JP6211781B2 - Flame-retardant curable resin composition, dry film, flame-retardant coating and printed wiring board - Google Patents

Description

  The present invention relates to a flame-retardant curable resin composition, a dry film, a flame-retardant coating, and a printed wiring board. A flame retardant curable resin composition capable of obtaining a flame retardant coating without bleed out of the flame retardant during pressing, a dry film comprising the composition, the composition or the dry film at least for thermosetting and photocuring The present invention relates to a flame retardant film obtained by any one of the above and a printed wiring board provided with the flame retardant film.

  Conventionally, a flexible printed circuit board (FPC) has been formed into a circuit by press punching and laminating an insulating film obtained by applying an adhesive to a polyimide film called a coverlay, and further thermosetting under pressure under a press. It was a cover layer on the surface of the flexible substrate. Since this cover lay is made of a low shrinkage thermosetting resin based on a polyimide film, the warpage after lamination and after press curing is very small. The warpage during the reflow of the mounting can be extremely reduced, and it is used in a large amount for FPC applications.

However, since punching is performed with a press, fine processing is difficult, and there is a disadvantage that alignment accuracy is not good when laminating with a circuit board on which a circuit is formed.
On the other hand, an alkali-developable photosensitive resin composition and its dry film have been proposed as a photosensitive coverlay (see Patent Document 1).

  On the other hand, since FPC is mounted on an electronic device, there is a demand for flame retardancy, and this FPC is also required for a solder resist. The FPC is usually a polyimide substrate and 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, the burden on the solder resist is relatively increased. On the other hand, a composition of a solder resist for FPC having a compound having an unsaturated double bond polymerizable with a halogenated aromatic ring has been proposed (see Patent Document 2). Is not preferable.

  In addition, as a non-halogen compound-containing resist composition, for example, a composition containing a specific phosphorus element-containing acrylate and a carboxyl group-containing resin has been proposed, but there is room for improvement in flexibility (patent document) 3).

  In addition, as a non-halogen compound-containing resist composition, for example, a composition containing a phenoxyphosphazene oligomer and an epoxy acrylate has been proposed, but if a press is performed at a high temperature to bond a reinforcing plate, a flame retardant There is a problem that bleed-out may occur (see Patent Document 4).

JP 2000-131836 A (Claims) Japanese Patent Publication No. 2007-10794 (Claims) Japanese Patent No. 4616863 (Claims) Japanese Patent No. 3091457 (Claims)

  Therefore, the object of the present invention is a non-halogen composition having a low environmental impact, excellent in flame retardancy and flexibility, and capable of obtaining a flame retardant coating without flame retardant bleed out during high temperature pressing. Resin composition, dry film comprising the composition, flame retardant coating obtained by heat curing or photo curing the composition or the dry film, and a printed wiring board provided with the flame retardant coating Is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by blending a specific phosphorus element-containing acrylate resin and a specific carboxyl group-containing resin. It came to complete.

（式中、Ｒ^１およびＲ^２は、それぞれ独立に、水素原子または炭素原子数１〜６の炭化水素基を表し、ｍおよびｎは、それぞれ独立に、０〜４の整数を表し、点線は２つのカルボキシル基が酸無水物を形成していてもよいことを示す。）
と、アクリレート化合物とを反応して得られるリン元素含有アクリレート樹脂、
（Ｂ）ビスフェノールＡ構造、ビスフェノールＦ構造、ビフェノール構造、ビフェノールノボラック構造、ビキシレノール構造、ビフェニルノボラック構造およびウレタン構造からなる群から選ばれる１種以上の部分構造を有するカルボキシル基含有樹脂、
（Ｃ）熱硬化性成分、および、
（Ｄ）光重合開始剤、
を含有することを特徴とするものである。 That is, the flame-retardant curable resin composition of the present invention is
(A) At least any one of phosphorus element-containing dicarboxylic acid represented by the following general formula (1) and its anhydride

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, m and n each independently represents an integer of 0 to 4; (Indicates that two carboxyl groups may form an acid anhydride.)
A phosphorus element-containing acrylate resin obtained by reacting an acrylate compound with
(B) bisphenol A structure, a bisphenol F structure, biphenol structure, biphenol novolak structure, bixylenol structure, carboxyl group-containing resin having at least one partial structure selected from the group consisting of biphenyl novolak structure and the urethane structure,
(C) a thermosetting component, and
(D) a photopolymerization initiator,
It is characterized by containing.

  The flame-retardant curable resin composition of the present invention is preferably used for forming a solder resist.

  The dry film of the present invention is obtained by applying and drying the flame retardant curable resin composition on a film.

  The flame retardant coating film of the present invention is characterized in that the flame retardant curable resin composition or the dry film is obtained by at least one of thermosetting and photocuring.

  The printed wiring board of the present invention comprises the flame retardant coating.

