 0.5 to 3 parts by mass.

[(C5) thiol group-containing compound]

The component (C5) is a thiol group-containing compound. The thiol group-containing compound effectively functions as a hydrogen donor and has an effect of further improving the photosensitivity and light-stability of the photosensitive resin composition.

Examples of the (C5) thiol group-containing compound include mercaptobenzoxazole, mercaptobenzothiazole, mercaptobenzimidazole, ethanethiol, benzenethiol, mercaptophenol, mercaptotoluene, 2- mercaptoethyl Amines, mercaptoethyl alcohols, mercaptoxylene, thiazolylenes, 2-mercaptokinolines, mercaptoacetic acids,? -Mercaptopropionic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thiosalicylic acid, mercaptocyclohexane , mercapto-diphenylmethane,? -mercaptodiphenylmethane, C-mercaptotetrazole, mercaponaphthalene, mercaptonaphthol, 4-mercaptobiphenyl, mercaptohefcoxanthin, mercaptopyridine, 2- mercaptothyrimidine, Thiocarbazone, thiocumazone, thiocumothiazone, butane-2,3-dithiol, thiocyanuric acid, 2,4,6-trimercapto-s-triazine, -s-triazine, 2-anilino-4,6-dimercapto-s-triazine, and the like.

These (C5) thiol group-containing compounds may be used singly or in combination of two or more. Among these, from the viewpoint of effectively functioning as a hydrogen donor and further improving the sensitivity and light-stability of the photosensitive resin composition, it is preferable to use mercaptobenzoxazole, mercaptobenzothiazole, mercaptobenzimidazole, 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 whole solid content of the photosensitive resin composition, from the viewpoint of obtaining a photosensitive resin composition capable of forming a pattern having excellent resolution , More preferably from 0.1 to 3 parts by mass, still more preferably from 0.2 to 1.5 parts by mass. When the content of the (C5) 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, while when it is 5 parts by mass or less, deterioration of the sensitivity can be suppressed.

&Lt; (D) Photopolymerizable compound &gt;

The photosensitive resin composition of the present embodiment contains a photopolymerizable compound as the component (D).

(D) The photopolymerizable compound is not particularly limited as long as it is a compound having a functional group showing photopolymerization, and examples thereof include a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, , A naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a nadimide group, and a (meth) acryloyl group.

Examples of the photopolymerizable compound (D) 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, methoxy tetraethylene 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; (Meth) acrylates of polyhydric alcohols such as hexanediol, trimethylol propane, pentaerythritol, ditrimethylol propane, dipentaerythritol, and tris-hydroxyethylisocyanurate, or ethylene oxide or propylene oxide adducts thereof ; (Meth) acrylates of an ethylene oxide or propylene oxide adduct of phenols such as phenoxyethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenol A; (Meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate; Melamine (meth) acrylate, and the like. These (D) photopolymerizable compounds may be used singly or in combination of two or more.

The content of the photopolymerizable compound (D) in the total amount of the solid content in the photosensitive resin composition 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, Particularly preferably 1.5 to 10 parts by mass. When the amount is 0.1 parts by mass or more, the exposed portions are hardly eluted during development, and the sensitivity and resolution of the photosensitive resin composition tend to be improved. When the amount is 30 parts by mass or less, heat resistance tends to be improved.

<(E) Inorganic filler>

The photosensitive resin composition of the present embodiment preferably contains an inorganic filler as the component (E).

The inorganic filler (E) is preferably used for the purpose of improving various properties such as adhesion, heat resistance and film hardness of the photosensitive resin composition. (E) inorganic filler, for example, silica (SiO _2), alumina (Al ₂ O _3), titania (TiO _2), tantalum oxide (Ta ₂ O _5), zirconia (ZrO _2), 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), titanate zirconate 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} ), silicate, barium (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, Can be preferably used. These (E) inorganic fillers may be used singly or in combination of two or more kinds.

The maximum particle diameter of the inorganic filler (E) is preferably from 0.1 to 20 μm, more preferably from 0.1 to 10 μm, even more preferably from 0.1 to 5 μm, particularly preferably from 0.1 to 1 μm. When the maximum particle diameter is 20 mu m or less, deterioration of electrical insulation can be suppressed. Here, the maximum particle diameter of the inorganic filler (E) is determined by the laser diffraction method (in accordance with JIS Z8825-1 (2001)).

Among the inorganic fillers (E), silica is preferable from the viewpoint of improving heat resistance, and solder heat resistance, crack resistance (thermal shock resistance) and adhesion strength between the underfill material and the cured film after the internal PCT test can be improved From the viewpoint, barium sulfate is preferable. The barium sulfate is preferably surface-treated with at least one member selected from alumina and organosilane compounds from the viewpoint of improving the coagulation preventing effect.

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

(E) an inorganic filler, the content of the inorganic filler (E) is preferably 15 to 80 parts by mass, more preferably 15 to 70 parts by mass, and most preferably 20 to 70 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive resin composition More preferably 20 to 50 parts by mass, and particularly preferably 20 to 45 parts by mass. When the content of the inorganic filler (E) 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.

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

<(F) Pigment>

The photosensitive resin composition of the present embodiment preferably contains a pigment as the component (F).

(F) The pigment is preferably used in accordance with a desired color when the wiring pattern is concealed. As the pigment (F), a coloring agent for coloring a desired color may be appropriately selected and used. The coloring agent is preferably a known coloring agent such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, etc. .

When the (F) pigment is contained, the content of the pigment (F) in the total amount of the solid content in the photosensitive resin composition is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass. When the content of the pigment (F) is within the above range, it is preferable from the viewpoint of hiding the wiring pattern.

<Other components>

In the photosensitive resin composition of the present embodiment, a diluent may be used as needed to adjust the viscosity. As the diluent, for example, an organic solvent, a photopolymerizable monomer and the like are preferably used. The organic solvent can be appropriately selected from solvents exemplified as organic solvents which can be used in the reaction between the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). As the photopolymerizable monomer, those exemplified above as the photopolymerizable compound (D) are preferably used.

The amount of the diluent to be used is preferably such that the total amount of solids in the photosensitive resin composition is 50 to 90% by mass, more preferably 60 to 80% by mass, and still more preferably 65 to 75% by mass. That is, when the diluent is used, the content of the diluent in the photosensitive resin composition is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, and still more preferably 25 to 35% by mass. By setting the amount of the diluting agent within the above range, the coating property of the photosensitive resin composition is improved, and a more precise pattern can be formed.

The photosensitive resin composition of the present embodiment may contain a curing agent. As the curing agent, there may be mentioned a compound which itself cures by heat, ultraviolet ray or the like, or a compound which is cured by a carboxyl group, a hydroxyl group, a heat and an ultraviolet ray of an epoxy resin containing an acid-modified vinyl group (A) as a photocurable resin component in the composition of the present embodiment Compounds are preferably used. By using a curing agent, heat resistance, adhesion, chemical resistance, etc. of the final cured film can be improved.

