JP5183425B2 - Flame-retardant photocurable resin composition, dry film and cured product thereof, and printed wiring board using them - Google Patents

Description

  The present invention relates to a flame retardant photocurable resin composition that can be developed with a dilute alkaline aqueous solution, in particular, a solder resist composition that is photocured by ultraviolet exposure or laser exposure, its dry film and cured product, and using them. The present invention relates to a printed wiring board having a formed flame-retardant cured film.

  Conventionally, printed wiring boards and flexible wiring boards (hereinafter abbreviated as FPC) have been required to be flame retardant because they are mounted on electronic devices, and solder resist, which is a part of these, also requires flame resistance. Has been. Among these, since the FPC is usually made of a polyimide substrate, it is a thin film unlike a printed wiring board of a glass epoxy substrate. However, since the solder resist to be applied has the same film thickness on both the printed wiring board and the FPC, in the case of a thin-film FPC, the burden on the solder resist is relatively increased.

  For this reason, various proposals have conventionally been made on the flame resistance of solder resist. For example, Japanese Patent Application Laid-Open No. 2007-10794 (Patent Document 1) describes (a) a binder polymer, (b) a halogenated aromatic ring such as a bromophenyl group, and a polymerizable ethylenic group such as a (meth) acryloyl group. Flame retardant for FPC containing a photopolymerizable compound having a saturated bond in the molecule, (c) a photopolymerization initiator, (d) a blocked isocyanate compound, and (e) a phosphorus-containing compound having a phosphorus atom in the molecule Photosensitive resin compositions have been proposed. However, the use of a halogen compound such as a compound having an unsaturated double bond polymerizable with a halogenated aromatic ring is not preferable from the viewpoint of environmental load.

In contrast, JP-A-2001-75270 (Patent Document 2) describes (a) epoxy acrylate resin, (b) epoxy resin, (c) diluent, (d) curing agent, and (e) curing acceleration. Agent, (f) sensitizer, (g) phosphazene oligomer and (h) inorganic filler as essential components, and the phosphazene oligomer of (g) is contained in a proportion of 2 to 50% by weight based on the entire resin composition. In the photosensitive resin composition characterized by containing, Unexamined-Japanese-Patent No. 2005-283762 (patent document 3), (a) It has a (meth) acryloyl group and a carboxyl group in 1 molecule, A photosensitive composition containing a resin component soluble in a dilute alkali solution, (b) a thermosetting component, (c) a photopolymerization initiator, (d) a phosphazene compound, and (e) a diluent is proposed. Has been. However, it is confirmed that the phosphazene compounds exemplified in these materials are once dissolved in the photosensitive composition and recrystallized during storage, or crystals precipitate over time after coating and drying the composition. However, there is a problem in the stability as a liquid composition and a dry film, and further, when it exists as a large recrystallized grain in a cured film, a problem occurs that a crack is generated at the time of bending from that point. Therefore, only a very small amount of the phosphazene compound can be used, and the flame retardant effect was very low.
JP 2007-10794 A (Claims) JP 2001-75270 A (Claims) JP 2005-283762 A (Claims)

The present invention has been made in view of the prior art as described above, has a non-halogen composition, has a low environmental load, is excellent in both flame retardancy and storage stability, is rich in flexibility of a cured film, and is suitable for various substrates. A flame retardant photocurable resin composition that can form a cured film with a fine pattern that is excellent in adhesion, solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, etc., and is particularly suitable for FPC It is intended to provide.
Furthermore, the object of the present invention is to provide a flame retardant dry film and cured product excellent in the above-mentioned various characteristics obtained by using such a photocurable resin composition, and a solder with the dry film or cured product. An object of the present invention is to provide a printed wiring board on which a flame-retardant cured film such as a resist is formed.

In order to achieve the above object, according to the present invention, (A) a carboxyl group-containing resin, (B) a soluble phosphazene compound that is soluble in the carboxyl group-containing resin (A) or its varnish by 5 wt% or more , ( C A flame-retardant photocurable resin composition comprising a photopolymerization initiator and (E) a thermosetting resin , wherein the thermosetting resin (E) includes an epoxy resin having a biphenyl skeleton. Is done. Preferably, the carboxyl group-containing resin (A) is a carboxyl group-containing polyurethane resin, and the phosphazene compound (B) is preferably a solid phenoxyphosphazene compound having a substituent containing a nitrogen atom.
In a preferred embodiment, that Yusuke contains further (D) a photopolymerizable monomer. In this case, the phosphazene compound (B), it is not preferable to photopolymerizable monomer (D) is more than 5 wt% soluble. Flame-retardant curable resin composition, in particular a photocurable and thermosetting resin composition of the flame retardant containing a thermosetting resin (E) such as this can be used suitably as a solder resist .

Further, according to the present invention, a flame retardant photocurable dry film obtained by applying and drying the flame retardant photocurable resin composition on a carrier film, or the flame retardant photocurable resin. A flame retardant cured product obtained by curing the composition or the dry film is also provided.
Furthermore, according to this invention, the printed wiring board characterized by having the flame-retardant cured film obtained by hardening | curing the said flame-retardant photocurable resin composition or a dry film is also provided.

The flame-retardant photocurable resin composition of the present invention uses a carboxyl group-containing resin (A) and a soluble phosphazene compound (B) that is soluble in the carboxyl group-containing resin (A) or its varnish by 5 wt% or more. Therefore, there is no phenomenon that the phosphazene compound once dissolved in the photocurable resin composition is recrystallized during storage or crystals are deposited with time after coating and drying as in the prior art. It can be blended in a relatively large amount, the flame retardancy effect becomes very large, and the stability as a liquid composition and a dry film is excellent. Therefore, non-halogen composition with low environmental impact and excellent flame retardancy, rich cured film flexibility, adhesion to various substrates, solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, etc. Can form a cured film with a fine pattern.
Therefore, the flame-retardant photocurable resin composition of the present invention can be advantageously applied to the formation of a flame-retardant cured film such as a printed wiring board, particularly an FPC solder resist.