  According to the present invention, a flame retardant curable resin composition that has a non-halogen composition, has a low environmental impact, is excellent in flame retardancy and flexibility, and can obtain a flame retardant coating without a flame retardant bleed out during high-temperature pressing. And a dry film comprising the composition, a flame retardant coating obtained by heat curing and photocuring the composition or the dry film, and a printed wiring board provided with the flame retardant coating It becomes possible.

（式中、Ｒ^１およびＲ^２は、それぞれ独立に、水素原子または炭素原子数１〜６の炭化水素基を表し、ｍおよびｎは、それぞれ独立に、０〜４の整数を表し、点線は２つのカルボキシル基が酸無水物を形成していてもよいことを示す。）
と、アクリレート化合物とを反応して得られるリン元素含有アクリレート樹脂、
（Ｂ）ビスフェノールＡ構造、ビスフェノールＦ構造、ビフェノール構造、ビフェノールノボラック構造、ビキシレノール構造、ビフェニルノボラック構造およびウレタン構造からなる群から選ばれる１種以上の部分構造を有するカルボキシル基含有樹脂、
（Ｃ）熱硬化性成分、および、
（Ｄ）光重合開始剤、
を含有するものである。
上記（Ａ）リン元素含有アクリレート樹脂と、上記（Ｂ）ビスフェノールＡ構造、ビスフェノールＦ構造、ビフェノール構造、ビフェノールノボラック構造、ビキシレノール構造、ビフェニルノボラック構造およびウレタン構造からなる群から選ばれる１種以上の部分構造を有するカルボキシル基含有樹脂とを配合することによって、ノンハロゲン組成で環境負荷が少なく、かつ、難燃性、可撓性に優れた難燃性被膜を得ることができる。
以下、各成分について詳細に説明する。 The flame-retardant curable resin composition of the present invention includes (A) at least one of a phosphorus element-containing dicarboxylic acid represented by the following general formula (1) and an anhydride thereof.

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, m and n each independently represents an integer of 0 to 4; (Indicates that two carboxyl groups may form an acid anhydride.)
A phosphorus element-containing acrylate resin obtained by reacting an acrylate compound with
(B) bisphenol A structure, a bisphenol F structure, biphenol structure, biphenol novolak structure, bixylenol structure, carboxyl group-containing resin having at least one partial structure selected from the group consisting of biphenyl novolak structure and the urethane structure,
(C) a thermosetting component, and
(D) a photopolymerization initiator,
It contains.
And the (A) elemental phosphorus-containing acrylate resin, the (B) bisphenol A structure, a bisphenol F structure, biphenol structure, biphenol novolak structure, bixylenol structure, one or more selected from the group consisting of biphenyl novolak structure and the urethane structure By blending with a carboxyl group-containing resin having a partial structure, it is possible to obtain a flame retardant coating having a non-halogen composition and a low environmental load and excellent in flame retardancy and flexibility.
Hereinafter, each component will be described in detail.

[(A) Phosphorus element-containing acrylate resin]
The (A) phosphorus element-containing acrylate resin used in the present invention is obtained by reacting an acrylate compound with at least one of the phosphorus element-containing dicarboxylic acid represented by the general formula (1) and its anhydride. And a compound containing one or more (meth) acrylates in the molecule. In addition, in this specification, (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

Examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R ¹ and R ² in the general formula (1) representing at least one of the phosphorus element-containing dicarboxylic acid and its anhydride include, for example, Examples thereof include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, a cycloalkyl group, and a phenyl group. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, secondary butyl group, tertiary butyl group, isobutyl group, pentyl group, isopentyl group, and tertiary pentyl group. Examples of the alkenyl group having 1 to 6 carbon atoms such as hexyl group include vinyl group, allyl group, 3-butenyl group, isobutenyl group, 4-pentenyl group, and 5-hexenyl group. The hydrocarbon group having 1 to 6 carbon atoms may be branched or substituted.

  Examples of the phosphorus element-containing dicarboxylic acid represented by the general formula (1) and its anhydride include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itaconic acid. The compound obtained by making it react, its anhydride, etc. are mentioned.

As the acrylate compound, an acrylate compound having a functional group that reacts with a carboxyl group or a carboxylic acid anhydride of the dicarboxylic acid or an anhydride thereof is preferable. An acrylate residue can be added by such a reaction. Such an acrylate compound may be a monofunctional acrylate containing one (meth) acrylate group in the molecule or a polyfunctional acrylate containing two or more (meth) acrylate groups in the molecule. Examples of the functional group include an epoxy group, a hydroxyl group, and an amino group. Examples of the acrylate compound having an epoxy group include glycidyl (meth) acrylate and 2-methyl-2,3-epoxypropyl (meth) acrylate. Examples of the acrylate compound having a hydroxyl group include 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate. Examples of the acrylate compound having an amino group include diethylaminoethyl acrylate. Among the functional groups, an epoxy group and a hydroxyl group are more preferable.
A conventionally known reaction method can be used as the reaction method for adding with the functional group.