As the curing agent, for example, an epoxy compound, a melamine compound, a urea compound, an oxazoline compound and the like are preferably used as the thermosetting compound. Examples of the epoxy compound include a bisphenol-type epoxy resin 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 resins; Heterocyclic epoxy resins such as triglycidyl isocyanurate; Non-ionene type epoxy resins, and the like. As the melamine compound, for example, triaminotriazine, hexamethoxy melamine, hexabutoxylated melamine and the like are preferably used. As the urea compound, dimethylol element and the like are preferably used.

From the viewpoint of further improving the heat resistance of the cured film, the curing agent preferably contains at least one selected from an epoxy compound (epoxy resin) and a block type isocyanate, more preferably an epoxy compound and a block type isocyanate in combination Do.

As the block type isocyanate, an addition reaction product of a polyisocyanate compound and an isocyanate block agent is used. Examples of the polyisocyanate compound include tolylene diisocyanate, xylene diisocyanate, phenylene diisocyanate, naphthylene diisocyanate, bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethyl Polyisocyanate compounds such as hexamethylene diisocyanate and isophorone diisocyanate, and adducts, buretes and isocyanurate compounds thereof, and the like.

Examples of the isocyanate blocking agent include phenolic block agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam-based blocking agents such as ε-caprolactam, δ-palrylactam, γ-butylolactam and β-propiolactam; Active methylene blockers such as ethyl acetoacetate and acetylacetone; But are not limited to 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, Alcohol-based blocking agents such as butyl glycolate, diacetone alcohol, methyl lactate, and ethyl lactate; Oxime-based blocking agents such as formaldehyde scouring, acetal decyl, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexane oxime; Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl thiophenol and ethyl thiophenol; Acid amide type block agents such as acetic acid amide, benzamide and the like; Imide block 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; And imine block agents such as methylene imine and propylene imine.

The curing agent may be used alone or in combination of two or more. The content of the curing agent is preferably 2 to 50 parts by mass, more preferably 2 to 40 parts by mass, more preferably 3 to 30 parts by mass, still more preferably 5 to 30 parts by mass, per 100 parts by mass of the total solid content in the photosensitive resin composition. 20 parts by mass is particularly preferable. When the content of the curing agent is within the above range, the heat resistance of the cured film to be formed can be further improved while maintaining good developing properties.

In the photosensitive resin composition of the present embodiment, an epoxy resin curing agent may be used together with the aim of further improving the properties of the final cured film such as heat resistance, adhesion, and chemical resistance.

Specific examples of such epoxy resin curing agents include, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2- Imidazoles such as phenyl-4-methyl-5-hydroxymethylimidazole; Guanamine 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-triazine, 2,4-diamino-S-triazine and 2,4-diamino-6-xylyl-S-triazine; (N-methyl) melamine, 2,4,6-tris (dimethylaminophenol), tetramethylguanidine, N, N-dimethyloctylamine, tertiary amines such as m-aminophenol; Polyphenols such as polyvinyl phenol, polyvinyl phenol bromide, phenol novolac, and alkylphenol novolak; Organic phosphines such as tributylphosphine, triphenylphosphine, and tris-2-cyanoethylphosphine; Phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, and hexadecyl tributylphosphonium chloride; Quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; The above polybasic acid anhydrides; Diphenyl iodonium tetrafluoroborate; Triphenylsulfonium hexafluoroantimonate; 2,4,6-triphenylthiopyrylium hexafluorophosphate, and the like.

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

The photosensitive resin composition of the present embodiment may contain, if necessary, a polymerization inhibitor such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like; Thickeners such as benton, montmorillonite and the like; Defoaming agents such as silicone, fluorine and vinyl resins; Silane coupling agents and the like can be used.

Furthermore, a flame retardant such as a brominated epoxy compound, an acid-modified brominated epoxy compound, an antimony compound, a phosphate compound as a phosphorus compound, an aromatic condensed phosphate ester, and a halogenated condensed phosphate ester can be used.

(Elastomer)

The photosensitive resin composition of the present embodiment may contain an elastomer. The elastomer is preferably used particularly when the photosensitive resin composition of the present embodiment is used for manufacturing a semiconductor package substrate. When the elastomer is added to the photosensitive resin composition of the present embodiment, the curing reaction proceeds by ultraviolet rays, heat, and the like. The curing reaction is caused by (A) the distortion (internal stress) inside the resin due to the curing shrinkage of the acid- It is possible to suppress deterioration of flexibility and adhesiveness.

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

Further, in addition to the above elastomer, rubber-modified epoxy resin can be used. The rubber-modified epoxy resin may be, for example, a resin obtained by partially or wholly containing the bisphenol F type epoxy resin, the bisphenol A type epoxy resin, the triphenolmethane type epoxy resin, the phenol novolak type epoxy resin or the cresol novolak type epoxy resin An epoxy group-modified butadiene-acrylonitrile rubber, a terminal amino-modified silicone rubber, or the like. Among these elastomers, from the viewpoint of shear adhesion, a polyester resin (ESPEL 1612, 1620 (trade name), manufactured by Hitachi Chemical Co., Ltd.), which is a polyester-based elastomer having a hydroxyl group and a hydroxyl group-modified butadiene- acrylonitrile copolymer, ) Can be preferably used.

The blending amount of the elastomer is preferably 2 to 30 parts by mass, more preferably 4 to 20 parts by mass, further preferably 10 to 20 parts by mass with respect to 100 parts by mass of (A) the acid-modified vinyl group-containing epoxy resin . If the amount is more than 2 parts by mass, the elasticity of the cured film in the high temperature region tends to be lowered. If the amount is less than 30 parts by mass, the unexposed portion tends to be eluted from the developer.

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

The photosensitive resin composition of the present embodiment is preferably in a liquid form. By employing a liquid shape, the permanent mask resist can be easily formed by various coating methods to be described later.

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

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

The photosensitive element of this embodiment includes a support and a photosensitive layer formed by using the photosensitive resin composition of the present embodiment on the support. As the support, for example, a polyester resin film such as polyethylene terephthalate and a polyolefin resin film such as polyethylene and polypropylene can be preferably used. In view of transparency, polyethylene terephthalate It is preferable to use a phthalate film. The thickness of the support is preferably 1 to 100 占 퐉, more preferably 1 to 50 占 퐉, and more preferably 1 to 30 占 퐉, in view of obtaining mechanical strength and good resolution.

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

The printed wiring board having the permanent mask resistors and the permanent mask resistors of the present embodiment is formed, for example, in the following manner. First of all, the photosensitive layer of the present embodiment is formed by a method such as a screen printing method, a spray method, a roll coating method, a curtain coating method, an electrostatic coating method, or the like by a method such as a screen printing method, The resin composition is applied with a film thickness (after drying: 10 to 200 탆) according to the application to form a coating film, and the coating film is dried at 60 to 110 캜. Instead of the coating film, the photosensitive layer of the photosensitive element may be transferred (laminated) onto a substrate on which the resist is to be formed. In this case, a dried film on the support is pasted on the substrate using a normal pressure laminator or a vacuum laminator, if necessary.

After the photosensitive layer (coating film) is formed on the substrate, the active film such as ultraviolet rays is irradiated with an energy amount of preferably 10 to 1,000 mJ / cm ² through direct contact with the negative film or through a transparent film, When the film is pasted, the resin film is peeled off to dissolve (develop) the unexposed portion with a diluted alkaline aqueous solution.