  As described above, the flame-retardant photocurable resin composition of the present invention is characterized by the solubility that is 5 wt% or more in the carboxyl group-containing resin (A) or its varnish together with the carboxyl group-containing resin (A). The phosphazene compound (B) is used. As a result, there is no phenomenon in which the phosphazene compound once dissolved in the photocurable resin composition is recrystallized during storage or crystals are deposited with time after coating and drying as in the past. Excellent stability as a film.

As the carboxyl group-containing resin (A) contained in the flame retardant photocurable resin composition of the present invention, a known and commonly used resin compound containing a carboxyl group in the molecule can be used. Furthermore, it is preferable to use a carboxyl group-containing photosensitive resin (A ′) having an ethylenically unsaturated double bond in the molecule because photocurability can be imparted and an alkali developable composition is obtained. The unsaturated double bond is preferably derived from (meth) acrylic acid or a (meth) acrylic acid derivative. In addition, when using only the carboxyl group-containing resin which does not have an ethylenically unsaturated double bond, in order to make a composition photocurable, it has two or more ethylenically unsaturated groups in the molecule | numerator mentioned later. It is necessary to use a photopolymerizable monomer (D) in combination.
As specific examples of the carboxyl group-containing resin (A), compounds listed below (any of oligomers and polymers) can be suitably used.

(1) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(2) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( Photosensitive carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its modified partial anhydride, carboxyl group-containing dialcohol compound and diol compound.
(3) During the synthesis of the resin of the above (1) or (2), a compound having one hydroxyl group and one or more (meth) acryl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( Photosensitive carboxyl group-containing urethane resin that has been meta-acrylated.
(4) During the synthesis of the resin of the above (1) or (2), one isocyanate group and one or more (meth) acryl groups are introduced into the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. The photosensitive carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.
(5) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
(6) A photosensitive carboxyl group obtained by reacting a bifunctional or higher polyfunctional (solid) epoxy resin as described later with (meth) acrylic acid and adding a dibasic acid anhydride to the hydroxyl group present in the side chain. Containing resin.
(7) Photosensitivity in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and a dibasic acid anhydride is added to the resulting hydroxyl group. Functional carboxyl group-containing resin.
(8) A carboxyl group-containing polyester resin obtained by reacting a bifunctional oxetane resin as described later with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.
(9) A photosensitive carboxyl group-containing resin obtained by adding a compound having one epoxy group and one or more (meth) acryl groups in one molecule to the resins (1) to (8).

Among these carboxyl group-containing resins, preferred are (X) carboxy group-containing urethane resins, particularly those in which the isocyanate groups of the urethane resin having isocyanate groups (including diisocyanates) are not directly bonded to the benzene ring. From the viewpoint of photosensitivity and flexibility, (Y) the polyfunctional epoxy resin used in the synthesis of the resins of (6) and (7) above is bisphenol A structure, bisphenol F structure, biphenol structure, bisxylenol. In the case of a compound having a structure and its hydrogenated compound, it is preferable from the viewpoints of heat resistance and flame retardancy. Further, in another aspect, the carboxylic group-containing urethane resins (1), (2), (3), and (4) and modified products such as (9) have a urethane bond in the main chain. And preferred for warping. Furthermore, in order to achieve both properties such as flexibility and solder heat resistance, the carboxyl group-containing urethane resins (1), (2), (3), (4) and modified products such as those (9) And, it is most preferable to use the carboxyl group-containing resins (5), (6), (7) and (8) and modified products such as (9) in combination.
In the present specification, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

Since the carboxyl group-containing resin (A) as described above has a large number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute aqueous alkali solution is possible.
The acid value of the carboxyl group-containing resin (A) is desirably in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary. Depending on the case, the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.

  Moreover, although the weight average molecular weight of the said carboxyl group-containing resin (A) changes with resin frame | skeletons, what is generally in the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. When the weight average molecular weight is less than 2,000, the tack-free performance of the coating film may be inferior, the moisture resistance of the coating film after exposure may be poor, the film may be reduced during development, and the resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.

  The amount of the carboxyl group-containing resin (A) as described above is 10 to 60% by mass, preferably 20 to 50% by mass in the total composition. When the amount is less than the above range, the coating strength is lowered, which is not preferable. On the other hand, when the amount is larger than the above range, the viscosity of the composition is increased or the coating property is lowered, which is not preferable.

式中、ｎは３〜１５の整数であり、Ｒ^１、Ｒ^２は、それぞれ独立して、それぞれ少なくとも１つ以上が有機基で置換されている、炭素数１〜８のアルコキシ基、フェノキシ基及びアリールオキシ基から選ばれる基である。ここで、置換している有機基は、フッ素を除くハロゲン基以外であり、好ましくは極性基、さらに好ましくは窒素原子を含む置換基を有しているものが良い。特に、Ｒ^１とＲ^２は共に窒素原子を含む置換基を有するフォノキシ基であることが好ましい。
また、一般式（Ｉ）で表されるホスファゼン化合物は、線状又は環状であってもよく、複数の混合物で分子量分布を持っていてもよい。
前記のような可溶性ホスファゼン化合物（Ｂ）の具体例としては、シアノフェノキシ構造を有するフェノキシホスファゼン化合物（伏見製薬所社製ＦＰ−３００）やフェノール性水酸基含有フェノキシホスファゼンなどがある。 As the soluble phosphazene compound (B) contained in the flame retardant photocurable resin composition of the present invention, an organic solvent, a carboxyl group-containing resin or a varnish thereof, preferably an epoxy resin which is another composition component, and further a photosensitive property. Those that are soluble in the resin are preferred, and those having the characteristics listed below are particularly preferred.
-Halogen free (other than ionic impurities).
-5% weight loss is 260 ° C or higher.
-It is a compound which has a structure shown by the following general formula (I).

In the formula, n is an integer of 3 to 15, and R ¹ and R ² are each independently an alkoxy group having 1 to 8 carbon atoms or a phenoxy group, each of which is substituted with at least one organic group. And a group selected from aryloxy groups. Here, the substituted organic group is other than a halogen group excluding fluorine, preferably a polar group, more preferably a substituent having a nitrogen atom. In particular, both R ¹ and R ² are preferably phonoxy groups having a substituent containing a nitrogen atom.
Further, the phosphazene compound represented by the general formula (I) may be linear or cyclic, and may have a molecular weight distribution in a plurality of mixtures.
Specific examples of the above-described soluble phosphazene compound (B) include a phenoxyphosphazene compound having a cyanophenoxy structure (FP-300 manufactured by Fushimi Pharmaceutical Co., Ltd.) and a phenolic hydroxyl group-containing phenoxyphosphazene.