  Examples of the (A) phosphorus element-containing acrylate resin include mono- or bifunctional phosphorus elements obtained by reacting the phosphorus element-containing dicarboxylic acid of the general formula (1) synthesized as in the above example with glycidyl methacrylate. And a bifunctional phosphorus element-containing acrylate resin obtained by reacting a phosphorus element-containing dicarboxylic acid of the general formula (1) with hydroxy (meth) acrylate and, if necessary, a dialcohol.

  Although the addition amount of the said acrylate compound with respect to the phosphorus element containing dicarboxylic acid represented by the said General formula (1) or its anhydride is not specifically limited, The phosphorus density | concentration of the said (A) phosphorus element containing acrylate resin is 2%-7% It is preferable that the acrylate compound is adjusted so as to be in the above range.

By using the phosphorus element-containing dicarboxylic acid represented by the general formula (1) or its anhydride, a phosphorus element-containing acrylate resin having both ends acrylated can be easily obtained. By using the terminal acrylated phosphorus element-containing acrylate resin thus obtained, it is possible to obtain a flame-retardant coating that is excellent in flexibility and low warpage and does not cause bleeding out during high-temperature pressing. An excellent flame retardant curable resin composition can be obtained.
The phosphorus element-containing acrylate resin of the present invention is preferably a bifunctional phosphorus element-containing acrylate from the viewpoint of flexibility. When the phosphorus element-containing acrylate resin is monofunctional, the heat resistance tends to be inferior, and when the phosphorus element-containing acrylate resin is trifunctional or more, the flexibility tends to decrease.
Moreover, the said (A) phosphorus element containing acrylate resin may be used individually by 1 type, and may use 2 or more types together.

  The blending amount of the (A) phosphorus element-containing acrylate resin is preferably 10 parts by mass or more and 100 parts by mass or less, and more preferably 20 with respect to 100 parts by mass of the (B) carboxyl group-containing resin in terms of solid content. It is a ratio of not less than 80 parts by mass. If it exceeds 100 parts by mass, the heat resistance and chemical resistance may be inferior. On the other hand, if it is less than 10 parts by mass, sufficient flame retardancy and low warpage may not be obtained.

  In addition, when (A) a phosphorus element-containing acrylate resin is blended so that the phosphorus concentration in the flame-retardant curable composition is 1% or more, sufficient effect is exhibited in flame-retardant properties, but if it is too much Since solder heat resistance may be inferior, it is not preferable to have too much. Also, depending on the type and amount of the acrylate compound used in the reaction, sufficient photocurability may not be obtained. Therefore, even if a conventionally known photopolymerizable monomer / oligomer is used in combination, the photocurability can be increased. Good. Moreover, in order to improve photocurability, you may add the oxime type photoinitiator described later.

[(B) carboxyl group-containing resin]
The (B) a carboxyl group-containing resin used in the present invention, in the molecule, selected bisphenol A structure, a bisphenol F structure, biphenol structure, biphenol novolak structure, bixylenol structure, from the group consisting of biphenyl novolak structure and the urethane structure It is a compound having one or more kinds of partial structures and a carboxyl group, and various conventionally known compounds can be used. Due to the presence of the carboxyl group, the resin composition can be made alkali developable. Further, from the viewpoint of making the flame retardant curable resin composition of the present invention photocurable and developing resistance, it is preferable to have an ethylenically unsaturated double bond in the molecule in addition to the carboxyl group. Only a carboxyl group-containing resin having no ethylenically unsaturated double bond can be used as the component (B). When the resin of component (B) does not have an ethylenically unsaturated double bond, in order to make the composition photocurable, a compound having one or more ethylenically unsaturated groups in the molecule (photopolymerization) Monomer / oligomer) must be used in combination. As the ethylenically unsaturated double bond, those derived from acrylic acid, methacrylic acid or derivatives thereof are preferable. The (B) carboxyl group-containing resin may be used alone or in combination of two or more.

  Specific examples of the (B) carboxyl group-containing resin include carboxyl group-containing resins having a partial structure selected from the above group among the following carboxyl group-containing resins.

  (1) 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.

  (2) 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.

  (3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

  (4) 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.

  (5) During the synthesis of the resin of the above (2) or (4), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( (Meth) acrylic carboxyl group-containing urethane resin.

  (6) During the synthesis of the resin of the above (2) or (4), one isocyanate group and one or more (meth) acryloyl groups are introduced into the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. The carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.

  (7) dibasic acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. are reacted with a hydroxyl group present in the side chain by reacting a polyfunctional (solid) epoxy resin as described later. A photosensitive carboxyl group-containing resin to which a product is added.

  (8) 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.

  (9) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin as described later with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.

  (10) Reaction product obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.

  (11) Obtained by reacting an unsaturated group-containing monocarboxylic acid with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.

  (12) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (meth) Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and then reacting with the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as an acid.

  (13) One epoxy group and one or more (meth) acryloyl in a molecule such as glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate and the like in any one of the resins (1) to (12) above A photosensitive carboxyl group-containing resin obtained by adding a compound having a group.