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

Since the permanent mask resistors thus obtained are less prone to undercuts that cut off the bottoms and are less liable to cause an upper portion of the resist, the line widths of the middle portion (central portion) and the deepest portion (bottom portion) The pattern outline has a good linearity, a resist shape is excellent, and a pattern having excellent resolution is obtained. This permanent mask resistor has a pattern having excellent size stability of formation of the size of the hole diameter and the interval pitch between the holes due to miniaturization and high performance of recent electronic apparatuses.

Example

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples at all.

(Assessment Methods)

(1) Evaluation of surface hardenability

The photosensitive resin compositions of each of the examples and the comparative examples were applied to a PET film having a thickness of 35 mu m by an applicator so that the film thickness after drying was 35 mu m to form a coating film. Then, it was dried at 80 캜 for 20 minutes using a hot air circulating dryer. The infrared absorption spectrum (ATR (Attenuated Total Reflection) method) of the obtained coating film surface was measured under the following conditions.

 Measurement apparatus: manufactured by Thermo Scientific Co., Ltd., trade name: Nicolet iS50R

 · Number of accumulation: 128 times

Next, exposure was performed at an exposure dose 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 change rate of the carbon-carbon double bond at 1470 cm ^-1 before and after exposure was obtained from the following equation, And the surface hardenability (%).

(%) Of double bond = 100 - (amount of carbon-carbon double bond after exposure / amount of carbon-carbon double bond before exposure × 100)

(2) Evaluation of photosensitivity

The photosensitive resin compositions of each of the examples and the comparative examples were applied to a PET film having a thickness of 35 mu m by an applicator so that the film thickness after drying was 35 mu m to form a coating film. Then, it was dried at 80 캜 for 20 minutes using a hot air circulating dryer. Next, a step tablet 41 (made by Hitachi Chemical Co., Ltd.) was adhered to the coated film, and ultraviolet rays of a predetermined cumulative exposure amount ("LI9200 (model number)", made by Dainippon Screen Co., Ltd.) 50 mJ / cm &lt; ² &gt;. Subsequently, after developing for 60 seconds with a 1% by mass aqueous solution of sodium carbonate, the number of remaining coating films without development was confirmed. Was evaluated by the following criteria.

A (good): more than 10 stages

B (good): 6 to 9 stages

C (poor): 5 or less stages

(3) Evaluation of bottom hardenability

The photosensitive resin compositions of each of the examples and the comparative examples were applied to a PET film having a thickness of 35 mu m by an applicator so that the film thickness after drying was 35 mu m to form a coating film. Then, it was dried at 80 캜 for 20 minutes using a hot air circulating dryer. The infrared absorption spectrum (ATR method) of the obtained coating film surface was measured under the following conditions.

 Measurement apparatus: manufactured by Thermo Scientific Co., Ltd., trade name: Nicolet iS50R

 · Number of accumulation: 128 times

Next, exposure was performed at an exposure dose of 600 mJ / cm ² using an ultraviolet exposure apparatus (trade name: HTE-5102S, manufactured by Hi-tech Co., Ltd.). Thereafter, the coated film exposed from the PET film was peeled off, and the infrared absorption spectrum (ATR method) of the coated film on the side of the PET film after exposure was measured under the same conditions as described above. The rate of change of the carbon-carbon double bond at 1470 cm ^-1 before and after exposure was determined from the following equation, and the average value of the number of times of integration multiplied by 3 was defined as the film bottom curability (%).

(%) Of double bond = 100 - (amount of carbon-carbon double bond after exposure / amount of carbon-carbon double bond before exposure × 100)

(4) Evaluation of resist shape

The photosensitive resin composition of each of the examples and the comparative examples was coated on a copper laminated substrate (MCL-E-67, manufactured by Hitachi Kasei Corporation) having a size of 50 cm x 50 cm and a thickness of 0.6 mm, Mu m to form a coating film, followed by drying at 80 DEG C for 20 minutes using a hot air circulating dryer.

Next, a negative mask shown in Fig. 2 having a hole diameter of 100 mu m and a hole pitch of 100 mu m, and a negative mask having a hole diameter of 80 mu m and a hole pitch pitch of 80 mu m, And exposed to a predetermined exposure amount shown in Tables 1 to 6 using an ultraviolet exposure apparatus (trade name: HTE-5102S, manufactured by Hi-tech Co., Ltd.).

Thereafter, the resultant was spray-developed with a 1% by mass aqueous sodium carbonate solution at a pressure of 0.18 MPa (1.8 kgf / cm ² ) for 60 seconds to dissolve and develop the unexposed portion. Next, the resist film was exposed to light at an exposure dose of 1000 mJ / cm ² using an ultraviolet exposure apparatus (trade name: Conveyor type UV exposure apparatus, manufactured by GS Yuasa Lighting), and then heated at 150 캜 for 1 hour to prepare test pieces.

The test piece on which the pattern was formed was molded with a thermosetting resin using an epoxy resin (Epikote 828 (trade name), manufactured by Mitsubishi Kagaku Co., Ltd.) and triethylenetetramine as a curing agent and sufficiently cured, , Brand name: Refine Polisher), the cross section of the pattern was cut out, and the shape of the resist was observed with a metallurgical microscope and evaluated according to the following criteria. Fig. 1 schematically shows the cross-sectional shape of the resist.

A (good): The shape of the resist indicates a rectangle or a trapezoid, and the linearity of the outline of the pattern was good.

B (poor): The shape of the resist was found to be undercut, lower width pulling, or thickening, or the linearity of the outline of the pattern was not good.

(5) Evaluation of the accuracy of the via diameter

The photosensitive resin composition of each of the examples and the comparative examples was coated on a copper laminated substrate (MCL-E-67, manufactured by Hitachi Kasei Corporation) having a size of 50 cm x 50 cm and a thickness of 0.6 mm, Mu m to form a coating film, followed by drying at 80 DEG C for 20 minutes using a hot air circulating dryer.

Next, a negative mask having a pattern shown in Fig. 2 was brought into close contact with the coating film, and exposed using an ultraviolet exposure apparatus (trade name: HTE-5102S, manufactured by Hi-tech Co., Ltd.) at an exposure dose of 600 mJ / cm ² . Thereafter, the resultant was spray-developed with a 1% by mass aqueous solution of sodium carbonate at a pressure of 0.18 MPa (1.8 kgf / cm ² ) for 60 seconds to dissolve and develop the unexposed portion to prepare a test piece. The pattern of the obtained test piece was evaluated according to the following criteria.

A (good): 80% pattern of 100 탆 and 80 탆 was reproduced.

B (defective): patterns of 100 탆 and 80 탆 were reproduced in less than 80%.

Here, a pattern of 100 탆 and 80 탆 was observed by magnifying it 700 times using a microscope, and in the case of a pattern of 100 탆, the pattern bottom was formed to have a size of 80 탆 or more (80% or more with respect to the pattern diameter) The pattern was reproduced. In the case of a pattern of 80 mu m, the case where the bottom of the pattern was formed to have a size of 64 mu m or more was regarded as a pattern reproduced. In the judgment of "A" and "B", the case where the total number of formed patterns was 80% or more with respect to the total number of patterns of 100 μm and 80 μm was evaluated as "A".