The soluble phosphazene compound (B) used in the present invention is particularly preferably soluble in the carboxyl group-containing resin (A) or its varnish. In general, phosphazene compounds, particularly heat-resistant phenoxyphosphazene compounds, are particularly poorly soluble in the carboxyl group-containing resin (A) and the photopolymerizable monomer (D). According to the preliminary experiments by the present inventors, the unsubstituted phenoxyphosphazene oligomer is a phenomenon in which crystals are precipitated even when the concentration is about 5 wt% after heating, dissolving and cooling the carboxyl group-containing resin (A) or its varnish. It was observed. Similarly, the unsubstituted phenoxyphosphazene oligomer was precipitated at a concentration of 5 wt% with respect to the photopolymerizable monomer (D).
Table 1 shows the solubility of the phenoxyphosphazene oligomer in a carboxyl group-containing resin (ZFR1601: Nippon Kayaku Co., Ltd. acid-modified epoxy acrylate solid content 70% carbitol acetate cut varnish).

Table 2 shows the solubility of the phenoxyphosphazene oligomer in the photopolymerizable monomer.

On the other hand, the epoxy resin showed relatively good solubility, but similarly, the cyano group-substituted phosphazene oligomer had higher solubility. Table 3 shows the solubility of the phenoxyphosphazene oligomer in the epoxy resin.

Furthermore, the solvent used for dilution of the composition was similarly evaluated. The results are shown in Table 4. Phenoxyphosphazene has a good solubility compared to the above-mentioned resin and is considerably dissolved. However, phenoxyphosphazene has a solubility of 5 wt% or less with respect to polar dipropylene glycol methyl ether containing a hydroxyl group, and also has a low polarity in toluene. On the other hand, contrary to the above results, phenoxyphosphazene substituted with a polar group (cyano group) crystallized at 25 wt%. On the other hand, in the aprotic polar solvents such as ketones such as methyl ethyl ketone and cyclohexanone, and N-methylpyrrolidone and γ-butyrolactone, the result of dissolving 25 wt% or more of any phosphazene oligomer was obtained.

From the results shown in Tables 1 to 4, while being diluted with an aprotic polar solvent or the like, any phosphazene compound is stable without precipitating, but when a dry coating film such as a dry film is formed. It is considered that the unsubstituted phosphazene compound is highly likely to precipitate. On the other hand, in the case of a phosphazene compound having a polar substituent such as a cyano group, it can be dissolved in a carboxyl group-containing resin varnish or a photopolymerizable monomer in an amount of 5 wt% or more, and the amount of the phosphazene compound is reduced to a concentration effective for flame retardancy. It can be increased and sufficient flame retardancy can be achieved.
The present invention aims to prevent crystals from being precipitated in the state of the photocurable resin composition, the dry film, and the cured film. If particles due to recrystallization of phosphazene are not observed at the stage of the dry coating before curing and at the stage of the coating after curing, the objective can be achieved, so it must be soluble in all composition components. Absent.

  A suitable blending amount of the soluble phosphazene compound (B) is 5 to 50 parts by mass, more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). If the blending amount of the soluble phosphazene compound (B) is less than the above range, sufficient flame retardancy of the resulting cured film cannot be obtained. It is not preferable because good results cannot be obtained.

式中、Ｒ^３及びＲ^４は、それぞれ独立に、炭素数１〜１０の直鎖状又は分岐状のアルキル基、炭素数１〜１０の直鎖状又は分岐状のアルコキシ基、シクロヘキシル基、シクロペンチル基、アリール基、又はハロゲン原子、アルキル基もしくはアルコキシ基で置換されたアリール基を表し、但し、Ｒ^３及びＲ^４の一方は、Ｒ−Ｃ（＝Ｏ）−基（ここでＲは、炭素数１〜２０の炭化水素基）を表してもよい。 As the photopolymerization initiator (C) used in the present invention, known and commonly used compounds can be used.
As a particularly preferred photopolymerization initiator, there is a phosphorus element-containing photopolymerization initiator, which has an effect of improving flame retardancy while being a photopolymerization initiator. As such a phosphorus element-containing photopolymerization initiator, an acylphosphine oxide photopolymerization initiator having a group represented by the following general formula (II-1) can be preferably used.

In the formula, R ³ and R ⁴ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a cyclohexyl group, or cyclopentyl. A group, an aryl group, or an aryl group substituted with a halogen atom, an alkyl group or an alkoxy group, provided that one of R ³ and R ⁴ is an R—C (═O) — group (where R is carbon (Hydrocarbon group of 1 to 20).

  Examples of the acylphosphine oxide photopolymerization initiator having the group represented by the general formula (II-1) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl)- Examples thereof include phenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO manufactured by BASF and Irgacure (registered trademark) 819 manufactured by Ciba Specialty Chemicals.

式中、Ｒ^３は前記と同様の意味を有し、Ｒ^５は、炭素数１〜１０の直鎖状又は分岐状のアルキル基、炭素数１〜１０の直鎖状又は分岐状のシクロヘキシル基、シクロペンチル基、アリール基、又はハロゲン原子、アルキル基で置換されたアリール基を表し、Ｒ−Ｃ（＝Ｏ）−基（ここでＲは、炭素数１〜２０の炭化水素基）を表してもよい。 Another preferable phosphorus element-containing photopolymerization initiator is an initiator represented by the following general formula (II-2), and a commercially available product is Lucilin TPO-L manufactured by BASF.

In the formula, R ³ has the same meaning as described above, and R ⁵ is a linear or branched alkyl group having 1 to 10 carbon atoms or a linear or branched cyclohexyl group having 1 to 10 carbon atoms. Represents a cyclopentyl group, an aryl group, or an aryl group substituted with a halogen atom or an alkyl group, and represents an R—C (═O) — group (where R is a hydrocarbon group having 1 to 20 carbon atoms). Also good.

  The compounding amount of such a phosphorus element-containing photopolymerization initiator is 5 to 80 parts by mass, preferably 10 to 50 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A).