Among the carboxyl group-containing resin, the resin used in the synthesis of the resin is chosen bisphenol A structure, a bisphenol F structure, biphenol structure, biphenol novolak structure, bixylenol structure, from the group consisting of biphenyl novolak structure and the urethane structure A resin having one or more types of partial structures or a carboxyl group-containing resin that is a hydrogenated compound thereof is preferable from the viewpoint of bending resistance of the obtained cured product.
Among the carboxyl group-containing resins having a urethane structure, a carboxyl group-containing urethane resin obtained by using a diisocyanate in which an isocyanate group is not directly bonded to a benzene ring is used as a component having an isocyanate group (including a diisocyanate). Since it has no change, it is effective for concealing the underlying layer and has little ultraviolet absorption, it is preferable because it has excellent resolution when used as an alkali-developable composition.

Since the carboxyl group-containing resin as described above has many carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.
The acid value of the carboxyl group-containing resin is desirably in the range of 20 to 200 mgKOH / g, more preferably in the range of 40 to 150 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 20 mgKOH / g, the adhesion of the coating film may not be obtained, or alkali development may be difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so that the line becomes thinner than necessary. In some cases, the developer is not distinguished between the exposed portion and the unexposed portion. This is not preferable because it may cause dissolution and peeling, and it may be difficult to draw a normal resist pattern.

  Moreover, although the weight average molecular weight of carboxyl group-containing resin used by this invention changes with resin frame | skeletons, 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, tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, film thickness may be reduced during development, and 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 blending amount of the (B) carboxyl group-containing resin is 5 to 60% by mass, preferably 10 to 60% by mass, more preferably 20 to 60% by mass in the flame-retardant curable resin composition in terms of solid content. %, Particularly preferably 30 to 50% by mass. 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 more than the above range, the viscosity of the composition may increase or the coating property may decrease, which is not preferable.

[(C) thermosetting component]
As the thermosetting component (C) of the present invention, any known one can be used as long as it is used as a thermosetting component in the thermosetting resin composition. (C) As thermosetting components, known and commonly used isocyanate compounds, blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, etc. The thermosetting resin can be used. The blending amount of the (C) thermosetting component is preferably 5 to 120 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the (B) carboxyl group-containing resin in terms of solid content. It is. When the said compounding quantity is less than 5 mass parts, it may be inferior to heat resistance, and is unpreferable. On the other hand, when the amount exceeds 120 parts by mass, developability may be deteriorated, which is not preferable.

  Among these, a preferable thermosetting component is a thermosetting component having at least one of a plurality of cyclic ether groups and cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in one molecule. . There are many commercially available thermosetting components having a cyclic (thio) ether group, and various properties can be imparted depending on the structure.

  The thermosetting component having a plurality of cyclic (thio) ether groups in the molecule includes a plurality of either one of the three-, four- or five-membered cyclic ether groups, or the cyclic thioether group, or two kinds of groups in the molecule. For example, a compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, and having a plurality of thioether groups in the molecule Examples thereof include compounds, that is, episulfide resins.

  Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840 manufactured by DIC, Epicron 850, Epicron 1050, Epicron 2055, Epototo YD-011, YD manufactured by Tohto Kasei Co., Ltd. -013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Sumitomo Epoxy ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Mitsubishi Chemical, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., manufactured by Dow Chemical Of D. E. R. 542, Sumitomo Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both trade names); jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd., EPPN-201, EOCN-1025, EOCN manufactured by Nippon Kayaku Co., Ltd. -1020, EOCN-104S, RE-306, NC-3000H, Sumitomo Epoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Co., Ltd., A.C. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Mitsubishi Chemical Co., Ltd. Epototo YDF-170, YDF-175, YDF-2004 manufactured by Tohto Kasei Co., Ltd. (All trade names) bisphenol F-type epoxy resin; hydrogenated bisphenol A-type epoxy resins such as Epototo ST-2004, ST-2007, ST-3000 (trade name) manufactured by Toto Kasei Co., Ltd .; jER604, Etototo YH-434 manufactured by Tohto Kasei Co., Ltd. Sumitomo Chemical Co., Ltd. Sumi-epoxy ELM-120, etc. (all trade names) glycidylamine type epoxy resin; Hydantoin type epoxy resin; 2021, CY179, etc. (all trade names) alicyclic epoxy resins; Mitsubishi Gakusha made of YL-933, manufactured by Dow Chemical Company of T. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 (all trade names) Type or biphenol type epoxy resin or a mixture thereof; Nippon Kayaku EBPS-200, ADEKA EPX-30, DIC EXA-1514 (trade name), etc .; bisphenol S type epoxy resin; Bisphenol A novolac type epoxy resin such as jER157S (trade name); tetraphenylolethane type epoxy resin such as jERYL-931 (all trade name) made by Mitsubishi Chemical; TEPIC made by Nissan Chemical Industries (all) Product name) heterocyclic epoxy resin; diglycy such as NOF's Bremer DGT Ruphthalate resin; Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Tohto Kasei Co., Ltd .; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700 manufactured by DIC Naphthalene group-containing epoxy resin; epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC, EXA-4816, EXA-4822, and EXA-4850 series flexible tough epoxy resin; CP made by NOF Corporation Examples include, but are not limited to, glycidyl methacrylate copolymer epoxy resins such as -50S and CP-50M; and copolymer epoxy resins of cyclohexylmaleimide and glycidyl methacrylate. These epoxy resins can be used alone or in combination of two or more. Among these, a bifunctional epoxy resin is preferable from the viewpoint of flexibility. In particular, a biphenyl novolac type epoxy resin, a bixylenol type epoxy resin or a mixture thereof is preferable from the viewpoint of flame retardancy.

