WO2006109890A1

WO2006109890A1 - Photosensitive resin composition, printed wiring board, and semiconductor package substrate

Info

Publication number: WO2006109890A1
Application number: PCT/JP2006/308166
Authority: WO
Inventors: Tatsuya Kiyota; Yukihiro Kiuchi; Masatoshi Iji
Original assignee: Tamura Kaken Corporation; Nec Corporation
Priority date: 2005-04-13
Filing date: 2006-04-12
Publication date: 2006-10-19
Also published as: CN101142528A; TW200641529A; TWI392965B; CN101142528B; JPWO2006109890A1; JP4878597B2

Abstract

A photosensitive resin composition which comprises: (A) a resin which is, e.g., one obtained by reacting a product of the reaction of an unsaturated monocarboxylic acid with an epoxy resin selected from the group consisting of compounds of the formula (1) and compounds of the formula (2) with a compound selected from the group consisting of polybasic acids and polybasic acid anhydrides; (a) a resin which is, e.g., one obtained by reacting a product of the reaction of an unsaturated monocarboxylic acid with an epoxy resin other than the compounds of the formula (1) and the compounds of the formula (2) with a compound selected from the group consisting of polybasic acids and polybasic acid anhydrides; (B) a photopolymerization initiator; (C) a reactive diluent; (D) an epoxy resin selected from the group consisting of compounds of the formula (1) and compounds of the formula (2); (d) an epoxy resin other than the compounds of the formula (1) and the compounds of the formula (2); and (E) a molybdenum compound.

Description

Specification

Photosensitive resin composition, printed wiring board, and semiconductor package substrate

The present invention is capable of forming an image by ultraviolet exposure and development with a dilute alkaline aqueous solution, and does not contain halogen, phosphorus, or antimony, and achieves, for example, “UL 9 4 V-0”. The present invention relates to a composition, a printed wiring board and a semiconductor package substrate using the composition. Background art

The printed wiring board is for mounting electronic circuits on the soldering land of the pattern by forming a conductor circuit on the board, excluding the soldering land. The conductor circuit part is covered with a solder resist film as a permanent protective film. This prevents solder from adhering to unnecessary parts when soldering electronic components to a printed circuit board, and also prevents circuit conductors from being directly exposed to air and being corroded by oxidation and humidity. To do.

These solder resist compositions are required to have high flame retardancy (UL 94 V-0), but as a flame retardant method, a halogen-containing thermosetting resin (a derivative of tetrabromobisphenol A) ( Japanese Patent No. 2 0 03-08442 9) is used. However, such halogen-containing thermosetting resins are concerned about the generation of toxic dioxin during incineration, and there is an increasing demand for dehalogenation.

In addition, as a flame-retarding technique using phosphorus, inorganic phosphorus such as red phosphorus (Tokukaihei 09-2 5 844 6) and organic phosphorus compounds (Tokuyo 2000 00 1-2)

2 1 24 5 publication) (Japanese patent 2 00 2 -040 6 3 publication 3) There is. However, halogen-free substrates using phosphorus-based flame retardants have been reported to have poor moisture resistance (Rajoo and EH Wong: "Moisture Characteristics and Performance of Halogen-Free Laminates", International Conference on Electronics Packaging (ICEP) , pp 4 80-4 85, 2 0 0 2).

Against this background, flame retardancy using a metal hydroxide such as aluminum hydroxide or magnesium hydroxide in the solder resist composition has been studied (Japanese Patent Application Laid-Open No. 2000-156748). However, with this method, it is difficult to achieve both the properties required for the solder resist composition and the flame retardancy.

In Japanese Patent Laid-Open No. 1-140 2777, (A) a novolac-structured phenolic resin containing a biphenyl derivative and / or a naphthenic derivative in the molecule is included in the total phenolic resin amount. 30 to 100 parts by mass of a phenolic resin, (B) a novolac-structured epoxy resin containing a biphenyl derivative and / or a naphthalene derivative in the molecule, (C) an inorganic filler, (D) An epoxy resin composition for encapsulating a semiconductor containing a curing accelerator as an essential component is disclosed. Disclosure of the invention

However, any of the prior arts exhibits a high level of flame retardancy, for example, as required for semiconductor applications, and a high level of sensitivity, tackiness, developability, resistance to resistance, for example, required for semiconductor solder resist films. Photosensitive resin compositions that exhibit chemical properties, heat resistance, and insulation resistance are not provided.

The subject of the present invention is a photosensitive resin which exhibits a high degree of sensitivity, tackiness, developability, chemical resistance, heat resistance, insulation resistance, and exhibits excellent flame retardancy without using a halogen-based or phosphorus-based compound. It is to provide a composition. Another object of the present invention is to provide a printed wiring board before or after mounting an electronic component having a cured film of a solder resist film of the photosensitive resin composition, or a structure for mounting an electronic component such as a semiconductor package substrate. It is to be. The photosensitive resin composition according to the present invention is

(A) one or more active energy ray-curable resins selected from the group consisting of (A 1) and (A 2),

(A 1) a reaction product of an epoxy resin selected from the group consisting of an epoxy resin of the formula (1) and an epoxy resin of the formula (2) and an unsaturated monocarboxylic acid, a polybasic acid and a polybasic acid anhydride A resin obtained by reacting a compound selected from the group consisting of:

(A2) a reaction product of an epoxy resin selected from the group consisting of an epoxy resin of the formula (1) and an epoxy resin of the formula (2) and an unsaturated monocarboxylic acid, a polybasic acid and a polybasic acid anhydride A resin obtained by reacting a resin selected from a group selected from the group consisting of a glycidyl compound having a radical polymerizable unsaturated group and an epoxy group;

(a) one or more active energy ray-curable resins selected from the group consisting of (a1) and (a2),

(a 1) selected from the group consisting of an epoxy resin of the formula (1) and an epoxy resin other than the epoxy resin of the formula (2) and an unsaturated monocarboxylic acid, a polybasic acid and a polybasic acid anhydride Resin obtained by reacting with the compound obtained,

(a2) selected from the group consisting of a reaction product of an epoxy resin of the formula (1) and an epoxy resin other than the epoxy resin of the formula (2) and an unsaturated monocarboxylic acid, a polybasic acid and a polybasic acid anhydride A resin obtained by further reacting a resin obtained by reacting the compound with a glycidyl compound having a radical polymerizable unsaturated group and an epoxy group, (B) a photopolymerization initiator,

(C) a reactive diluent,

(D) an epoxy resin selected from the group consisting of a compound of formula (1) and a compound of formula (2),

(d) an epoxy resin other than the compound of formula (1) and the compound of formula (2), and

(E) It contains a molybdenum compound.