式中、Ｒ^６は、水素原子、フェニル基（炭素数１〜６のアルキル基、フェニル基、もしくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基もしくはフェニル基で置換されていてもよい）を表し、
Ｒ^７は、フェニル基（炭素数１〜６のアルキル基、フェニル基もしくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基もしくはフェニル基で置換されていてもよい）を表し、
Ｒ^８及びＲ^９は、それぞれ独立に、炭素数１〜１２のアルキル基又はアリールアルキル基を表し、
Ｒ^１０及びＲ^１１は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、又は２つが結合した環状アルキルエーテル基を表す。 The photopolymerization initiator that can be added in addition to the phosphorus element-containing photopolymerization initiator includes an oxime ester photopolymerization initiator having a group represented by the following general formula (III), represented by the following general formula (IV): There are α-aminoacetophenone photopolymerization initiators having the following groups.

In the formula, R ⁶ represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R ⁷ is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups). Well, it may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having 1 to 6 carbon atoms) Which may be substituted with an alkyl group or a phenyl group of
R ⁸ and R ⁹ each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group,
R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded.

The oxime ester photopolymerization initiator having a group represented by the general formula (III) is preferably 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the following formula (V), The compound represented by the following general formula (VI) and the compound represented by the following general formula (VII) are mentioned.

式中、Ｒ^１２は、水素原子、ハロゲン原子、炭素数１〜１２のアルキル基、シクロペンチル基、シクロヘキシル基、フェニル基、ベンジル基、ベンゾイル基、炭素数２〜１２のアルカノイル基、炭素数２〜１２のアルコキシカルボニル基（アルコキシル基を構成するアルキル基の炭素数が２以上の場合、アルキル基は１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、又はフェノキシカルボニル基を表し、
Ｒ^１３、Ｒ^１５は、それぞれ独立に、フェニル基（炭素数１〜６のアルキル基、フェニル基もしくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基もしくはフェニル基で置換されていてもよい）を表し、
Ｒ^１４は、水素原子、フェニル基（炭素数１〜６のアルキル基、フェニル基もしくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基もしくはフェニル基で置換されていてもよい）を表す。

In the formula, R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, or 2 to 2 carbon atoms. 12 alkoxycarbonyl groups (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, and one or more oxygen atoms are placed in the middle of the alkyl chain. Which may have), or a phenoxycarbonyl group,
R ¹³ and R ¹⁵ are each independently a phenyl group (which may be substituted with a C 1-6 alkyl group, a phenyl group or a halogen atom), a C 1-20 alkyl group (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R ¹⁴ is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (substituted with one or more hydroxyl groups). And may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having a carbon number). 1-6 alkyl groups or phenyl groups optionally substituted).

式中、Ｒ^１６、Ｒ^１７及びＲ^２２は、それぞれ独立に、炭素数１〜１２のアルキル基を表し、
Ｒ^１８、Ｒ^１９、Ｒ^２０及びＲ^２１は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表し、
Ｍは、Ｏ、Ｓ又はＮＨを表し、
ｍ及びｐは、それぞれ独立に０〜５の整数を表す。

In the formula, R ¹⁶ , R ¹⁷ and R ²² each independently represent an alkyl group having 1 to 12 carbon atoms,
R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
M represents O, S or NH;
m and p each independently represents an integer of 0 to 5.

  Among the oxime ester photopolymerization initiators described above, 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the formula (V) and a compound represented by the formula (VI) are more preferable. Examples of commercially available products include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Specialty Chemicals, N-1919 manufactured by ADEKA Corporation, and the like. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.

  Examples of the α-aminoacetophenone photopolymerization initiator having a group represented by the general formula (IV) include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone, N, N-dimethylaminoacetophenone and the like. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.

The amount of the photopolymerization initiator (C) as described above is 0.01 to 50 parts by mass, preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). Is appropriate. When the blending amount of the photopolymerization initiator (C) is less than 0.01 parts by mass, the photocurability on copper is insufficient, and the coating film is peeled off or the coating properties such as chemical resistance are deteriorated. Therefore, it is not preferable. On the other hand, if it exceeds 50 parts by mass, light absorption on the surface of the solder resist coating film of the photopolymerization initiator (C) becomes violent and the deep curability tends to decrease, which is not preferable.
In the case of the oxime ester photopolymerization initiator having a group represented by the formula (III), the blending amount is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). 20 mass parts, More preferably, the range of 0.01-5 mass parts is desirable.

  Other photopolymerization initiators, photoinitiator assistants, and sensitizers that can be suitably used in the photocurable resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenones. A compound, a xanthone compound, a tertiary amine compound, etc. can be mentioned.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone.

Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.
Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.

Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.
Specific examples of the benzophenone compound include, for example, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, 4-benzoyl-4′-propyldiphenyl. Sulfide.

  Specific examples of the tertiary amine compound include, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4,4′-diethylamino. Dialkylamino benzophenone such as benzophenone (EAB manufactured by Hodogaya Chemical Co.), and dialkylamino groups such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin) Containing coumarin compound, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-dimethylaminobenzoic acid ( -Butoxy) ethyl (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (manufactured by Van Dyk) Esolol 507), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.).

Among the above-mentioned compounds, thioxanthone compounds and tertiary amine compounds are preferable. The composition of the present invention preferably contains a thioxanthone compound from the viewpoint of deep curable properties. Among them, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone A thioxanthone compound such as
The amount of such a thioxanthone compound is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the carboxyl group-containing resin (A). If the amount of the thioxanthone compound is too large, the thick film curability is lowered and the cost of the product is increased, which is not preferable.

  As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable. As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. The dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has a maximum absorption wavelength in the ultraviolet region, so that it is less colored and uses a colored pigment as well as a colorless and transparent photosensitive composition. A colored solder resist film reflecting the color can be provided. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

  The amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). Is appropriate. When the amount of the tertiary amine compound is 0.1 parts by mass or less, there is a tendency that a sufficient sensitizing effect cannot be obtained. When the amount exceeds 20 parts by mass, light absorption on the surface of the dried solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease.