(6) Evaluation of Solder Heat Resistance (i)

A water-soluble flux (trade name: K-183, manufactured by Alpha Metals Co., Ltd.) was applied to a test piece prepared under the same conditions as the test piece used in the evaluation of the resist shape described in (4) above and immersed in a solder bath at 265 캜 for 10 seconds Then, it was taken out from the solder layer. After immersing and extruding into one cycle and repeating 6 cycles, the outer appearance of the coating film was visually observed and evaluated according to the following criteria.

A (good): Within 30 cm x 30 cm of the coating film, no change in appearance was observed.

B (Good): Within one coat of 30 cm x 30 cm, one to five coatings were lifted or parts were identified.

C (poor): Within the range of 30 cm x 30 cm of the film, six or more films were lifted or parts were confirmed.

(7) Evaluation of Solder Heat Resistance (ii)

(4) A non-glued flux (trade name: RMA SR-209, manufactured by Senzoku Kogyo Kogyo Co., Ltd.) was applied to a test piece prepared under the same condition as the test piece used in the evaluation of the resist shape, And then removed from the solder layer. The immersing and extruding were performed in one cycle, and after repeating 10 cycles, the outer appearance of the coated film of the test piece taken out was visually observed and evaluated according to the following criteria.

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

B: The coating film of the resist was slightly peeled off, but it was practically insignificant.

C: Parts or peeling of the coating film of the resist were confirmed.

(8) Evaluation of crack resistance

After repeating 1000 cycles of the step of (4) holding the specimen prepared under the same condition as the test specimen used in the evaluation of the resist shape for 30 minutes at -65 占 폚 and holding the specimen at 150 占 폚 for 30 minutes , And the outer appearance of the coating film of the test piece was visually observed and evaluated according to the following criteria.

A (good): Within 30 cm x 30 cm of the coating film, no change in appearance was observed.

B (Good): One to five coatings were lifted or parts were found within a range of 30 cm x 30 cm.

C (poor): Within the range of 30 cm x 30 cm of the film, six or more films were lifted or parts were confirmed.

(9) Evaluation of adhesion

Each of the photosensitive resin compositions of the examples and the comparative examples was laminated on a copper laminated substrate (MCL-E (trade name) manufactured by Hitachi Kasei Co., Ltd.) having a thickness of 0.6 mm and having a copper surface buffed (5 占 퐉 roughening in the depth direction) (Trade name: MCL-E-67, manufactured by Hitachi Chemical Co., Ltd.) having a thickness of 0.6 mm and having a thickness of 0.5 mm and a thickness of 0.5 mm and a thickness of 0.5 mm, By a screen printing method so as to have a film thickness after drying of 35 mu m to form a coating film and then dried using a hot air circulating dryer at 80 DEG C for 20 minutes.

Next, a negative mask having a pattern shown in Fig. 2 was brought into close contact with the coating film, and exposed using an ultraviolet exposure apparatus (trade name: HTE-5102S, manufactured by Hi-tech Co., Ltd.) at an exposure dose of 600 mJ / cm ² . Thereafter, the resultant was spray-developed with a 1% by mass aqueous sodium carbonate solution at a pressure of 0.18 MPa (1.8 kgf / cm ² ) for 60 seconds to dissolve and develop the unexposed portion. Next, exposure was performed at an exposure amount of 1000 mJ / cm ² using an ultraviolet ray exposure apparatus (trade name: conveyor type UV irradiation apparatus, manufactured by GS Yuasa Lighting Co., Ltd.) and heated at 150 캜 for 1 hour to prepare a test piece.

100 sheets of 1 mm checkerboard scales were prepared in accordance with JIS K5600, and a cellophane tape (manufactured by Nichiban Co., Ltd., trade name: Cellotape (registered trademark)) was stuck thereon and then a cellophane tape A peeling test was performed forcibly peeling off. The peeled state of the checkerboard scale was observed and evaluated according to the following criteria.

A (good): 90/100 or more did not peel off.

B (good): not less than 50/100 and less than 90/100.

C (poor): 0/100 or more, less than 50/100, no peeling.

(10) Solvent resistance

The specimens prepared under the same conditions as in the above (4) evaluation of the resist shape were immersed in isopropyl alcohol for 30 minutes at room temperature to confirm whether there was any abnormality in appearance. Next, a peel test was performed in which a cellophane tape (manufactured by Nichiban Co., Ltd., trade name: Cellotape (registered trademark)) was stuck on the coating film of the test piece after immersion and then the cellophane tape was forcibly peeled in the direction of 90 degrees. The presence or absence of peeling was checked on the basis of the following criteria.

A (good): No abnormality was found on the appearance of the coating film, and no peeling was observed.

B (defective): An abnormality was confirmed on the outer surface of the coating film, or peeling was observed.

(11) Acid resistance

A test piece prepared under the same conditions as in (4) evaluation of the resist shape was immersed in a 10 mass% aqueous hydrochloric acid solution at room temperature for 30 minutes to confirm whether or not there was any abnormality in appearance. Next, a peel test was performed in which a cellophane tape (manufactured by Nichiban Co., Ltd., trade name: Cellotape (registered trademark)) was stuck on the coating film of the test piece after immersion and then the cellophane tape was forcibly peeled in the direction of 90 degrees. The presence or absence of peeling was checked on the basis of the following criteria.

A (good): No abnormality was observed on the outer appearance of the coating film, and no peeling was observed.

B (poor): An abnormality was found in the outer appearance of the coating film or peeling was observed.

(12) Alkalinity

A test piece prepared under the same conditions as the test piece used in the evaluation of the resist shape (4) was immersed in a 5 mass% aqueous sodium hydroxide solution at room temperature for 30 minutes to confirm whether or not the appearance was abnormal. Next, a peel test was performed in which a cellophane tape (manufactured by Nichiban Co., Ltd., trade name: Cellotape (registered trademark)) was stuck on the coating film of the test piece after immersion and then the cellophane tape was forcibly peeled in the direction of 90 degrees. The presence or absence of peeling was checked on the basis of the following criteria.

A (good): No abnormality was observed on the outer appearance of the coating film, and no peeling was observed.

B (poor): An abnormality was found in the outer appearance of the coating film or peeling was observed.

(13) Evaluation of flux corrosion resistance

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 replaced with a lattice pattern of 1 mm square shown in Fig. Then, a highly active water-soluble flux (product name: K-183, manufactured by Alpha Metals Co., Ltd.) 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 DEG C for 1 minute, then immersed in a solder bath at 280 DEG C for 20 seconds, and then taken out of the solder bath. After cooling for 1 minute at room temperature, the plate was washed with water, and the appearance of the plate was observed while wiping off the water droplets. A cellophane tape (manufactured by Nichiban Co., Ltd., trade name: Cellotape (registered trademark)) having a width of 24 mm was attached to the minimum circuit width of the test piece, and the cellophane tape was forcibly peeled in the direction of 90 degrees , The appearance of the test piece after peeling was visually observed and evaluated according to the following criteria.

5: Peeling of the portion where the resist was present was not observed at all after the peeling test.