(n = 1 or more, 10 or less)

(2) (n = 1 or more, 1 or less)

The present invention also relates to a printed wiring board or a semiconductor package substrate before or after mounting an electronic component, comprising the photosensitive resin composition. This substrate is not limited to a plate shape, and may be a sheet that is flexibly curved or a deformed shape such as a spherical shape.

The photosensitive resin composition of the present invention is sensitive to active energy rays and can be developed with a dilute aqueous solution. When used as a solder resist for printed wiring boards, A coating film excellent in adhesion and insulating properties and excellent in flame retardancy can be formed, and is suitable for a solder resist of a printed wiring board substrate.

That is, a formula having a specific selected aromatic skeleton and glycidyl group side chain

(1) By using the active energy ray curable resin (A 1) (A 2) obtained by synthesizing the compound of (2) as a starting point, the flame retardancy and heat resistance of the coating can be improved. Can do. However, the active energy ray-curable resin (A) alone can increase the flame retardancy and heat resistance of the coating, but it satisfies the sensitivity, especially the sensitivity required when used as a solder resist. It turns out that you can't. For this reason, for example, in order to satisfy the sensitivity required as a solder resist, (a) an active energy ray-curable resin composition synthesized from an epoxy resin other than the formulas (1) and (2) is used in combination.

However, if the amount of the component (a) is increased to such a degree that sufficiently high sensitivity can be obtained, the flame retardancy of the coating tends to decrease. Here, in the present invention, the epoxy resin (D) component is further used in combination. This is a specific epoxy resin containing a phenyl group or a biphenyl group in the molecule, and has the same structure as (A). By using such an epoxy resin in combination, it is covered by the decomposition gas generated inside the cured product of the resin composition when ignited. The film surface expands on the rubber, and a foamed layer is easily generated.

Based on such a composition, the present inventors further added (E) a molybdenum compound to maintain the sensitivity and film properties derived from the active energy ray-curable resin (a). However, it effectively strengthens the foamed layer that forms the cured product composed of the active energy ray-curable resin (A) and epoxy resin (D) when ignited, thereby achieving high flame retardancy. I found out. BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, the (A) active energy ray-curable resin is one or more active energy ray-curable resins selected from the group consisting of (A 1) and (A2).

(A1) a reaction product of an epoxy resin selected from the group consisting of an epoxy resin of formula (1) and an epoxy resin of formula (2) and an unsaturated monocarboxylic acid, a polybasic acid and a polybasic acid anhydride A resin obtained by reacting a compound selected from the group consisting of:

(A2) a reaction product of an epoxy resin selected from the group consisting of an epoxy resin of formula (1) and an epoxy resin of formula (2) and an unsaturated monocarboxylic acid, a polybasic acid and a polybasic acid anhydride A resin obtained by reacting a resin obtained by reacting with a compound selected from the group consisting of a glycidyl compound having a radical polymerizable unsaturated group and an epoxy group.

The resin of (A) may be selected from one or more types from (A 1), may be selected from one or more types from (A 2), and may be either (A l) or (A 2) May be selected.

Also, one or more of the epoxy resins of formula (1) may be reacted as described above, and one or more of the epoxy resins of formula (2) may be reacted as described above. Or a mixture of both the epoxy resin of formula (1) and the epoxy resin of formula (2) may be reacted as described above.

In the present invention, the active energy linear curable resin synthesized from the compounds of the formulas (1) and (2) contains a rigid functional group such as a biphenyl group or a phenyl group in the main chain. And since the active energy ray curable resin containing a phenyl group or biphenyl group in the molecule reacts to form a crosslinked structure, it is generated inside the cured product of the resin composition when ignited. The cracked gas expands the surface like a rubber to form a foamed layer, confining volatile substances due to thermal decomposition. This foamed layer cuts off the supply of heat and oxygen to the unburned area and exhibits high flame retardancy. In addition, when a resin synthesized from the compounds of formulas (1) and (2) is used with a similar structure, it is possible to improve various properties such as high flame retardancy and sensitivity, heat resistance, and developability. I found it.

In the formula (1) and the formula (2), n is 1 to 10: 1. If n exceeds 11, the resin viscosity becomes too high. From the viewpoint of the present invention, n is more preferably 7 or less.

The epoxy resins of the formulas (1) and (2) can be obtained by glycidyl etherification of each phenol resin having a structure corresponding thereto.

In the present invention, in addition to the component (A), one or more active energy ray-curable resins selected from the group consisting of (a) (a 1) and (a 2) are used in combination.

(a 1) selected from the group consisting of an epoxy resin of formula (1) and a reaction product of an epoxy resin other than the epoxy resin of formula (2) and an unsaturated monocarboxylic acid, and a polybasic acid and a polybasic acid anhydride A resin obtained by reacting with the compound obtained,

(a2) An epoxy resin of the formula (1) and an epoxy resin other than the epoxy resin of the formula (2) and an unsaturated monocarboxylic acid, and a polybasic acid And a resin obtained by reacting a resin selected from the group consisting of polybasic acid anhydrides with a glycidyl compound having a radically polymerizable unsaturated group and an epoxy group.

Although the active energy ray curable resin (A) alone can increase the flame retardancy and heat resistance of the coating, it must satisfy the sensitivity, especially the sensitivity required when used as a solder resist. I found it impossible. Therefore, for example, in order to satisfy the sensitivity required as a solder resist, (a) an active energy line curable resin composition synthesized from an epoxy resin other than the formula (1) and formula (2) is used in combination. To do.

Here, as the epoxy resin other than those represented by formulas (1) and (2), a polyfunctional epoxy resin having two or more epoxy groups in the molecule is preferable. Further, it is preferable that the main chain skeleton does not have a condensed aromatic ring skeleton such as a biphenyl skeleton or a naphthalene skeleton.