These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more.
The total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably in a range of 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin (A). When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

  As described above, when only a carboxyl group-containing resin having no ethylenically unsaturated double bond is used, in order to make the composition photocurable, two or more ethylenically unsaturated groups are contained in the molecule. It is necessary to use together the photopolymerizable monomer (D) which has. The compounding quantity of a photopolymerizable monomer (D) is 1-100 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (A), More preferably, the ratio of 10-80 mass parts is desirable. When the blending amount is less than 1 part by mass, the photocurability is lowered, and pattern development becomes difficult by alkali development after irradiation with active energy rays, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the dryness to the touch is poor or the solder heat resistance is inferior.

  As the photopolymerizable monomer (D) blended to form an image with light in the composition of the present invention, a conventionally known (meth) acrylate monomer can be used. Commonly known (meth) acrylate monomers include glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl. Polyhydric alcohols such as isocyanurates or polyhydric acrylates such as these ethylene oxide adducts, propylene oxide adducts or caprolactone adducts; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene of these phenols Polyhydric acrylates such as oxide adducts; and urethane acrylates of the above polyalcohols; Phosphorus diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or the like each methacrylates corresponding to the acrylates.

式中、Ｒ^２３はアクリレート残基であり、Ｒ^２４とＲ^２５は水素もしくはハロゲン以外の有機基であるアクリレート誘導体である。このようなリン含有化合物変性アクリレートは、一般に、９，１０−ジヒドロー９−オキサ−１０−フォスファフェナンスレン−１０−オキサイドと慣用公知の多官能アクリレートとのマイケル付加反応により合成することができる。 Among the (meth) acrylate monomers, a phosphorus element-containing acrylate is preferable from the viewpoint of flame retardancy. For example, phosphate polyfunctional acrylates typified by trisacryloyloxyethyl phosphate, or specifically phosphorus-containing compound-modified acrylates represented by the following general formula (VIII) can be mentioned.

In the formula, R ²³ is an acrylate residue, and R ²⁴ and R ²⁵ are acrylate derivatives which are organic groups other than hydrogen or halogen. Such phosphorus-containing compound-modified acrylates can generally be synthesized by a Michael addition reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with a conventionally known polyfunctional acrylate. .

  In order to give heat resistance to the photocurable resin composition of this invention, a thermosetting resin (E) can be added as a thermosetting component. Particularly preferred is a thermosetting component (E) having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule. Among these, a bifunctional epoxy resin is preferable, and diisocyanate or its polyfunctional blocked isocyanate can also be used.

  The thermosetting component (E) having two or more cyclic (thio) ether groups in such a molecule is either a three-, four- or five-membered cyclic ether group or a cyclic thioether group in the molecule. Or a compound having two or more of two kinds of groups, for example, a compound having at least two epoxy groups in the molecule, that is, a polyfunctional epoxy compound (E-1), and at least two oxetanyl in the molecule A compound having a group, that is, a polyfunctional oxetane compound (E-2), a compound having two or more thioether groups in the molecule, that is, an episulfide resin (E-3), and the like.

  As the polyfunctional epoxy compound (E-1), for example, JER828, JER834, JER1001, JER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 1050, Epicron 2055, Toto, manufactured by Dainippon Ink & Chemicals, Inc. Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Kasei Co., Ltd., D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Specialty Chemicals' Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Industries Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo Co., Ltd. A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. 664 etc. (all trade names) bisphenol A type epoxy resin; Japan Epoxy Resin JERYL903, Dainippon Ink & Chemicals Epicron 152, Epicron 165, Toto Kasei Epototo YDB-400, YDB-500 D. Chemicals manufactured by Dow Chemical Company. E. R. 542, Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.D. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (all trade names); JER152 and JER154 manufactured by Japan Epoxy Resin, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, Etototo YDCN-701, YDCN-704 from Toto Kasei Co., Ltd., Araldide ECN1235 from Ciba Specialty Chemicals, Araldide ECN1273, Araldide ECN1299, Araldide XPY307, Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Industries Sumi-epoxy ESCN-195X, ESCN- 220, manufactured by Asahi Kasei Corporation. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by Dainippon Ink & Chemicals, JER807 manufactured by Japan Epoxy Resin, Epotot YDF-170 manufactured by Toto Kasei Co., YDF- 175, YDF-2004, Araldide XPY306 manufactured by Ciba Specialty Chemicals, etc. (both trade names); Epototo ST-2004, ST-2007, ST-3000 (trade names, manufactured by Toto Kasei) Hydrogenated bisphenol A type epoxy resin such as JER604 manufactured by Japan Epoxy Resin Co., Epotot YH-434 manufactured by Toto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Specialty Chemicals Co., Ltd., Sumi-Epoxy ELM manufactured by Sumitomo Chemical Co., Ltd. -120 etc. (both Product name) glycidylamine type epoxy resin; Hydantoin type epoxy resin such as LARDAID CY-350 (trade name) manufactured by Ciba Specialty Chemicals; Celoxide 2021 manufactured by Daicel Chemical Industries, Araldide manufactured by Ciba Specialty Chemicals CY175, CY179, etc. (both trade names); YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Japan Epoxy Resin YL-6056, YX-4000, YL-6121 (all trade names), etc. Xylenol type or biphenol type epoxy resin or a mixture thereof; bisphenol S type such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin; Bisphenol A novolak type epoxy resin such as JER157S (trade name) manufactured by Japan Epoxy Resin; YL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Specialty Chemicals, etc. (all trade names) Tetraphenylolethane type epoxy resin; Bicyclic novolac resins such as NC-3000 and NC-3100 manufactured by Nippon Kayaku Co., Ltd .; Araldide PT810 manufactured by BA Specialty Chemicals, TEPIC manufactured by Nissan Chemical Industries, Ltd. (both trade names) Diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; tetraglycidyl xylenoyl ethane resin such as ZX-1063 manufactured by Tohto Kasei Co., Ltd .; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., manufactured by Dainippon Ink & Chemicals, Inc. Naphthalene group-containing epoxy resins such as HP-4032, EXA-4750, and EXA-4700; Epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink and Chemicals; CP- manufactured by Nippon Oil & Fats Co., Ltd. 50S, CP-50M and other glycidyl methacrylate Compound epoxy resin; Copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Daicel Chemical Industries), CTBN-modified epoxy resin (for example, YR-102 manufactured by Tohto Kasei Co., Ltd.) , YR-450 and the like), but is not limited thereto. These epoxy resins can be used alone or in combination of two or more. Among these, an epoxy resin having a biphenyl skeleton such as a biphenyl novolac type epoxy resin is particularly preferable.