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

3: Whitening was slightly observed in the portion where the resist existed before the peeling test, and peeling of 20% or less of the portion where the resist was present after the peeling test was confirmed, but practically no problem was found.

2: Bleaching was observed at the portion where the resist existed before the peeling test, and peeling at 20% or more of the portion where the resist was present after the peeling test was confirmed.

1: Significant whitening was observed in the portion where the resist was present before the peeling test, and significant peeling was confirmed after peeling test.

(14) Domestic Electrolytic (Electroless) Plating

The test pieces prepared under the same conditions as those of the test specimens used in the evaluation of the resist shape (4) were coated with a nickel plating bath of 5 μm thickness and a gold plating thickness of 0.05 μm using a commercially available electroless nickel plating bath and electroless gold plating bath The plating was carried out. After the plating, the presence or absence of impregnation of the plating was confirmed. Next, a peel test was performed in which a cellophane tape (manufactured by Nichiban Co., Ltd., trade name: Cellotape (registered trademark)) was stuck on the coating film of the test piece after immersion and then the cellophane tape was forcibly peeled in the direction of 90 degrees. The presence or absence of peeling was checked on the basis of the following criteria.

A: I could not see the smim, and the exfoliation.

B: After the plating, the smim was visible, but the peeling could not be seen.

C: Peeling was observed after plating.

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

Cresol novolak type epoxy resin (sinnit Tetsu Sumi kinga Kagaku Co., Ltd., trade name: YDCN704, in the formula (I), Y ¹ = a glycidyl group, R ¹¹ = methyl group) 220 parts by weight, acrylic acid 72 parts by weight, 1.0 part by mass of hydroquinone and 180 parts by mass of carbitol acetate were mixed and heated to 90 DEG C and stirred to dissolve the reaction mixture. Subsequently, the mixture was cooled to 60 占 폚, and 1 part by mass of benzyltrimethyl ammonium chloride was mixed and heated to 100 占 폚 and reacted until the solid dispersion value became 1 mg KOH / g. Subsequently, 152 parts by weight of tetrahydrophthalic anhydride and 100 parts by weight of carbitol acetate were mixed and heated to 80 DEG C and stirred for 6 hours. After cooling to room temperature, the solution was diluted with carbitol acetate to a solid content concentration of 60% by mass to obtain a solution containing an acid-modified vinyl group-containing epoxy resin (I).

In addition, the solid dispersion amount in the examples was measured according to the neutralization titration method. Specifically, 30 g of acetone was added to 1 g of the solution containing an acid-modified vinyl group-containing epoxy resin, and the solution was uniformly dissolved. Then, phenolphthalein as an indicator was added in an appropriate amount to the solution containing the acid-modified vinyl group-containing epoxy resin , And titration was carried out using 0.1 N aqueous potassium hydroxide solution.

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

, 475 parts by mass of a bisphenol F type epoxy resin (trade name: YDF2001, trade name: Y ² = glycidyl group, R ¹² = H, manufactured by Shinnitetsu Sumiki Kagaku Co., Ltd.), 72 parts by mass of acrylic acid, 0.5 part by mass of quinone and 120 parts by mass of carbitol acetate were mixed and heated to 90 DEG C and stirred to dissolve the reaction mixture. Subsequently, the mixture was cooled to 60 DEG C and 2 parts by mass of benzyltrimethylammonium chloride was mixed, heated to 100 DEG C, and reacted until the solid acid value became 1 mgKOH / g. Subsequently, 230 parts by weight of tetrahydrophthalic anhydride and 85 parts by weight of carbitol acetate were mixed and heated to 80 DEG C and stirred for 6 hours. After cooling to room temperature, the solution was diluted with carbitol acetate to a solid content concentration of 60% by mass to obtain a solution containing an acid-modified vinyl group-containing epoxy resin (II) -a.

(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 占 폚 was placed in a flask equipped with a thermometer, dropping funnel, cooling tube and stirrer and stirring was started at 80 占 폚. 3 parts by mass of methanephosphonic acid was added thereto, and 16.3 parts by mass of paraformaldehyde aqueous solution (concentration: 92% by mass) was added dropwise over 1 hour so that the temperature of the liquid remained within a range of 80 to 90 占 폚. After completion of the dropwise addition, 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 reaction mixture was transferred to a separating funnel and washed with water. After washing with water until the washing water showed neutrality, a 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) 164 parts by mass of a bisphenol-based novolac resin. The obtained bisphenol-based novolac resin had a softening point of 74 占 폚 and a hydroxyl group equivalent of 154 g / eq.

Then, 154 parts by mass of the bisphenol-based novolak resin obtained above, 463 parts by mass of epichlorohydrin, 139 parts by mass of n-butanol , And 2 parts by mass of tetraethylbenzylammonium chloride were mixed and dissolved. Subsequently, the mixture was heated to 65 DEG C to reduce the pressure to an azeotropic pressure, and then 90 parts by mass of an aqueous sodium hydroxide solution (concentration: 49% by mass) was added dropwise over 5 hours at a constant rate and stirred for 30 minutes . In the meantime, the effluent distilled out by azeotropy was separated by a Deanstock trap, the water layer was removed, and the oil layer was returned to the flask (reaction system). Thereafter, unreacted epichlorohydrin was removed by vacuum distillation (temperature: 22 ° C, pressure: 1.87 kPa) to obtain a crude epoxy resin, 590 parts by mass of methyl isobutyl ketone, 177 parts by mass of n-butanol And then dissolved. To this solution, 10 parts by mass of an aqueous solution of sodium hydroxide (concentration: 10% by mass) was added. After reacting at 80 DEG C for 2 hours, washing with water was repeated three times with 150 parts by mass of water until the pH of the washing liquid became neutral. It was confirmed that the pH of the washing liquid used for the third washing with water was neutral. Subsequently, the inside of the flask (in the reaction system) was dehydrated by azeotropic distillation, subjected to microfiltration, and then the solvent was distilled off under reduced pressure (pressure: 1.87 kPa) to obtain a viscous liquid of the bisphenol- (Epoxy resin (a) having a constituent unit of Y ⁴ = glycidyl group and R ¹³ = H in the general formula (IV)) was obtained. The epoxy equivalent of the epoxy resin was 233 g / eq.

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

The softening point of the resin was measured in accordance with the ring method defined by JIS-K7234: 1986 (temperature raising rate: 5 DEG 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 占 폚 was placed in a flask equipped with a thermometer, dropping funnel, cooling tube and stirrer and stirring was started at 80 占 폚. 3 parts by mass of methanephosphonic acid was added thereto, and 16.3 parts by mass of paraformaldehyde (92% by mass) was added dropwise over 1 hour so that the temperature of the liquid remained within a range of 80 to 90 占 폚. After completion of the dropwise addition, 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 reaction mixture was transferred to a separating funnel and washed with water. After washing with water until the washing water showed neutrality, a 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) And 164 parts by mass of a bisphenol-based novolak resin which is a brown solid. The obtained bisphenol-based novolak resin had a softening point of 87 占 폚 and a hydroxyl group equivalent of 174 g / eq.