Any polyfunctional epoxy resin can be used as long as it is a bifunctional or higher functional epoxy resin. Usually, an epoxy equivalent having an epoxy equivalent of 1,00 or less, preferably from 100 to 500 is used. For example, bisphenol type epoxy resins such as bisphenol A type and bisphenol F type, novolac type epoxy resins such as o-cresol novolak, cyclic aliphatic polyfunctional epoxy resin, glycidyl ester type epoxy resin, glycidylamine type Examples thereof include epoxy resins, heterocyclic polyfunctional epoxy resins, bisphenol-modified novolak epoxy resins, and the like. These epoxy resins may be used alone or in combination of two or more.

Hereinafter, the synthesis of each component of (A l) (A 2) (a 1) (a 2) will be further described.

(A 1) is the reaction of an epoxy resin selected from the group consisting of the epoxy resin of formula (1) and the epoxy resin of formula (2) with an unsaturated monocarboxylic acid And a compound selected from the group consisting of a polybasic acid and a polybasic acid anhydride.

(a 1) is a group consisting of a reaction product of an epoxy resin of formula (1) and an epoxy resin other than the epoxy resin of formula (2) and an unsaturated monocarboxylic acid, a polybasic acid and a polybasic acid anhydride. It can be obtained by reacting with a selected compound. This process is described.

First, an epoxy resin of formula (1), an epoxy resin of formula (2), or a formula

(1) At least a part of the epoxy resin other than (2) is reacted with a radically polymerizable 'unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid, and the resulting hydroxyl group is polybasic acid or anhydride thereof. Make things react. Epoxy resin of formula (1), epoxy resin of formula (2), or formula (1)

When an epoxy resin other than (2) is reacted with a radically polymerizable unsaturated monocarboxylic acid, the epoxy resin is cleaved by the reaction between the epoxy group and the carboxyl group, and a hydroxyl group and an ester bond are formed. The radically polymerizable unsaturated monocarboxylic acid to be used is not particularly limited, and examples thereof include (meth) acrylic acid, crotonic acid, cinnamic acid, and (meth) acrylic acid is most preferable. The reaction method of the epoxy resin and the radically polymerizable unsaturated monocarboxylic acid is not particularly limited. For example, the epoxy resin and (meth) acrylic acid can be reacted by heating and stirring together with a catalyst in an appropriate solvent. . Examples of the solvent include ketones such as methylethylketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, isopropanol, and cyclohexanol, cyclohexanone, and methylcyclohexane. Alicyclic hydrocarbons such as xanone, petroleum-based solvents such as petroleum ether and petroleum naphtha, cellosolves such as cellosolve and petroleum sorbate, carbitols such as carbitol and butylcarbitol, ethyl acetate, acetic acid Butyl, Butyl Seguchi Solbucetate And acetates such as citrate, carbitol acetate, and butyl carbitol acetate. Examples of the catalyst include amines such as tritylamine, tributylamine and dimethylbenzylamine, and phosphorous compounds such as triphenylphosphine and triphenylphosphate.

In the reaction of each of the above epoxy resins with the radically polymerizable unsaturated monocarboxylic acid, it is preferable to react 0.7 to 1.0 equivalent of the radically polymerizable unsaturated monocarboxylic acid with respect to 1 equivalent of the epoxy group of the epoxy resin. When (meth) acrylic acid is used, the reaction is more preferably carried out in an amount equivalent to 0.8 to 1.0. If the amount of the radically polymerized unsaturated monocarboxylic acid is less than 0.7 equivalent, gelation may occur during the subsequent synthesis reaction, and the storage stability of the resin may be deteriorated. In addition, if the radically polymerizable unsaturated monocarboxylic acid is excessive, a large amount of unreacted carboxylic acid remains, which may deteriorate various properties of the cured product. The reaction between the epoxy resin and the radically polymerizable unsaturated monocarboxylic acid is preferably performed in a heated state, and the reaction temperature is preferably 80 to 140 ° C. If the reaction temperature exceeds 140 ° C, the radically polymerizable unsaturated monocarboxylic acid may cause thermal polymerization and may be difficult to synthesize, and if it is less than 80 ° C, the reaction rate becomes slow. In some cases, it is not preferable in actual production. The reaction product of the epoxy resin and the radically polymerizable unsaturated monocarboxylic acid can be subjected to the reaction with the following polybasic acids in the solution without isolation.

A polybasic acid or an anhydride thereof is reacted with the unsaturated monocarboxylic oxide epoxy resin which is a reaction product of the epoxy resin and the radically polymerizable unsaturated monocarboxylic acid. The polybasic acid or its anhydride is not particularly limited, and either saturated or unsaturated can be used. Such polybasic acids include succinic acid, maleic acid, adipic acid, fuuric acid, tetrahydrohydride. Fuuric acid, 3-methyltetrahydrodrofuric acid, 4-methyltetrahydrodrofuric acid, 3-ethylactetrahidrofuric acid, 4-ethylethyltrachrofurauric acid, hexahydrodrofuric acid, 3- Methylhexahydrofurauric acid, 4-Methylhexadolofuric acid, 3-Ethylhexahydrofuranuric acid, 4-Ethylhexahydrophthalic acid, Trimellitic acid, Pyromellitic acid and And diglycolic acid, and polybasic acid anhydrides include all of these anhydrides. These compounds can be used alone or

Two or more types may be mixed. The polybasic acid or polybasic acid anhydride reacts with a hydroxyl group formed by the reaction of each of the above epoxy resins with a radically polymerizable unsaturated monocarboxylic acid, thereby giving the resin a free carboxyl group.

The amount of the polybasic acid or its anhydride is preferably 0.2 to 1.0 mol with respect to 1 mol of the hydroxyl group of the reaction product of each epoxy resin and radically polymerizable unsaturated monocarboxylic acid. . From the point that a highly sensitive resin film can be obtained at the time of exposure, the reaction is carried out at 0.3 to 0.9 mol, more preferably at 0.4 to 0.9 mol. If it is less than 0.2 mol, the solubility of the resulting resin in dilute aqueous solutions may be reduced, and if it exceeds 1.0 mol, the properties of the cured film finally obtained will be reduced. May decrease. It is preferable that the polybasic acid or its anhydride is added to the above unsaturated monocarboxylic oxide epoxy resin and subjected to a dehydration condensation reaction, and the water produced during the reaction is continuously taken out from the reaction system. The reaction is preferably performed in a heated state, and the reaction temperature is preferably 70 to 130 ° C. When the reaction temperature exceeds 130 ° C, synthesis may be difficult due to thermal bonding of those bonded to the epoxy resin or unreacted radically polymerizable unsaturated groups. If it is less than 70 ° C, the reaction rate becomes slow, which may be undesirable in actual production. Polybasic acid-modified unsaturated carboxylic acid which is a reaction product of the above polybasic acid or its anhydride and unsaturated monocarboxylic epoxy resin The acid value of the epoxy resin is preferably 60 to 130 mg KOH / g. The acid value of the reaction product can be adjusted by the amount of the polybasic acid or its anhydride to be reacted.