  Examples of the polyfunctional oxetane compound (E-2) include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3- In addition to polyfunctional oxetanes such as ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane Alcohol and novolak resin, poly (p-hydroxystyrene), cardo type Scan phenols, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Examples of the compound (E-3) having two or more cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resins. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

  The amount of the thermosetting component (E) having two or more cyclic (thio) ether groups in the molecule is preferably 0.6 relative to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A). -2.5 equivalent, More preferably, it exists in the range used as 0.8-2.0 equivalent. When the blending amount of the thermosetting component (E) having two or more cyclic (thio) ether groups in the molecule is less than 0.6 equivalents, carboxyl groups remain in the solder resist film, heat resistance, alkali resistance, This is not preferable because the electrical insulation property is lowered. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.

式中、Ｒ^２６、Ｒ^２７及びＲ^２８は、それぞれ独立に、ハロゲン原子以外の置換基を示す。
上記一般式（IX）で表される化合物の市販品としてはＨＣＡ、ＳＡＮＫＯ−２２０、Ｍ−ＥＳＴＥＲ、ＨＣＡ−ＨＱ等がある。 The photocurable resin composition of the present invention can further contain a phosphorus-containing compound as a flame retardant auxiliary. As the phosphorus-containing compound, those conventionally known as organic phosphorus flame retardants may be used, and examples include phosphoric acid esters and condensed phosphoric acid esters, cyclic phosphazene compounds, phosphazene oligomers, and compounds represented by the following general formula (IX).

In the formula, R ²⁶ , R ²⁷ and R ²⁸ each independently represent a substituent other than a halogen atom.
Commercial products of the compound represented by the general formula (IX) include HCA, SANKO-220, M-ESTER, HCA-HQ and the like.

  When using the thermosetting component (E) having two or more cyclic (thio) ether groups in the molecule, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide; benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, as long as it is a thermosetting catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with the thermosetting catalyst.

  The compounding amount of these thermosetting catalysts is sufficient in the usual quantitative ratio, for example, a carboxyl group-containing resin (A) or a thermosetting component (E) having two or more cyclic (thio) ether groups in the molecule. Preferably it is 0.1-20 mass parts with respect to 100 mass parts, More preferably, it is 0.5-15.0 mass parts.

  The photocurable resin composition of this invention can mix | blend a coloring agent. As the colorant, conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and dyes may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.

Blue colorant:
Blue colorants include phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds classified as Pigment, specifically, the following color index (CI; The Society of Dyers and Colorists) (Issued by The Society of Dyers and Colorists) can be listed with numbers: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4 , Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60.
The dye systems include Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant:
Similarly, green colorants include phthalocyanine, anthraquinone, and perylene. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. are used. be able to. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant:
Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.
Isoindolinone type: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.
Condensed azo series: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.
Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.
Monoazo: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116 , 167, 168, 169, 182, 183.
Disazo: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

Red colorant:
Examples of red colorants include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. It is done.
Monoazo: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.
Disazo: Pigment Red 37, 38, 41.
Monoazo lakes: Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1,68.
Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.
Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.
Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.
Condensed azo series: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 and Pigment Red 242.
Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.
Kinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

In addition, a colorant such as purple, orange, brown, or black may be added for the purpose of adjusting the color tone.
Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black And the like.

  The blending ratio of the colorant as described above is not particularly limited, but is preferably 0 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). Is sufficient.

  The photocurable resin composition of the present invention can be blended with a filler as necessary in order to increase the physical strength of the coating film. As such a filler, at least one selected from the group consisting of known and commonly used inorganic fillers and organic fillers can be used, but inorganic fillers, particularly barium sulfate, spherical silica and talc are preferably used. Furthermore, it is good also as a white resist by adding a titanium oxide as a white filler. In order to further impart flame retardancy, metal oxide fine particles may be added, and specific examples include aluminum hydroxide, magnesium hydroxide, boehmite and the like. These fillers can be blended alone or in combination of two or more.

  The blending amount of these fillers is preferably 300 parts by mass or less, more preferably 0.1 to 300 parts by mass, and particularly preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). Part. When the blending amount of the filler exceeds 300 parts by mass, it is not preferable because the viscosity of the photocurable resin composition becomes high and the printability is lowered or the cured product becomes brittle.

Furthermore, the photocurable resin composition of the present invention uses an organic solvent for the synthesis of the carboxyl group-containing resin (A) and the preparation of the composition, or for adjusting the viscosity for application to a substrate or a carrier film. can do.
Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, hydrocarbons such as toluene, xylene, solvent naphtha, normal hexane, cyclohexane, and normal heptane that are suitably used in the composition, alcohols such as ethanol, isopropanol, and 2-ethylhexyl alcohol, acetone, methyl ethyl ketone, Ketones such as methyl isobutyl ketone, cyclohexanone, diacetone alcohol, ester groups such as ethyl acetate, butyl acetate, cellosolve acetate, methyl lactate, butyl lactate, ethyl lactate, methyl cellosolve, cellosolve, butyl cellosolve, carbitol, butyl carbitol , Diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diglyme, triglyme, propylene glycol monomethyl ether, 3-methoxy Glycol ethers such as 3-methyl-1-butanol and dipropylene glycol monomethyl ether, glycols such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, carbitol acetate and dipropylene glycol monomethyl ether acetate Ester, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, etc., ethyl 3-ethoxypropionate, dibasic acid ester, dimethyl carbonate, N, N-dimethylformamide, N-methyl-2-pyrrolidone 1,3-dioxolane, γ-butyrolactone, dimethyl sulfoxide, dimethylformamide And the like. Such organic solvents are used alone or as a mixture of two or more.

  The photocurable resin composition of the present invention may further include, as necessary, known and commonly used thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, and phenothiazine, finely divided silica, organic bentonite, and montmorillonite. Known and commonly used thickeners, silicone-based, fluorine-based and polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, antioxidants, rust inhibitors, etc. The known and conventional additives such as can be blended.