  Examples of the polyfunctional oxetane compound 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-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolac resin, Poly (p-hydroxystyrene), cardo-type bisphe Lumpur acids, 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 episulfide resin having a plurality of cyclic (thio) ether groups in the molecule include YL7000 (bisphenol A type episulfide resin) manufactured by Mitsubishi Chemical Corporation and YSLV-120TE manufactured by Tohto Kasei Co., Ltd. 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 having a plurality of cyclic (thio) ether groups in the molecule is preferably 0.3 to 2.5 equivalents with respect to 1 equivalent of the carboxyl group of the (B) carboxyl group-containing resin. More preferably, it is the range which becomes 0.5-2.0 equivalent. When the amount of thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is less than 0.3 equivalents, carboxyl groups remain in the cured film, resulting in decreased heat resistance, alkali resistance, electrical insulation, etc. This is not preferable. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dried coating film, which is not preferable because the strength of the cured coating film may be reduced.

  When using the thermosetting component which has a some cyclic | annular (thio) ether group in the said molecule | numerator, 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, the present invention is not limited to these, and any epoxy resin or oxetane compound thermosetting catalyst or any one that promotes the reaction of a carboxyl group with at least one of an epoxy group and an oxetanyl group may be used alone or in combination. A mixture of seeds or more may 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 / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used, and preferably also as an adhesion-imparting agent A functional compound is used in combination with the thermosetting catalyst.

  The blending amount of these thermosetting catalysts is preferably 0.1 to 20 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of thermosetting component having a plurality of cyclic (thio) ether groups in the molecule in terms of solid content. Is 0.5-15.0 parts by mass.

  Examples of the amino resin include amino resins such as melamine derivatives and benzoguanamine derivatives. Examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds. Furthermore, the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound and alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. In particular, a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.

  Examples of commercially available amino resins include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, and the like. 1156, 1158, 1123, 1170, 1174, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx -290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw -750LM, (manufactured by Sanwa Chemical Co., Ltd.) and the like.

  As the isocyanate compound, a polyisocyanate compound having a plurality of isocyanate groups in the molecule can be used. As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adduct bodies, burette bodies and isocyanurate bodies of the isocyanate compounds mentioned above may be mentioned.

  The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.

  As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As an isocyanate compound used in order to synthesize | combine a block isocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is mentioned, for example. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.

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

  The block isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117. , Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, Nippon Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B 846, B-870, B-874, B-882 (above, Mitsui Takeda Chemicals, trade name), TPA-B80E, 17B-60PX, E402-B80T (above, Asahi Kasei Chemicals, trade name), etc. Can be mentioned. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

  The blending amount of the polyisocyanate compound or the blocked isocyanate compound is preferably 1 to 100 parts by weight, more preferably 2 to 70 parts by weight, based on 100 parts by weight of the (B) carboxyl group-containing resin, in terms of solid content. It is. When the said compounding quantity is less than 1 mass part, sufficient toughness of a coating film may not be acquired and it is unpreferable. On the other hand, when the amount exceeds 100 parts by mass, the storage stability may decrease, which is not preferable.

  A urethanization catalyst can be added to the flame retardant curable resin composition of the present invention in order to accelerate the curing reaction of hydroxyl groups, carboxyl groups and isocyanate groups. As the urethanization catalyst, one or more urethanization catalysts selected from the group consisting of at least one of tin-based catalysts, metal chlorides, metal acetylacetonate salts, metal sulfates, amine compounds and amine salts are used. It is preferable to use it.

  Examples of the tin catalyst include organic tin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds.

  The metal chloride is a metal chloride selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al. For example, cobaltous chloride, ferrous nickel chloride, ferric chloride, and the like. Can be mentioned.

  The metal acetylacetonate salt is a metal acetylacetonate salt selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu and Al. For example, cobalt acetylacetonate, nickel acetylacetonate, iron acetyl Examples include acetonate.

  The metal sulfate is a metal sulfate selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al. Examples thereof include copper sulfate.