In the present invention, the above polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin can be used as a photosensitive resin. This corresponds to the active energy ray curable resin (A1) (a1).

On the other hand, by reacting the carboxyl group of the polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin (A 1) (a 1) with one or more radically polymerizable unsaturated groups and an glycidyl compound having an epoxy group. Further, a photosensitive resin (A 2) (a 2) in which a radically polymerizable unsaturated group is further introduced to further improve the photosensitivity may be used. This photosensitive resin with improved photosensitivity has high radical polymerizability because the radical polymerizable unsaturated group is bonded as a side chain of the photosensitive resin by the reaction with the final glycidyl compound. Photosensitive properties can be imparted.

Examples of the glycidyl compound having one or more radically polymerizable unsaturated groups and an epoxy group include glycidyl (meth) acrylate, allylic glycidyl ether, pentaerythritol triacrylate monoglycidyl ether, and the like. A plurality of glycidyl groups may be present. The glycidyl compound is added to the solution of the polybasic acid-modified unsaturated monocarbon-oxidized epoxy resin and allowed to react. Usually, 0.05 mol to 0.5 mol per mol of the carboxyl group introduced into the resin. Respond at the rate of. Considering the photosensitivity, thermal management width, and insulation characteristics of the resulting photosensitive resin composition containing the photosensitive resin, the reaction should be carried out at a rate of 0.1 to 0.5 mol, and the reaction temperature is 8 0 to 120 ° C is preferred. The acid value of the photosensitive resin comprising the glycidyl compound-added polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin thus obtained is 45 to 25 O mg KOH / g. It is desirable.

The active energy ray-curable resin (A) is preferably added at a ratio of 2 to 40% by weight in the photosensitive resin composition of the present invention. If the amount added is less than 2% by weight, it is difficult to obtain sufficient flame retardancy. If this added amount exceeds 40% by weight, the photosensitivity of the resin composition is lowered, and for example, it tends to be difficult to satisfy the requirements as a solder resist.

The active energy ray-curable resin ( _a ) is preferably added in a proportion of 5 to 30% by weight in the photosensitive resin composition of the present invention. When the amount added is less than 5% by weight, the photosensitivity of the resin composition is lowered, and for example, it tends to be difficult to satisfy the requirements as a solder resist. If this amount is more than 30% by weight, flame retardancy is difficult to obtain.

The photopolymerization initiator (B) is not particularly limited, and any conventionally known photopolymerization initiator (B) can be used. Specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin sobutyl ether, acetophenone, dimethylaminoacetophenone, 2, 2- Dimethoxy-2 -phenylacetophenone, 2,2-diethoxy-2 -phenylacetophenone, 2-hydroxy-2--2-methyl-1-phenylpropane-1-one, 2-methyl-1- (4- (methylthio) Phenyl)-2 -morpholino -propan-1 -one, 4-(2 -hydroxyethoxy) phenyl-2-(hydroxy -2 -provir) ketone, 2-benzyl-2-dimethylamino-1 -(4-morpholino) buevenone, benzophenone, p-phenylbenzophenone, 4, 4, -jetylaminobenzophenone, Chloro base Nzofuenon, 2 - methyl anthraquinone, 2 - Echiruan Torakinon, 2 - tert - Buchiruan Torakinon, 2 - Aminoan DOO Rakinon, 2 - methylthioxanthone, & 2, 4 - GETS Chi Lucio hexane Bokun Etc. These can be used alone or in combination of two or more.

The amount of the photopolymerization initiator (B) used is 0.5 to 50 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin of the component (A), and less than 0.5 parts by mass. Then, the photopolymerization reaction of the active energy ray-curable resin (A) component becomes insufficient, and if it exceeds 50 parts by mass, the effect of the photopolymerization on the ratio of the added amount is not improved.

As the reactive diluent (C), the active energy ray-curable resin of the above component (A) is further sufficiently photocured to impart chemical resistance, and at least in one molecule. A compound having one or more double bonds, preferably two or more. The reactive diluent is preferably a liquid at room temperature and has a boiling point of 100 ° C. or higher or less than 10 ° C. and does not sublime. If the solder resist composition containing a reactive diluent is exposed to a solid at room temperature, the reactive diluent molecules hardly move in the coating film, and a sufficient curing depth can be obtained. Absent. Further, when the boiling point or sublimation point is less than 10 ° C., the reactive diluent also evaporates at the same time when the solvent contained in the solder resist composition is dried. Commonly used reactive diluents include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentylglycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, neopentylglycol adipate di (meth) acrylate, hydroxypivalic acid neopentylglycol di (meth) acrylate, di-sic mouth pen genil di (meth) acrylate, force prolacton modified disic (Meth) acrylate, ethylene oxide-modified phosphate di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentyl ester Reactive diluents such as triethyl (meth) acrylate, pen erythritol triacrylate (meth) acrylate, tris (acrylochelate) isocyanurate, dipentaerythritol hexa (meth) acrylate, etc. Can be mentioned. The reactive diluents described above can be used alone or in mixed systems.

The addition amount of the reactive diluent (C) is usually in the range of 2 to 40 parts by mass per 100 parts by mass of the active energy ray-curable resin of the component (A). If the addition amount is less than 2 parts by mass, sufficient photocuring cannot be obtained, and it is difficult to obtain sufficient performance in terms of chemical resistance and plating resistance of the cured coating film. If it exceeds, the tack becomes strong and the exposure mask substrate tends to adhere during the exposure process using a contact type exposure apparatus, making it difficult to obtain the desired cured coating film.