The photocurable resin composition of the present invention can also be in the form of a dry film comprising a carrier film (support) and a layer made of the photocurable resin composition formed on the carrier film. .
When forming a dry film, the photocurable resin composition of the present invention is diluted with the above organic solvent to adjust to an appropriate viscosity, and is applied to a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll. A film can be obtained by applying a uniform thickness on a carrier film with a coater, gravure coater, spray coater or the like and drying at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Although there is no restriction | limiting in particular about a coating film thickness, Generally, it is 10-150 micrometers by the film thickness after drying, Preferably it selects suitably in the range of 20-60 micrometers.

  As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used. Although there is no restriction | limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers.

After the film is formed on the carrier film, it is desirable to further laminate a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film.
As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, etc. can be used, and when the cover film is peeled off, the adhesive strength between the film and the carrier film What is necessary is just to have a smaller adhesive force between the membrane and the cover film.

  Moreover, the photocurable resin composition which concerns on this invention, or this dry film turns into hardened | cured material by photocuring on copper. Photocuring can be performed by an ultraviolet exposure device, but it can also be cured by laser light having a wavelength of 350 to 410 nm.

  Specifically, a dry film, a cured product, and a printed wiring board are formed as follows. That is, the photocurable resin composition of the present invention is adjusted to a viscosity suitable for the coating method using, for example, the organic solvent, and is applied on the substrate by a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen. A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (preliminary drying) at a temperature of about 60 to 100 ° C. In addition, after applying the above composition onto a carrier film, drying and winding it up as a film, the photocurable resin composition layer is laminated on the substrate so that the carrier film is in contact with the carrier film. By peeling off, a resin insulating layer can be formed. Then, the contact type (or non-contact type) is selectively exposed with active energy rays through a photomask having a pattern formed, and the unexposed portion is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3% sodium carbonate aqueous solution). Thus, a resist pattern is formed. Furthermore, in the case of the composition containing the thermosetting component (E), for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxyl group-containing resin (A) and the molecule The thermosetting component (E) having two or more cyclic ether groups and / or cyclic thioether groups reacted with each other, and was excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics. A cured coating film can be formed. In addition, even when the thermosetting component (E) is not contained, by performing heat treatment, the ethylenically unsaturated bond remaining in an unreacted state at the time of exposure undergoes thermal radical polymerization, and the coating film characteristics are improved. Depending on the purpose and application, heat treatment (thermosetting) may be performed.

  As the substrate, in addition to a printed circuit board and a flexible printed circuit board in which circuits are formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin , Glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, copper-clad laminate of all grades (FR-4 etc.) using polyimide, polyethylene, PPO, cyanate ester, etc., polyimide film, PET A film, a glass substrate, a ceramic substrate, a wafer plate, or the like can be used.

  The volatile drying performed after the photocurable resin composition of the present invention is applied is a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (with a heat source of an air heating method using steam, Can be carried out using a method in which the hot air is brought into countercurrent contact, or a method in which the hot air is blown onto the support from a nozzle.

As mentioned above, after apply | coating the photocurable resin composition of this invention and evaporating and drying, exposure (irradiation of an active energy ray) is performed with respect to the obtained coating film. In the coating film, the exposed portion (the portion irradiated by the active energy ray) is cured.
The exposure equipment used for the active energy ray irradiation includes a laser direct lithography system (laser direct imaging system), an exposure machine equipped with a metal halide lamp, an exposure machine equipped with a (super) high-pressure mercury lamp, and a mercury short arc lamp. Or a direct drawing apparatus using an ultraviolet lamp such as a (super) high-pressure mercury lamp can be used. As long as a laser beam having a maximum wavelength in the range of 350 to 410 nm is used as the active energy ray, either a gas laser or a solid laser may be used. Further, the exposure amount varies depending the thickness or the like, typically 5 to 200 mJ / cm ^2, preferably from 5 to 100 mJ / cm ^2, more preferably be in the range of 5~50mJ / cm ^2. As the direct drawing device, for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any device may be used as long as it oscillates laser light having a maximum wavelength of 350 to 410 nm. .

  The developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

<Preparation of base varnish>
Main agent formulation examples 1-5
The components shown in Table 5 were blended in the proportions (parts by mass) shown in Table 5, preliminarily mixed with a stirrer, and then kneaded with a three-roll mill to prepare a varnish of a main composition for solder resist. Here, when the dispersion degree of the obtained varnish was evaluated by particle size measurement using a grindometer manufactured by Eriksen, it was 15 μm or less.

<Preparation of curing agent varnish>
Curing agent formulation examples 1-5
Each component shown in Table 6 was blended in the proportions (parts by mass) shown in Table 6, preliminarily mixed with a stirrer, and then kneaded with a three-roll mill to prepare a varnish of a hardener composition for solder resist. Here, when the dispersion degree of the obtained varnish was evaluated by particle size measurement using a grindometer manufactured by Eriksen, it was 15 μm or less.

<Grade stability over time>
The varnishes shown in Tables 5 and 6 were allowed to stand for 1 week in a refrigerator set at 5 ° C. After returning to room temperature, the varnish was applied to a glass plate to confirm the grains. The results are shown in Table 7.

<Preparation of composition for performance evaluation>
The varnish of the main agent composition shown in Table 5 above and the varnish of the curing agent composition shown in Table 6 above were blended in the proportions (parts by mass) shown in Table 8 below, mixed with a stirrer, and the composition for performance evaluation A product varnish was prepared.

Performance evaluation:
<Optimum exposure amount>
The flame curable resin compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were coated on the entire surface by screen printing after washing a circuit board with a copper thickness of 35 μm after buffing, washing with water and drying. , And dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. After drying, it is exposed through a step tablet (Kodak No. 2) using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and developed (1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. with a spray pressure of 0. 2MP) was performed in 60 seconds, and the amount of the step tablet pattern remaining when it was 6 steps was determined as the optimum exposure amount.