Then, 154 parts by mass of the bisphenol-based novolak resin obtained above, 463 parts by mass of epichlorohydrin, 139 parts by mass of n-butanol And 2 parts by mass of tetraethylbenzylammonium chloride were mixed and dissolved. Subsequently, this was heated to 65 占 폚, reduced to an azeotropic pressure, and then 90 parts by mass of an aqueous solution of sodium hydroxide (concentration: 49% by mass) was added dropwise over 5 hours at a constant rate and stirred for 30 minutes. In the meantime, the effluent discharged by the azeotropic distillation was separated by Dean Stark trap, the water layer was removed, and the oil layer was returned to the flask (reaction system). Thereafter, unreacted epichlorohydrin was distilled off by vacuum distillation (temperature: 22 ° C, pressure: 1.87 kPa), and 590 parts by mass of methyl isobutyl ketone and 177 parts by mass of n-butanol were added to the obtained crude epoxy resin . To this solution, 10 parts by mass of an aqueous solution of sodium hydroxide (concentration: 10% by mass) was added. After reacting at 80 DEG C for 2 hours, washing with water was repeated three times with 150 parts by mass of water until the pH of the washing liquid became neutral. It was confirmed that the pH of the washing liquid used in the third washing with water was neutral. Subsequently, the inside of the flask (in the reaction system) was dehydrated by azeotropic distillation, subjected to microfiltration, and then the solvent was distilled off under reduced pressure (pressure: 1.87 kPa) to obtain a viscous liquid of the bisphenol- (Epoxy resin (a) having Y ⁴ = glycidyl group and R ¹³ = methyl group constituent unit in the general formula (IV)) was obtained. The epoxy equivalent of the epoxy resin was 233 g / eq.

To 450 parts by mass of the epoxy resin (a) obtained above, 124 parts by mass of acrylic acid, 1.5 parts by mass of hydroquinone and 250 parts by mass of carbitol acetate were mixed and heated to 90 占 폚 and stirred to dissolve the reaction mixture. Subsequently, the mixture was cooled to 60 占 폚, and 2 parts by mass of benzyltrimethylammonium chloride was mixed and heated to 100 占 폚 until the acid value became 1 mg KOH / g. Subsequently, 230 parts by weight of tetrahydrophthalic anhydride and 180 parts by weight of carbitol acetate were mixed with the above reaction product, heated to 80 DEG C, and reacted for 6 hours. Subsequently, the mixture was cooled to room temperature and diluted with carbitol acetate to a solid content concentration of 60% by mass to obtain a solution containing an acid-modified vinyl group-containing epoxy resin (IV) -b.

(Synthesis Example 5: Synthesis of acid-modified vinyl group-containing epoxy resin (IV) -c)

A flask equipped with a thermometer, a dropping funnel, a cooling tube and a stirrer was charged with a bisphenol F novolac epoxy resin (trade name: EXA-7376, manufactured by DIC Corporation, Y ⁴ and Y ⁵ = a glycidyl group, R ¹³ = hydrogen atom) to 350 parts by mass of acrylic acid 70 parts by mass of methyl hydroquinone, 0.5 parts by mass of carbitol to acetate mixture of 120 mass parts of the reaction by stirring and heated to 90 ℃, completely dissolving the mixture Respectively. Next, the resulting solution was cooled to 60 占 폚, 2 parts by mass of triphenylphosphine was added, and the mixture was heated to 100 占 폚 and reacted until the acid value of the solution became 1 mgKOH / g. To the solution after the reaction, 98 parts by weight of tetrahydrophthalic anhydride (THPAC) and 85 parts by weight of carbitol acetate were added, and the mixture was heated to 80 DEG C and reacted for 6 hours. Thereafter, the solution was cooled to room temperature to obtain a solution containing an acid-modified vinyl group-containing epoxy resin (IV) -c having a solid content of 73 mass%.

(Synthesis Example 6: Synthesis of acid-modified vinyl group-containing epoxy resin (II) -b)

(Manufactured by Mitsubishi Chemical Corporation, trade name: 4004, epoxy equivalent: 526 g / eq, and Y in the general formula (II)) was added to a flask equipped with a stirrer, a thermometer, a dropping funnel, ² = a hydrogen atom, R ¹² = a hydrogen atom), 1052 parts by mass of acrylic acid (b) by mixing 144 parts by mass of methyl hydroquinone, 1 part by mass, carbitol acetate 850 parts by mass and solvent naphtha 100 parts by weight, the mixture was heated and stirred at 70 ℃ To dissolve the mixture. Next, the solution was cooled to 50 占 폚, 2 parts by mass of triphenylphosphine and 75 parts by mass of solvent naphtha were mixed and heated to 100 占 폚 until the solid acid value became 1 mgKOH / g or less. Next, the obtained solution was cooled to 50 캜, and 745 parts by mass of tetrahydrophthalic anhydride (THPAC), 75 parts by mass of carbitol acetate and 75 parts by mass of solvent naphtha were mixed and heated to 80 캜 for reaction for 6 hours. Thereafter, the solution was cooled to room temperature to obtain a solution containing an acid-modified vinyl group-containing epoxy resin (II) -b having a solid content of 80 mgKOH / g and a solid content of 62 mass%.

Examples 1 to 32 and Comparative Examples 1 to 32

The composition was compounded according to the composition shown in Tables 1 to 6 and kneaded by three roll mills to prepare a photosensitive resin composition. Carbitol acetate was added so that the solid concentration became 70% by mass to obtain a photosensitive resin composition. The obtained photosensitive resin composition was evaluated based on the evaluation method described above. The evaluation results are shown in Tables 1 to 6. The unit of the blending amount of each component in the table is parts by mass, and the blending amount of the component (A) in the table means the blending amount as the solution containing the epoxy resin obtained in each of the synthesis examples.

Examples 33 and 34 and Comparative Examples 33 and 34

A photosensitive resin composition was prepared in the same manner as in Example 1, according to the formulation composition shown in Table 6. Each of the obtained photosensitive resin compositions was diluted with methyl ethyl ketone, applied onto a PET film, and then dried at 90 캜 for 10 minutes to form a photosensitive layer composed of a photosensitive resin composition having a thickness of 25 탆. Further, a polyethylene film (protective layer) was laminated thereon to prepare a photosensitive element.

The protective layer was peeled off from the photosensitive element obtained above, and the photosensitive element was laminated on the copper foil substrate of the beta. Then, a negative mask shown in Fig. 2 having a hole diameter of 100 mu m and a spacing pitch of 100 mu m, or a pattern having a hole diameter of 80 mu m and a spacing pitch of 80 mu m, And exposed in a predetermined exposure amount shown in Table 6 using an ultraviolet exposure apparatus (trade name: HTE-5102S, manufactured by Hi-tech Co., Ltd.). Thereafter, the resultant was spray-developed with a 1% by mass aqueous sodium carbonate solution at a pressure of 0.18 MPa (1.8 kgf / cm ² ) for 60 seconds to dissolve and develop the unexposed portion. Next, exposure was performed at an exposure dose of 1000 mJ / cm ² using an ultraviolet exposure apparatus (trade name: Conveyor type UV irradiation apparatus, manufactured by GS Yuasa Lighting Co., Ltd.) and then heated at 150 캜 for 1 hour to prepare test pieces. Using the obtained test piece, the same evaluation as in Example 31 was carried out. The evaluation results are shown in Table 6.