In the present invention, (D) the epoxy resin selected from the group consisting of the epoxy resin of the formula (1) and the epoxy resin of the formula (2) is exposed to the coating film in the photosensitive resin of the present invention, Post-curing, a process after development, improves the performance of the coating film.

In the present invention, the epoxy resin of component (D) contains a rigid functional group such as biphenyl or phenyl in the main chain. The epoxy resin containing a phenyl group or a biphenyl group in the molecule reacts to form a cross-linked structure. Therefore, when ignited, the surface is rubberized by the decomposition gas generated inside the cured product of the resin composition. It expands upward to form a foamed layer that traps volatiles from pyrolysis. This foamed layer cuts off the supply of heat and oxygen to the unburned part and exhibits a high degree of flame retardancy. (D) Although the epoxy resin selected from the group consisting of the epoxy resin of the formula (1) and the epoxy resin of the formula (2) has been described above, specifically, “NC-3 300”, “NC-3” “0 0 0—H” (Nippon Kayaku Co., Ltd.) and “XL” · “XLC” series (special phenolic resin, zylock) Epoxidized products (Mitsui Chemicals) are listed.

In addition to the component (D), the epoxy resin of the present invention can be used in combination with (d) an epoxy resin having at least two epoxy groups in one molecule other than the compounds of the formulas (1) and (2). . Specific examples of phenol novolak resins include Epicoat 152, 1 54 (hereinafter, Japan Epoxy Resin), Epiclon N-740, N-770 (above, Dainippon Ink & Chemicals), Cresol Novolac. Epiclone N-680, N-695 (manufactured by Dainippon Ink & Chemicals, Inc.), Epiclone HP-7200 (Dinippon Ink & Chemicals, Inc.), glycidylamine As the type epoxy resin, TEPIC-S, TEP IC-H (Nissan Chemical Co., Ltd.), Bisphenol A type epoxy resin, Epicoat 100 1, 1002, 1003, 1004 (above, Japan Epoxy Resin Co., Ltd.) ), Ebicron 1050, 3050 (above, Dainippon Ink Chemical Co., Ltd.), Araldite AER 60 71, AER 6072 (above, Asahi Ciba), Potato YD-0 1 1, YD-0 12 (above, manufactured by Tohto Kasei), Bisphenol F type epoxy resin Epototo YDF-200 1, YDF-2004 (above, manufactured by Tohto Kasei), water Epiclone EXA-7015 (Dainippon Ink Industries Co., Ltd.) as bisphenol A type epoxy resin, Epoxy Coat YX-4000, Epoxy resin as other epoxy resin having skeleton, 103 IS (manufactured by Japan Epoxy Resin Co., Ltd.), Epotote YSLV-80XY ( Manufactured by Tohto Kasei Co., Ltd.).

The (D) epoxy thermosetting resin is preferably added at a ratio of 5 to 30 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin (A). Moreover, (d) epoxy-type thermosetting resin is the ratio of 5-30 mass parts with respect to 100 mass parts of active energy ray curable resin of said (A) component. It is preferable to add. The total amount of the component (D) and the component (d) is preferably 20 to 50 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin of the component (A). .

When the amount of the component (D) (d) added is less than the lower limit, it is difficult to obtain sufficient heat resistance, adhesion, and plating resistance as a solder resist after post-curing. When the amount of the component (D) (d) exceeds the upper limit, it becomes difficult to dissolve in the dilute alkaline aqueous solution, and the solder resist composition remains on the soldering land, so-called scum is likely to occur. These epoxy thermosetting resins may be used alone or in combination of two or more. As a reaction accelerator, a known epoxy resin curing accelerator such as a melamine compound, an imidazole compound, or a phenol compound can be used in combination.

In the present invention, the (E) molybdenum compound is a compound containing a molybdenum element, but a material containing molybdate is preferable, and the use of this material improves the flame retardancy. This is composed of a resin containing aromatics such as a phenyl group or a biphenyl group in the molecule, such as the active energy ray-curable resin (A) or epoxy resin (D) of the present application, by adding a molybdenum compound. It is considered that the result of the thermal decomposition of the cured product is a result of a specific and efficient suppression, and the formation of a strong carbonized film on the surface of the foam layer formed by the cured product upon ignition. Specific examples of molybdate include zinc molybdate, a composite of zinc molybdate and magnesium silicate, calcium molybdate, and zinc calcium molybdate. The amount of the molybdenum compound added is usually in the range of 5 to 40 parts by mass per 100 parts by mass of the active energy ray-curable resin (A). If the addition amount is less than 5 parts by mass, sufficient flame retardancy cannot be obtained, and if the addition amount exceeds 40 parts by mass, there is a possibility that it will adversely affect the repelling property and the strength re-developability. There is.

In addition to the above components, the solder resist composition of the present invention may contain various additives such as silica, alumina, talc, calcium carbonate, barium sulfate, magnesium hydroxide, aluminum hydroxide and the like. Inorganic pigments, copper phthalocyanine, isoindoline, carbon black and other known color pigments, antifoaming agents, leveling agents and other coating additives can be incorporated.

The solder resist soot composition obtained as described above is applied to a circuit board having a conductive circuit by etching, for example, a copper foil of a copper clad laminate, and is applied at a predetermined thickness. After the solvent is evaporated by heating at a temperature of 15 to 60 minutes, the mask with a light-shielded pattern is brought into close contact with the soldering land of the above circuit, and the soldering land is irradiated with ultraviolet rays. The coating film is developed by removing the non-exposed areas corresponding to the above with a dilute alkaline aqueous solution. As this dilute alkali aqueous solution, a 0.5 to 5 mass% sodium carbonate aqueous solution is generally used, but other alkalis can also be used. Subsequently, the target solder resist film can be obtained by performing a post cure for 10 to 60 minutes in a hot air circulating drying oven at 140 to 160 ° C. In this way, a printed wiring board coated with a solder resist film is obtained, and electronic components are connected and mounted on the printed wiring board by a jet soldering method or a reflow soldering method. After mounting the semiconductor chip, the semiconductor chip is resin-sealed by transfer molding, or fixed with underfill resin, and mounted on another substrate as the semiconductor package substrate by the soldering method described above . In the present invention, a printed wiring board coated with a solder resist before mounting an electronic component or a semiconductor chip, a printed wiring board having an electronic component or a semiconductor chip mounted on the printed wiring board, and this printed wiring board None of the electronic devices used Include in subject. Example

Examples The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the following description, “part” means “part by mass” unless otherwise specified.