  Examples of the amine compound include conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′. , N ", N" -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N'- (2-hydroxyethyl) -N, N, N′-trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethyl-N '-(2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) ) -N, N ', N ", N" -tetramethyldiethylenetriamine, N- (2-hydroxypropyl) -N, N', N ", N" -tetramethyldiethylenetriamine, N, N, N'-trimethyl -N '-(2-hydroxyethyl) propanediamine, N-methyl-N'-(2-hydroxyethyl) piperazine, bis (N, N-dimethylaminopropyl) amine, bis (N, N-dimethylaminopropyl) Isopropanolamine, 2-aminoquinuclidine, 3-aminoquinuclidine, 4-aminoquinuclidine, 2-quinuclidol, 3-quinuclidinol, 4-quinuclidinol, 1- (2′-hydroxypropyl) imidazole, 1 -(2'-hydroxypropyl) -2-methylimidazole, 1- (2'-hydroxyethyl) imida 1- (2′-hydroxyethyl) -2-methylimidazole, 1- (2′-hydroxypropyl) -2-methylimidazole, 1- (3′-aminopropyl) imidazole, 1- (3′- Aminopropyl) -2-methylimidazole, 1- (3′-hydroxypropyl) imidazole, 1- (3′-hydroxypropyl) -2-methylimidazole, N, N-dimethylaminopropyl-N ′-(2-hydroxy) Ethyl) amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxypropyl) amine, N, N-dimethylaminoethyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminoethyl-N ′, N′-bis (2-hydroxypropyl) amine, melamine, and / or benzoguanamine can be used.

  Examples of the amine salt include organic acid salt amine salts such as DBU (1,8-diaza-bicyclo [5.4.0] undecene-7).

  The compounding amount of the urethanization catalyst is preferably 0.01 to 20 parts by mass, more preferably 0.5 to 10.0 parts by mass, in terms of solid content, with respect to 100 parts by mass of the (B) carboxyl group-containing resin. Part.

[(D) Photopolymerization initiator]
The flame retardant curable resin composition of the present invention contains a photopolymerization initiator. (D) As a photoinitiator, a well-known photoinitiator can be used, for example, the oxime ester type photoinitiator which has an oxime ester group, an alpha-aminoacetophenone type photoinitiator, an acyl phosphine oxide. One or more photopolymerization initiators selected from the group consisting of a photopolymerization initiator and a titanocene photopolymerization initiator can be suitably used.

（式中、Ｘは、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）を表し、Ｙ、Ｚはそれぞれ、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、結合か、炭素数１〜１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５−ピロール−ジイル、４，４’−スチルベン−ジイル、４，２’−スチレン−ジイルで表し、ｎは０か１の整数である。） Examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, NCI-831 manufactured by ADEKA, and the like as commercially available products. Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.

(In the formula, X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms). Group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group, a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms), Represents an amino group, an alkylamino group having a C 1-8 alkyl group or a dialkylamino group, and Y and Z are each a hydrogen atom, a C 1-17 alkyl group, and a carbon number 1 Alkoxy group having ˜8 alkoxy group, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkyl group having 1 to 8 carbon atoms) Substituted with a mino group or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms) Or substituted with a dialkylamino group), anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar is a bond or alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, (Thiophene, anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl, and n is an integer of 0 or 1)

  In particular, in the above general formula, X and Y are each a methyl group or an ethyl group, Z is a methyl group or a phenyl group, n is 0, Ar is a bond, a phenylene group, a naphthylene group, a thiophene Group or thienylene group is preferred.

（式中、Ｒ^３は、炭素原子数１〜４のアルキル基、または、ニトロ基、ハロゲン原子もしくは炭素原子数１〜４のアルキル基で置換されていてもよいフェニル基を表す。
Ｒ^４は、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、または、炭素原子数１〜４のアルキル基もしくはアルコキシ基で置換されていてもよいフェニル基を表す。
Ｒ^５は、酸素原子または硫黄原子で連結されていてもよく、フェニル基で置換されていてもよい炭素原子数１〜２０のアルキル基、炭素原子数１〜４のアルコキシ基で置換されていてもよいベンジル基を表す。
Ｒ^６は、ニトロ基、または、Ｘ−Ｃ（＝Ｏ）−で表されるアシル基を表す。Ｘは、炭素原子数１〜４のアルキル基で置換されていてもよいアリール基、チエニル基、モルホリノ基、チオフェニル基、または、下記式で示される構造を表す。）

Moreover, the compound which can be represented by the following general formula can also be mentioned as a preferable carbazole oxime ester compound.

(Wherein, R ³ represents an alkyl group or a nitro group, a halogen atom or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms.
R ⁴ represents a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkyl group or alkoxy group having 1 to 4 carbon atoms.
R ⁵ may be connected with an oxygen atom or a sulfur atom, and may be substituted with an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 4 carbon atoms which may be substituted with a phenyl group. Represents a good benzyl group.
R ⁶ represents a nitro group or an acyl group represented by X—C (═O) —. X represents an aryl group, a thienyl group, a morpholino group, a thiophenyl group, or a structure represented by the following formula, which may be substituted with an alkyl group having 1 to 4 carbon atoms. )

  Other preferable carbazole oxime ester compounds include JP-A No. 2004-359639, JP-A No. 2005-097141, JP-A No. 2005-220097, JP-A No. 2006-160634, and JP-A No. 2008-094770. Examples include carbazole oxime ester compounds described in Table 2008-509967, JP-T 2009-040762, and JP 2011-80036.