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

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

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

Irgacure 907: 2-methyl- [4- (methylthio) phenyl] morpholino-1-propanone (trade name,

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

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

BaSO ₄ : manufactured by Sakai Kagaku Kogyo Co., Ltd.

SiO ₂ : Tatsumori Co., Ltd.

Epicoat 828: bisphenol A type epoxy resin (trade name, manufactured by Mitsubishi Kagaku Co., Ltd.)

It can be seen from the results shown in Table 1 that the pattern of the permanent mask resist (solder resist) of the present invention of Examples 1 to 6 is a pattern in which the hole diameter is 100 mu m and the interval pitch between the holes is 100 mu m, Or even a high-precision pattern in which the hole diameter is 80 占 퐉 and the interval pitch between the holes is 80 占 퐉, a via shape excellent in resist shape can be obtained while maintaining excellent surface curability and bottom curability, And it was confirmed that the Bayer diameter was excellent. Further, it was confirmed that not only excellent resist shapes but also other properties such as solder heat resistance were confirmed. This is considered to be an effect that can be obtained by the combination of the photosensitive resin composition of the present invention, particularly (B) the acylphosphine oxide-based photopolymerization initiator and the (C1) alkylaminobenzene derivative as the hydrogen donor.

On the contrary, in Comparative Examples 1 to 4, the problems of the bottom curing property and the resist shape were not solved, and thickening around the pattern of the permanent mask resist (solder resist) also occurred, which was insufficient.

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

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

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

Irgacure 907: 2-methyl- [4- (methylthio) phenyl] morpholino-1-propanone (trade name,

Irgacure 369: 2-Benzoyl-2-dimethylamino-1- (4-morpholino-phenyl) butanone- 1 (trade name, BASF Japan)

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

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

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

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

BaSO ₄ : manufactured by Sakai Kagaku Kogyo Co., Ltd.

SiO ₂ : Tatsumori Co., Ltd.

Epicoat 828: bisphenol A type epoxy resin (trade name, manufactured by Mitsubishi Kagaku Co., Ltd.)

From the results shown in Table 2, the photosensitive resin composition of the present invention of Examples 7 to 12 was able to obtain a via shape having excellent photosensitivity, low curability, and excellent resist shape even with digital exposure. The pattern of the permanent mask resist (solder resist film) is a pattern in which the size of the hole diameter is 100 mu m and the pitch of the interval between the holes is 100 mu m or the pattern in which the size of the hole diameter is 80 mu m and the pitch pitch of the holes is 80 mu m It was confirmed that even though a high-precision pattern was formed, the thickening around the periphery could be reduced and the bore diameter was excellent. Further, it was confirmed that not only excellent resist shapes but also other properties such as solder heat resistance and the like were confirmed. This is considered to be an effect that can be obtained by the combination of 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 problems of the bottom curing property and the resist shape were not solved, and the pattern of the permanent mask resist (solder resist) (the pattern having the hole diameter size of 100 mu m, Or a pattern in which the size of the hole diameter is 80 mu m and the distance between the holes is 80 mu m), which is insufficient.

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

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

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

Irgacure 907: 2-methyl- [4- (methylthio) phenyl] morpholino-1-propanone (trade name,

Anthracene-based sensitizers 1: 9,10-dibutoxyanthracene

Anthracene-based sensitization Second: 9,10-diethoxyanthracene

Anthracene-based sensitizers (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.)

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

BaSO ₄ : manufactured by Sakai Kagaku Kogyo Co., Ltd.

SiO ₂ : Tatsumori Co., Ltd.

Epicoat 828: bisphenol A type epoxy resin (trade name, manufactured by Mitsubishi Kagaku Co., Ltd.)

From the results shown in Table 3, it can be seen that the photosensitive resin composition of the present invention of Examples 13 to 18 has excellent photo-curability, and the pattern of the permanent mask resist (solder resist) has a hole diameter of 100 mu m, Even if a pattern with a pitch of 100 占 퐉 or a high-precision pattern with a hole diameter of 80 占 퐉 and a spacing pitch of 80 占 퐉 has excellent bottom curability and undercut, bottom width pulling, or thickening is confirmed, or It was confirmed that the linearity of the pattern outline is not deteriorated, an excellent resist shape can be obtained, and the degree of the via diameter is excellent. Further, it was confirmed that not only it has excellent solder heat resistance and flux corrosion resistance but also excellent in various performances such as adhesion, solvent resistance, chemical resistance (acid resistance, alkali resistance) and the like.

On the contrary, in Comparative Examples 13 to 20, the photo-curability and bottom curability were low, and the resist shape was undercut, and the resist shape was bad.

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

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

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

Irgacure 907: 2-methyl- [4- (methylthio) phenyl] morpholino-1-propanone (trade name,

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

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

Tin nanocene: 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.,

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

BaSO ₄ : manufactured by Sakai Kagaku Kogyo Co., Ltd.

SiO ₂ : Tatsumori Co., Ltd.

Epicoat 828: bisphenol A type epoxy resin (trade name, manufactured by Mitsubishi Kagaku Co., Ltd.)

From the results shown in Table 4, it is understood that the photosensitive resin composition of the present invention of Examples 19 to 24 can stably obtain a vier shape excellent in resist shape while maintaining the bottom curability, and the pattern of the permanent mask resist (solder resist) , A pattern having a hole diameter of 100 mu m and a hole pitch of 100 mu m, or a high-precision pattern having a hole diameter of 80 mu m and an interval pitch of 80 mu m can also reduce surrounding thickening , And the diameter of the via was excellent. Further, it was confirmed that not only excellent resist shapes but also other properties such as solder heat resistance and the like were confirmed. This is considered to be an effect obtainable by the combination of the photosensitive resin composition of the present invention, particularly (B) the acylphosphine oxide-based photopolymerization initiator and (C3) the photopolymerization initiator.

On the contrary, in Comparative Examples 21 to 24, problems of the bottom curing property and the resist shape were not solved, and thickening around the pattern of the permanent mask resist also occurred, which was insufficient.

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

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

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

Irgacure 907: 2-methyl- [4- (methylthio) phenyl] morpholino-1-propanone (trade name,

(Irgacox 1010: pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name,

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

(Irgacox 1076: octadecyl [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name,

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

BaSO ₄ : manufactured by Sakai Kagaku Kogyo Co., Ltd.

SiO ₂ : Tatsumori Co., Ltd.

Epicoat 828: bisphenol A type epoxy resin (trade name, manufactured by Mitsubishi Kagaku Co., Ltd.)

From the results shown in Table 5, it can be seen that the patterns of the permanent mask resist (solder resist) of the present invention of Examples 25 to 30 are patterns in which the hole diameter is 100 mu m and the interval pitch between the holes is 100 mu m, Or a high-precision pattern in which the hole diameter is 80 mu m and the interval pitch between the holes is 80 mu m, the undercut, the bottom width pulling, or the thickening can be confirmed while maintaining excellent surface curability and bottom curability, It is possible to obtain an excellent resist shape without deteriorating the properties, and it has been confirmed that the Bayer diameter is excellent. Further, it was confirmed that not only it has excellent solder heat resistance and flux corrosion resistance but also excellent in various performances such as adhesion, solvent resistance, chemical resistance (acid resistance, alkali resistance) and the like.