<(A) Preparation of active energy ray-curable resin>

(Synthesis Example 1)

Nippon Kayaku Co., Ltd., NC-3300 (Epoxy equivalent 2 73) 2 7 3 parts, dissolved in carbitol acetate 1 1 3 parts by heating, 70.5 parts acrylic acid and 0.5 parts methylhydroquinone And 0.5 part of triphenylphosphine are added, and the mixture is reacted at 110 to 120 ° C for 8 hours. When the acid value of this reaction solution becomes 2 or less, 76 parts of anhydrous tetrahydrofuran acid and 3 parts of petroleum naphtha are added and reacted at 90 to 100 ° C for 2 hours. An active energy line curable resin solution was obtained. This resin solution contains 17.5 parts carbitol acetate and 17.5 parts petroleum naphtha.

(Synthesis Example 2)

Made by Mitsui Chemicals Co., Ltd. Millex XL C-LL (Hydroxyl equivalent 1 6 9) 1 6 9 parts are dissolved in carbitol acetate 1 03.7 by heating to give glycidyl methacrylate 1 3 9. 2 parts and methyl hydroquinone 0 Add 5 parts and 0.5 part of dimethylbenzylamine, and react at 110-120 ° C for 8 hours. When the acid value of this reaction solution becomes 2 or less, add 76 parts of anhydrous hydrofluoric anhydride and 10.7. 7 parts of petroleum naphtha, and react for 90 hours at L 00 ° C for 2 hours. Thus, an active energy ray curable resin solution was obtained. This resin solution contains 17.5 parts carbitol acetate and 17.5 parts petroleum naphtha. ' <Preparation of active energy ray-curable resin (a)>

(Synthesis Example 3)

A cresol novolac type epoxy resin made by Nippon Kayaku Co., Ltd., E 0 CN — 1 04 S (epoxy equivalent 2 2 0) 2 20 parts was heated and dissolved in 98.9 parts of carbitol acetate, and then acrylic. Add 70.5 parts of acid, 0.5 parts of methylhydroquinone and 0.5 part of triphenylphosphine, and react at 1 10 to 120 ° C. for 8 hours. After the acid value of the reaction solution became 2 or less, 76 parts of anhydrous tetrahydrofuran acid and 98.9 parts of petroleum naphtha were added and reacted at 90 to 100 ° C. for 2 hours. An active energy ray-curable resin solution was obtained, which contained 17.5 parts carbitol acetate and 17.5 parts petroleum naphtha.

(Synthesis Example 4)

KA YAR ADR— 7 50 9 (epoxy equivalent: 32 0) 3 20 parts of bisphenol F type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., is dissolved in carbitol acetate 1 2 5. 8 parts by heating. 70. 5 parts, 0.5 part of methylhydroquinone and 0.5 part of triphenylphosphine are added and reacted at 110 to 120 ° C for 8 hours. When the acid value of the reaction solution reaches 2 or less, add 76 parts of tetrahydrophthalic anhydride and 15.8.8 parts of petroleum naphtha and react at 90 to 100 ° C for 2 hours to activate. An energy ray curable resin solution was obtained. This resin solution contains 17.5 parts carbitol acetate and 17.5 parts petroleum naphtha.

(Example 1)

(A) 100 parts of the active energy ray-curable resin solution obtained in Synthesis Example 1 to 100 parts of (a) 100 parts of the active energy ray-curable resin solution obtained in Synthesis Example 3 (B) Light Irgacure 9 07 as a polymerization initiator [2 -Methyl-1-(Methylthio) Feni, manufactured by Ciba Specialty Chemicals )-2 -morpholinopropane-1 -one) 17 parts, DE TX -S (Nippon Kayaku Co., Ltd., 1 part) (C) D PHA ( Nippon Kayaku Co., Ltd. Dipentaerythritol Hexaacrylate) 2 3 parts, (D) 20 parts of NC-300 as epoxy-based cured resin, (d) Epiclone N-770 as epoxy-based cured resin (Dainippon KEMGARD 9 11 C (compound of Nippon Molybdenum Japan, zinc molybdate and magnesium silicate) with 20 parts of (Eno) a phenol novolac type epoxy resin made by Ink Chemical Co., Ltd. 25 parts, KS-6 6 (made by Shin-Etsu Chemical Co., Ltd.) as an antifoaming agent, 3 parts melamine, 1 part dicyandiamide, 120 parts barium sulfate, 1 part phthalocyanine blue Add 3 parts of carbitol acetate and knead in 3 roll mill It was prepared solder registry composition Te. The composition of this photosensitive resin composition is shown in Table 1, and the results of UL 94 V flammability, sensitivity, developability, and coating film performance tested by the test methods described below are shown in Tables 1 and 2.

(Example 2)

In Example 1, it was the same except that (A) the active energy ray-curable resin solution obtained in Synthesis Example 1 was used instead of 100 parts of the active energy ray-curable resin solution obtained in Synthesis Example 2. Tables 1 and 2 show the results of preparing a photosensitive resin composition and testing the same as in Example 1.

(Example 3)

In Example 1, (a) Synthesis as active energy ray-curable resin solution Synthesis of active energy ray-curable resin solution obtained in Synthesis Example 4 instead of active energy ray-curable resin solution obtained in Example 3 1 0 0 Tables 1 and 2 show the results obtained by preparing a photosensitive resin composition in the same manner except that the parts are used, and testing in the same manner as in Example 1.

(Example 4) In Example 1, instead of Epiclone N-7700 as (d) Epoxy Curing Resin, YX-4000 (2,2,-(3,3,5,5,5-Tetra made by Japan Epoxy Resin Co., Ltd.) A photosensitive resin composition was prepared in the same manner except that methyl (1,1'-biphenyl) -4,4, -diyl) bis (oxymethylene)) bisoxysilane) was used and tested in the same manner as in Example 1. The results are shown in Tables 1 and 2.

(Example 5)

In Example 1, a photosensitive resin composition was prepared in the same manner except that (d) Epotot YS LV-8 00 XY (manufactured by Tohto Kasei Co., Ltd.) was used instead of Epiclone N-770 as the epoxy-based cured resin. Tables 1 and 2 show the results prepared and tested in the same manner as in Example 1.