Characteristic test:
The flame-retardant photocurable resin compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were applied onto the patterned polyimide film substrate by screen printing, dried at 80 ° C. for 30 minutes, and brought to room temperature. Allow to cool. Using this exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, this substrate is exposed to a solder resist pattern at an optimal exposure amount, and developed (1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. spray pressure 0.2 MPa). A resist pattern was obtained in 60 seconds. This substrate was cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.

<Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin-type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.
○: No peeling is observed even if the immersion for 10 seconds is repeated twice or more.
(Triangle | delta): It peels for a while when immersion for 10 seconds is repeated twice or more.
X: The resist layer swells and peels off once in 10 seconds.

<Electroless gold plating resistance>
Using a commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 3 μm and gold 0.03 μm, and the presence or absence of peeling of the resist layer or plating penetration is confirmed by tape peeling. After the evaluation, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.
○: Infiltration and peeling are not seen.
Δ: Slight penetration is observed after plating, but does not peel off after tape peeling.
X: Permeation is observed after plating, and peeling is also observed after tape peeling.

<Electrical characteristics>
Using an IPC B-25 comb-type electrode B coupon instead of a copper foil substrate, an evaluation board was prepared under the above conditions, and a bias voltage of DC 100 V was applied to the comb-type electrode, and 85 ° C., 85% R.D. H. The resistance value after 1,000 hours and the presence or absence of migration were confirmed in a constant temperature and humidity chamber. The judgment criteria are as follows.
A: Insulation resistance value after humidification of 10 ¹² Ω or more, no copper migration ○: Insulation resistance value after humidification of less than 10 ¹² Ω, 109 Ω or more, no copper migration Δ: Insulation resistance value after humidification of 10 ⁹ Ω or more, With copper migration ×: Insulation resistance value after humidification of 10 ⁸ Ω or less, with copper migration

<Flame retardance>
The compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were applied to the entire surface by screen printing on a 25 um-thick polyimide film (Kapton 100H) or 12.5 um-thick polyimide film (Kapton 50H). Dry in minutes and allow to cool to room temperature. Further, the entire back surface was similarly applied by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature to obtain a double-side coated substrate. Using this exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, the entire surface of the solder resist is exposed on this substrate at an optimum exposure amount, and development (1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. with a spray pressure of 0.2 MPa) is performed. It was performed in 60 seconds, and thermosetting was performed at 150 ° C. for 60 minutes to obtain an evaluation sample. This flame retardant evaluation sample was subjected to a thin material vertical combustion test based on the UL94 standard. Evaluation was expressed as VTM-0 or VTM-1 based on the UL94 standard.

<Flexibility>
The compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were applied to a 25 um thick polyimide film (Kapton 100H) by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Using this exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, the entire surface of the solder resist is exposed on this substrate at an optimum exposure amount, and development (1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. with a spray pressure of 0.2 MPa) is performed. It was performed in 60 seconds, and thermosetting was performed at 150 ° C. for 60 minutes to obtain an evaluation sample. The prepared sample was repeatedly bent 180 ° by goblet folding several times, and the occurrence of cracks in the coating film at that time was observed visually and with an optical microscope with a magnification of 200 to evaluate the number of times that cracks did not occur.

Table 9 shows the results of the evaluation tests.

  As is clear from the results shown in Tables 7 and 9, the flame-retardant photocurable resin compositions of Examples 1 to 4 of the present invention are not only excellent in storage stability but also flexible. It was excellent. On the other hand, in the case of the flame-retardant photocurable resin compositions of Comparative Examples 1 to 4 using phenoxyphosphazene having a strong solid crystallinity at room temperature, the storage stability and flexibility were inferior.

Examples 5-8
A flame-retardant photocurable resin composition prepared according to Examples 1 to 4 shown in Table 8 was diluted with methyl ethyl ketone, applied onto a carrier film, and dried by heating to form a photosensitive resin composition layer having a thickness of 20 μm. Then, a cover film was laminated thereon to obtain a dry film. Thereafter, the cover film was peeled off, and the film was bonded to the patterned copper foil substrate using a laminator. The substrate is exposed to an optimal exposure amount using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp on this substrate, the carrier film is peeled off, and then developed (1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. A spray pressure of 0.2 MPa was performed for 60 seconds to obtain a resist pattern. Thereafter, heat curing was performed for 60 minutes in a hot air dryer at 150 ° C. to prepare a test substrate. About the test board | substrate which has the obtained cured film, the evaluation test of each characteristic was done like the test method and evaluation method which were mentioned above. The result was almost equivalent to Examples 1-4. Moreover, the dry film produced at this time showed no generation of grains even after being stored at 5 ° C. for 1 week. On the other hand, dry films were similarly produced using the photocurable resin compositions prepared according to Comparative Examples 1 to 4 in Table 8. There was no problem immediately after the preparation, but when it was stored at 5 ° C. for 1 week, partial grain formation was observed.

Claims (8)

(A) a carboxyl group-containing resin, (B) a soluble phosphazene compound that is soluble in the carboxyl group-containing resin (A) or its varnish by 5 wt% or more , ( C) a photopolymerization initiator, and (E) a thermosetting resin . A flame retardant photocurable resin composition comprising: a thermosetting resin (E) containing an epoxy resin having a biphenyl skeleton .   The flame-retardant photocurable resin composition according to claim 1, wherein the phosphazene compound (B) is a solid phenoxyphosphazene compound having a substituent containing a nitrogen atom.   Furthermore, (D) a photopolymerizable monomer is contained, The flame-retardant photocurable resin composition of Claim 1 or 2 characterized by the above-mentioned.   The flame retardant photocurable resin composition according to claim 3, wherein the phosphazene compound (B) is soluble in the photopolymerizable monomer (D) by 5 wt% or more. Furthermore, it is a soldering resist containing a coloring agent, The flame-retardant photocurable resin composition as described in any one of Claims 1 thru | or 4 characterized by the above-mentioned. The flame-retardant photocurable dry film obtained by apply | coating and drying the flame-retardant photocurable resin composition as described in any one of Claims 1 thru | or 5 on a carrier film. A flame retardant cured product obtained by curing the flame retardant photocurable resin composition according to any one of claims 1 to 5 or the dry film according to claim 8. A print having a flame retardant cured film obtained by curing the flame retardant photocurable resin composition according to any one of claims 1 to 5 or the dry film according to claim 6. Wiring board.