On the contrary, in Comparative Examples 25 to 30, the surface curability and the bottom curability were low, and the resist shape was in the undercut. In Comparative Examples 29 and 30, the irradiation dose at the time of development was increased and the surface curability and bottom curability were good. The line width of the intermediate portion (central portion) and the deepest portion (bottom portion) becomes larger with respect to the line width of the surface portion (upper portion) of the cross section of the pattern, and the resist shape is deteriorated.

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

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

Irgacure 907: 2-methyl- [4- (methylthio) phenyl] morpholino-1-propanone (trade name,

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

MBI: mercaptobenzimidazole

Phthalocyanine pigments: manufactured by San Yoshikiso Co., Ltd.

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

BaSO ₄ : manufactured by Sakai Kagaku Kogyo Co., Ltd.

SiO ₂ : Tatsumori Co., Ltd.

YSLV-80XY: Tetramethylbisphenol F type epoxy resin (trade name, manufactured by Shinnitetsu Kagaku Co., Ltd.)

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

PB-3600: Epoxidized polybutadiene (trade name, manufactured by Daicel Chemical Industries, Ltd.)

· SP1108: polyester resin (trade name, manufactured by Hitachi Chemical Co., Ltd.)

· DICY 7: Dicyandiamide

From the results shown in Table 6, it can be understood that the photosensitive resin composition of the present invention of Examples 31 to 34 is such that the patterns of the photosensitive element and the permanent mask resist (solder resist) have a hole diameter of 100 mu m, Even if the size of the pattern or hole diameter is 80 占 퐉 and the interval pitch between the holes is 80 占 퐉, the undercut, the lower end pulling, or the thickening is confirmed, or the linearity of the outline of the pattern is not bad, It was confirmed that an excellent resist shape can be obtained.

Further, it was confirmed that it was also excellent in various performances such as internal electric field plating ability, solder heat resistance, crack resistance, adhesion, solvent resistance, chemical resistance (acid resistance, alkali resistance).

In contrast, the photosensitive resin compositions of Comparative Examples 31 to 34 were inferior in solder heat resistance and crack resistance as well as deteriorated in resist shape.

Industrial availability

According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a pattern having good linearity of pattern contour, excellent resist shape and excellent resolution without causing occurrence of undercuts that are cut off at the bottom portion, It is possible to obtain a permanent mask resistor which can form a pattern with excellent hole-diameter size and hole-pitch pitch stability. The permanent mask resistors are suitably used for printed wiring boards.

Claims (15)

(A) an acid-modified vinyl group-containing epoxy resin, (B) an acylphosphine oxide-based photopolymerization initiator, (C1) an alkylaminobenzene derivative, (C2) a pyrazoline- or anthracene-based sensitizer, (C4) hindered phenol antioxidant, a quinone antioxidant, an amine antioxidant, a sulfur-based antioxidant, an antioxidant, an antioxidant, an antioxidant, (C) at least one kind of (C) additive selected from the group consisting of a compound containing a thiol group, and (D) a photopolymerizable compound. The method according to claim 1,
(A) an epoxy resin having an acid-modified vinyl group, an epoxy resin having a structural unit represented by the general formula (I), an epoxy resin having a structural unit represented by the general formula (II), and a structural unit represented by the general formula At least one epoxy resin selected from epoxy resins, bisphenol novolak type epoxy resins having constituent units represented by formula (IV) and bisphenol novolak type epoxy resins having constituent units represented by formula (V) is a resin obtained by reacting a resin (a ') obtained by reacting a polyisocyanate (a) and a vinyl group-containing monocarboxylic acid (b) with a saturated group or an unsaturated group-containing polybasic acid anhydride (c).

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

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

[Wherein 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 s} may be the same or different]

[Formula (IV) of, R ¹³ is methyl to be a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a sulfone group, or a tree, Y ⁴ represents a hydrogen atom or glycidyl, at least one of Y ⁴ is Glycidyl group, and plural R &lt; ¹³ &gt; s may be the same or different.]

[Formula (V) of, R ¹⁴ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a sulfone group, or a trihalomethyl, Y ⁵ represents a hydrogen atom or glycidyl, at least one of Y ⁵ is A plurality of R &lt; ¹⁴ &gt; may be the same or different.] 3. The method according to claim 1 or 2,
(B) the acylphosphine oxide-based photopolymerization initiator is at least one compound selected from the group consisting of (2,6-dimethoxybenzoyl) -2,4,6-trimethylbenzoyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) Trimethylbenzoyldiphenylphosphine oxide, ethyl-2,4,6-trimethylbenzoylphenylphosphinate, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, ( (P-hydroxyphenyl) diphenylphosphine oxide, bis (p-hydroxyphenyl) phenylphosphine oxide, and tris (p-hydroxyphenyl) Phosphine oxide, and a phosphine oxide. 4. The method according to any one of claims 1 to 3,
Wherein the (C) additive is at least one (C1) alkylaminobenzene derivative selected from phenylglycine derivatives, aminobenzoic acid derivatives, and aminobenzoic acid ester derivatives. 4. The method according to any one of claims 1 to 3,
Wherein the (C) additive is a (C2) pyrazoline type sensitizer represented by the following general formula (VI).

A, b, and c each represent an integer of 0 to 2; and the sum of a, b, and c is 1 to 6, and R is an alkyl group having 4 to 12 carbon atoms. When the sum of a, b and c is 2 to 6, plural R in the same molecule may be the same or different.] 4. The method according to any one of claims 1 to 3,
Wherein the (C) additive is at least one (C2) anthracene type sensitizer selected from dialkyl anthracene, diphenylanthracene, and dialkoxyanthracene. 4. The method according to any one of claims 1 to 3,
(C) the additive is selected from the group consisting of 2,4,5-triarylimidazole dimer, 1,7-bis (9,9'-acridinyl) heptane, bis (η ⁵ -cyclopentadienyl) (2,4-cyclopentadienyl) -bis (2,6-difluoro-3- (1, 2-difluoro- - (pyrryl) phenyl) titanium. The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator is (C3) a photopolymerization initiator. 4. The method according to any one of claims 1 to 3,
Wherein the (C) additive is at least one (C4) antioxidant selected from hindered phenol-based antioxidants, sulfur-based antioxidants and phosphorus-based antioxidants. 4. The method according to any one of claims 1 to 3,
Wherein the (C) additive is at least one (C5) thiol group-containing compound selected from mercaptobenzoxazole, mercaptobenzothiazole, and mercaptobenzimidazole. 10. The method according to any one of claims 1 to 9,
Wherein the photopolymerizable compound (D) is a compound containing a (meth) acryloyl group. 11. The method according to any one of claims 1 to 10,
(E) an inorganic filler. 12. The method according to any one of claims 1 to 11,
A photosensitive resin composition used for forming a permanent mask resistor. A photosensitive element comprising a support and a photosensitive layer comprising the photosensitive resin composition according to any one of claims 1 to 12 on the support. A permanent mask resistor formed by the photosensitive resin composition according to any one of claims 1 to 12. A printed wiring board comprising the permanent mask resist according to claim 14.

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