(Example 6)

In Example 1, (d) Epoxy Coat 807 (Bisphenol F type epoxy type cured resin manufactured by Japan Poxy Resin Co., Ltd.) was used instead of Epiclone N-770 as epoxy type cured resin. Tables 1 and 2 show the results of preparing a photosensitive resin composition and testing it in the same manner as in Example 1.

(Example 7)

In Example 1, (C) Photosensitive R-684 (Nippon Kayaku Co., Ltd. dicyclopentyl diacrylate) instead of DP HA was used as the reactive diluent. Tables 1 and 2 show the results of preparing a functional resin composition and testing the same as in Example 1.

(Example 8)

In Example 1, a photosensitive resin composition was prepared in the same manner as in Example 1 except that KEMGARD 9 11 B (Nihon Shaw Williams, a compound of zinc molybdate) was used as (E). And tested as The results are shown in Tables 1 and 2.

(Comparative Example 1)

A photosensitive resin composition was prepared in the same manner as in Example 1 except that (E) was not contained, and the results of the same tests as in Example 1 are shown in Tables 1 and 2.

(Comparative Example 2)

In Example 1, (a) Synthesis as an active energy ray-curable resin solution Using only 200 parts of the active energy ray-curable resin solution obtained in Example 3,

(A) A photosensitive resin composition was prepared in the same manner except that the active energy ray-curable resin was not used, and the results of testing in the same manner as in Example 1 are shown in Tables 1 and 2.

(Comparative Example 3)

In Example 1, (a) Synthesis as an active energy ray-curable resin solution Using only 200 parts of the active energy ray-curable resin solution obtained in Example 3, (A) Using an active energy ray-curable resin Furthermore, a photosensitive resin composition was prepared in the same manner except that magnesium hydroxide was used instead of barium sulfate, and the results of tests similar to Example 1 are shown in Tables 1 and 2.

(Comparative Example 4)

In Example 1, the same procedure was used except that (A) 200 parts of the active energy ray-curable resin solution obtained in Synthesis Example 1 was used alone, and (a) the active energy ray-curable resin solution was not used. Tables 1 and 2 show the results of preparing a photosensitive resin composition and testing it in the same manner as in Example 1. table 1

Table 2

(Example 9)

In Example 1, (A) active energy ray-curable resin solution obtained in Synthesis Example 1 was 173 parts, and (a) active energy ray-curable resin solution obtained in Synthesis Example 3 was 27 parts. Tables 3 and 4 show the results of adjusting the photosensitive resin composition in the same manner except that, and testing in the same manner as in Example 1.

(Example 10)

In Example 1, 130 parts of (A) active energy ray-curable resin solution obtained in Synthesis Example 1 and 70 parts of (a) active energy ray-curable resin solution obtained in Synthesis Example 3 were used. Tables 3 and 4 show the results of adjusting the photosensitive resin composition in the same manner except that, and testing in the same manner as in Example 1.

(Example 1 1)

In Example 1, (A) 70 parts of the active energy ray-curable resin solution obtained in Synthesis Example 1 and (a) 125 parts of the active energy ray-curable resin solution obtained in Synthesis Example 3 (d) Tables 3 and 4 show the results of the same test as in Example 1 except that the photosensitive resin composition was prepared in the same manner except that 15 parts of Epiclone N-770 was used as the epoxy-based cured resin.

(Example 12)

In Example 1, (A) 165 parts of the active energy line curable resin solution obtained in Synthesis Example 1 and (a) 35 parts of the active energy ray curable resin solution obtained in Synthesis Example 3 ( Tables 3 and 4 show the results obtained by preparing a photosensitive resin composition in the same manner except that KEMGARD 9 1 1 C was 9 parts as E) and testing in the same manner as in Example 1. Table 3 Examples

Table 3

9 10 11 12

(A) Active energy ray Resin (Synthesis example 1) 173 130 70 165 Cured resin Resin (Synthesis example 2)

(a) Active energy Resin (Synthesis example 3) 27 70 125 35 Wire-curing resin Resin (Synthesis example 4.)

Irgacure

17 17 17 17

(B) Photopolymerization initiator 907

DETX-S 1 1 1 1

DPHA '23 23 23 23

(C) Reactive diluent force ladder

R-684

(D) Epoxy system

NC-3000 20 20 20 20 Cured resin

Epiclon

20 20 15

N-770

(d) Epoxy system

YX-4000 20 Cured resin

YSLV-80XY

Epicote 807

KEMGARD 911C 25 25 25 9

(E) Molybdenum compound

KEMGARD 911B

Melamine 3 3 3 3 Dicyandiamide 1 1 1 1 Phthalocyanine Blue 1 1 1 1 Barium sulfate 120 120 120 120 Magnesium hydroxide

Carbitol acetate 3 3 3 3

Table 4

The test method is as follows.

(1) Flammability

Halogen-free substrate made by Hitachi Chemical Co., Ltd. MCL-E-6 7 9 FG (0.3 mmt material) was coated on both sides by 30 / m on one side by screen printing, and this test piece conformed to UL 94 flammability test. Measured.

(2) Sensitivity

A puffed copper clad laminate was subjected to the above-mentioned Examples 1 to 4 by screen printing.

8. Each photosensitive resin composition of Comparative Examples 1 to 4 was applied at a thickness of 20 μm (after drying), dried at 80 ° C. for 20 minutes, and then Kodak C ONT RO LS CAL ET-1 4 (Eastman Kodak) is placed on the coating surface, and the scattered light exposure device with blue filter (9-8900, manufactured by Ono Sokki) on the resist surface. Irradiated / cm ² . After that, using a 1% aqueous sodium carbonate solution and developing at a spray pressure of 0.2 MPa for 90 seconds, the number of stages where the photocurable / thermosetting resin coating film remains without being developed. Was the sensitivity.

(3) Tackiness

The puffed copper clad laminate was coated with the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 4 in a thickness of 20 μm (after drying) by screen printing. After drying at 80 ° C. for 20 minutes, the stickiness of the coating film cooled to room temperature was confirmed by touch and evaluated according to the following criteria.