  It is preferable that the compounding quantity of such an oxime ester system photoinitiator shall be 0.01-5 mass parts with respect to 100 mass parts of said (B) carboxyl group-containing resin in conversion of solid content. If it is less than 0.01 parts by mass, the photocurability may be insufficient, and the coating properties such as chemical resistance may deteriorate. On the other hand, when the amount exceeds 5 parts by mass, light absorption on the surface of the coating film becomes intense, and the deep curability tends to decrease. More preferably, it is 0.5-3 mass parts.

  As the α-aminoacetophenone photopolymerization initiator, specifically, 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 BASF Japan.

  Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO manufactured by BASF Japan and Irgacure 819 manufactured by BASF Japan.

  The blending amounts of these α-aminoacetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator are 0.01 to 15 masses per 100 parts by mass of the (B) carboxyl group-containing resin in terms of solid content. Part. If it is less than 0.01 parts by mass, the photocurability may be insufficient, and the coating properties such as chemical resistance may deteriorate. On the other hand, when the amount exceeds 15 parts by mass, the effect of reducing the outgas cannot be obtained, the light absorption on the surface of the coating film becomes intense, and the deep curability tends to decrease. More preferably, it is 0.5-10 mass parts.

  Specific examples of titanocene photopolymerization initiators include bis (cyclopentadienyl) -di-phenyl-titanium, bis (cyclopentadienyl) -di-chloro-titanium, and bis (cyclopentadienyl) -bis. (2, 3, 4, 5, 6 pentafluorophenyl) titanium, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyrrol-1-yl) phenyl) titanium and the like. Examples of commercially available products include Irgacure 784 manufactured by BASF Japan.

  The amount of the titanocene photopolymerization initiator used is preferably 0.05 to 2 parts by mass, more preferably 100 parts by mass of the (B) carboxyl group-containing resin, more preferably in terms of solid content. 0.05 to 1 part by mass. When the amount is less than 0.05 parts by mass, improvement in deep part curability is not confirmed. On the other hand, if it exceeds 2 parts by mass, there is a possibility of causing great halation, which is not preferable. More preferably, it is 0.1-1 mass part.

  Further, Irgacure 389 manufactured by BASF Japan can also be suitably used as a photopolymerization initiator.

  In addition to the photopolymerization initiator, a photoinitiator assistant and a sensitizer can be used. Photoinitiators, photoinitiators and sensitizers that can be suitably used in the flame-retardant curable resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenones. Compounds, tertiary amine compounds, and xanthone compounds.

  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, 1,1-dichloroacetophenone, and the like.

  Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, and the like.

  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 benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, and 4-benzoyl-4′-propyldiphenyl. And sulfides.

  Specifically, as the tertiary amine compound, 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, Dialkylaminobenzophenone such as 4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc. Dialkylamino group-containing coumarin compounds, ethyl 4-dimethylaminobenzoate (Kayacure EPA, manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB, manufactured by International Bio-Synthetics), 4-dimethylamino Nobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylhexyl 4-dimethylaminobenzoic acid (Esolol 507 manufactured by Van Dyk).

  Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, the inclusion of a thioxanthone compound is preferable from the viewpoint of deep curability. Among them, it is preferable to include a thioxanthone compound such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.

  As a compounding quantity of such a thioxanthone compound, it is preferable that it is 20 mass parts or less with respect to 100 mass parts of said (B) carboxyl group-containing resin in conversion of solid content. When the blending amount of the thioxanthone compound exceeds 20 parts by mass, the thick film curability is lowered and the cost of the product is increased. More preferably, it is 10 parts by mass or less.

  As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength in the range of 350 to 450 nm, and ketocoumarins are particularly preferable. .

  As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. Dialkylamino group-containing coumarin compounds have a maximum absorption wavelength in the ultraviolet region of 350 to 410 nm, so they are less colored and use a colored pigment as well as a colorless and transparent cured coating, and a colored cured coating that reflects the color of the colored pigment itself 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.

  As a compounding quantity of such a tertiary amine compound, it is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of said (B) carboxyl group-containing resin in conversion of solid content. When the amount of the tertiary amine compound is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained. On the other hand, when it exceeds 20 parts by mass, light absorption on the surface of the coating film by the tertiary amine compound becomes violent, and the deep curability tends to decrease. More preferably, it is 0.1-10 mass parts.

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

  In addition, since the above photoinitiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, the sensitivity may be lowered in some cases and may function as an ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the composition. Absorbs light of a specific wavelength as necessary to enhance the photoreactivity of the surface, and changes the resist line shape and opening to vertical, tapered, and inversely tapered, and processing accuracy of line width and opening diameter Can be improved.