○: No sticky coating

Δ: The coating film has a slight stickiness

X: The film is very sticky

(4) Al power re-developability

The puffed copper-clad laminate was coated with the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 4 in a thickness of 20 μm (after drying) by screen printing. After drying at 80 ° C. at intervals of 10 minutes each, the longest drying time that can be developed in 90 seconds at a spray pressure of 0.2 MPa using a 1% aqueous sodium carbonate solution was measured.

(5) Coating film performance

The photosensitive resin composition of each of Examples 1 to 8 and Comparative Examples 1 to 4 was applied to a conductor circuit (conductor thickness 3 5 Π1) puffed on the conductor circuit by screen printing. After coating at 80 ° C and drying at 80 ° C for 20 minutes, a mask film with a pattern corresponding to the conductor circuit is placed on the coating surface, and a scattered light exposure device with a blue filter ( TN-890B (manufactured by Ono Sokki Co., Ltd.) was irradiated at 500 mJ / cm ² on the resist surface. Thereafter, the film was developed for 90 seconds at a spray pressure of 0.2 MPa using a 1% aqueous sodium carbonate solution. Subsequently, this substrate was thermally cured at 150 ° C. for 60 minutes to prepare a printed wiring board having a cured coating film, and the coating film performance was evaluated.

(Ii) Acid resistance · (5) After immersing the test piece prepared by the method described above in 10% by weight sulfuric acid solution at room temperature for 30 minutes, and thoroughly wiping off the water of the test piece that has been washed, cellophane adhesive tape Name), a peeling test was conducted, and the state of the coating film was visually observed and evaluated according to the following criteria.

○: Things that cannot be changed at all

△: Slight change

: The coating is swollen and peeled

(Mouth) Solvent resistance

(5) After immersing the test piece prepared in the above-mentioned method for 30 minutes in dichloromethane at room temperature, thoroughly wiping off the water of the test piece washed with water, and then performing a peeling test with a cellophane adhesive tape to determine the state of the coating film. It was observed visually and evaluated according to the following criteria.

○: Things that cannot be changed at all

△: Slight change

X: The coating film is swollen and peeled

(C) Gold plating resistance

After performing the gold plating treatment on the test piece prepared by the method described in (5) above, a peeling test was conducted with a cellophane adhesive tape, and the state of the coating film was visually observed and evaluated according to the following criteria.

○: Things that cannot be changed at all

△: Slight change

X: The coating film is swollen and peeled

(2) Solder heat resistance

For the test piece prepared by the method described in (5) above, after being immersed in a solder bath at 26 ° C for 30 seconds in accordance with the test method of JISC 6 4 8 1, the peeling test with cellophane adhesive tape is defined as one cycle. 1 to 3 cycles The state of the coating film after the observation was visually observed and evaluated according to the following criteria. .

◎: No change in coating after 3 cycles

〇: Exfoliation occurs after 3 cycles

Δ: Peeling after 2 cycles

X: Exfoliation occurs after 1 cycle

(E) Pressure-k resistance test

(5) After the test piece prepared by the method described above was treated at 1 2 1 ° 1 00% RH (relative humidity) for 5 o'clock, a peeling test was conducted with a cellophane adhesive tape, The condition was visually observed and evaluated according to the following criteria.

○: Things that cannot be changed at all

△: Slight change

X: The coating film is swollen and peeled

(To) Insulation resistance ■

(5) Using the IPC-TM-650 IPC-SM-8 40 CB-25 test coupon interdigitated electrode as described above in (5) for 500 hours in an atmosphere of 85 ° C and 85% RH. The insulation resistance value of the coating film was measured by applying DC (direct current) 50 V.

From Table 1 above, Examples 1 to 8 achieve combustibility V-0 while sufficiently satisfying the requirements for solder resist.

From Comparative Examples 1 and 2, the flammability V-0 cannot be achieved unless both (A) the active energy ray-curable resin and (E) are contained.

As shown in Comparative Example 3, the use of magnesium hydroxide, which is one of the conventional flame retardant technologies, significantly reduces acid resistance and gold plating resistance, and is a requirement as a solder resist. Can not be satisfied. As shown in Comparative Example 4, (a) When the active energy linear curable resin solution is not used, the “sensitivity” of the photosensitive resin composition is significantly reduced, and the exposure amount is 50 OmJ / cm ² . In this case, it will not be possible to satisfy the requirements as a solder registry.

Claims

The scope of the claims

1. (A) one or more active energy ray-curable resins selected from the group consisting of (A 1) and (A 2),

(A 1) a reaction product of an epoxy resin selected from the group consisting of an epoxy resin of formula (1) and an epoxy resin of formula (2) and an unsaturated monocarboxylic acid, a polybasic acid and a polybasic acid anhydride A resin obtained by reacting with a compound selected from the group consisting of:

(A2) a reaction product of an epoxy resin selected from the group consisting of the epoxy resin of formula (1) and the epoxy resin of formula (2) and an unsaturated monocarboxylic acid, a polybasic acid and a polybasic acid anhydride A resin obtained by reacting a resin selected from a group selected from the group consisting of a glycidyl compound having a radical polymerizable unsaturated group and an epoxy group;

(a) one or more active energy ray-curable resins selected from the group consisting of (al) and (a2),

(a1) selected from the group consisting of an epoxy resin of formula (1) and an epoxy resin other than the epoxy resin of formula (2) and an unsaturated monocarboxylic acid, and a polybasic acid and polybasic acid anhydride Resin obtained by reacting with the compound obtained,

(a2) selected from the group consisting of an epoxy resin of the formula (1) and an epoxy resin other than the epoxy resin of the formula (2) and an unsaturated monocarboxylic acid, a polybasic acid and a polybasic acid anhydride A resin obtained by further reacting a resin obtained by reacting the compound with a glycidyl compound having a radical polymerizable unsaturated group and an epoxy group,

(B) a photopolymerization initiator,

(C) a reactive diluent, (D) an epoxy resin selected from the group consisting of an epoxy resin of formula (1) and an epoxy resin of formula (2);

(d) an epoxy resin of formula (1) and an epoxy resin other than the epoxy resin of formula (2), and

(E) A photosensitive resin composition comprising a molybdenum compound.

10 or less)

(2)

(n = 1 or more, 10 or less)

2. A printed wiring board before or after mounting an electronic component, comprising the photosensitive resin composition according to claim 1.

3. A semiconductor package substrate having the photosensitive resin composition according to claim 1 before or after mounting an electronic component.