(Photopolymerizable monomer / oligomer)
The curable resin composition of this invention can mix | blend a photopolymerizable monomer / oligomer. Examples of the photopolymerizable monomer / oligomer include compounds having at least one ethylenically unsaturated group in a conventionally known molecule, and specifically, polyester (meth) acrylate, polyether (meth) acrylate, urethane (Meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate and the like can be mentioned. More specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N, N-dimethyl Acrylamides such as acrylamide, N-methylol acrylamide, N, N-dimethylaminopropyl acrylamide; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate; Hexanediol, Trimethylolpropane Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or the like Multivalent acrylates such as ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone adducts; phenoxy acrylates, bisphenol A diacrylates, and many of these phenols such as ethylene oxide adducts or propylene oxide adducts. Polyvalent acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate; not limited to the above; polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene Polyacrylate polyols and other polyols can be directly acrylated or urethane acrylated via diisocyanates. Examples thereof include at least one of acrylates and melamine acrylates, and methacrylates corresponding to the acrylates.

  Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, or a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. A photopolymerizable monomer / oligomer such as an epoxy urethane acrylate compound reacted with a half urethane compound may be used in combination. Such an epoxy acrylate resin or compound can improve photocurability without deteriorating finger touch drying properties.

  In particular, in the present invention, polyhydric acrylates such as polyhydric alcohols or their ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone adducts, and polyphenols such as ethylene oxide adducts or propylene oxide adducts of phenols. Acrylates and further (meth) acrylate-containing urethane oligomers are preferred, and the photopolymerizable monomer / oligomer used is more preferably bifunctional from the viewpoint of flexibility.

  The blending amount of the photopolymerizable monomer / oligomer is preferably 5 to 100 parts by mass, more preferably 5 to 70 parts by mass with respect to 100 parts by mass of the (B) carboxyl group-containing resin in terms of solid content. It is a ratio. When the amount is less than 5 parts by mass, the photocurability is lowered, and pattern development may be difficult due to alkali development after irradiation with active energy rays, which is not preferable. On the other hand, when the amount exceeds 100 parts by mass, the solubility in an aqueous alkali solution is lowered, and the coating film may become brittle.

(Flame retardants)
The flame retardant curable resin composition of the present invention may further contain a flame retardant such as a phosphorus-containing compound in order to further improve the flame retardancy.

（式中、Ｒ^７、Ｒ^８およびＲ^９は、それぞれ独立に、ハロゲン原子以外の置換基を示す。） (Phosphorus-containing compound)
As the phosphorus-containing compound, conventionally known compounds can be used. For example, phosphoric acid esters and condensed phosphoric acid esters, cyclic phosphazene compounds, phosphazene oligomers, phosphinic acid metal salts, and the following general formula Compounds.

(In the formula, R ⁷ , R ⁸ and R ⁹ each independently represent a substituent other than a halogen atom.)

In the above general formula, R ⁷ and R ⁸ are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁹ has 1 to 1 carbon atoms optionally substituted with a hydrogen atom or a cyano group. 4 is preferably an alkyl group, 2,5-dihydroxyphenyl group, or 3,5-di-t-butyl-4-hydroxyphenyl group.

  Examples of commercially available phosphorus-containing compounds represented by the above general formula include HCA, SANKO-220, M-ESTER, and HCA-HQ (all are trade names manufactured by Sanko).

A compound in which R ⁷ and R ⁸ in the above general formula are hydrogen atoms and R ⁹ is a (meth) acrylate derivative is also preferable. Such a compound can be generally synthesized by a Michael addition reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a known and commonly used polyfunctional (meth) acrylate monomer.

  Examples of the known and commonly used (meth) acrylate monomers include diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxy. Polyhydric acrylates such as polyhydric alcohols such as ethyl isocyanurate or their ethylene oxide adducts, propylene oxide adducts or caprolactone adducts; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts of these phenols or Polyhydric acrylates such as propylene oxide adducts; and urethane acrylates of the above polyalcohols Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyglycerides of glycidyl ether such as triglycidyl isocyanurate; and melamine acrylate, and at least one of the methacrylates corresponding to the acrylate 1 type etc. are mentioned.

  The phosphorus-containing compound having a phenolic hydroxyl group has high hydrophobicity and heat resistance, does not deteriorate electrical characteristics due to hydrolysis, and has high solder heat resistance. Further, as an appropriate combination, when an epoxy resin is used among thermosetting resins, there is an advantage that it does not bleed out after curing because it reacts with the epoxy group and is taken into the network. Commercially available products include HCA-HQ manufactured by Sanko Co., Ltd.

  Phosphorus-containing compounds that are oligomers or polymers have the advantage that there is little decrease in bendability due to the influence of the alkyl chain, and there is no bleedout after curing due to the large molecular weight. Commercially available products include M-Ester-HP manufactured by Sanko Co., Ltd. and phosphorus-containing Byron 337 manufactured by Toyobo Co., Ltd.

  As the phosphazene oligomer, a phenoxyphosphazene compound is effective, and there are a substituted or unsubstituted phenoxyphosphazene oligomer, a trimer, a tetramer, and a pentamer, and a liquid or solid powder. However, any of them can be preferably used. Commercially available products include FP-100, FP-300, and FP-390 manufactured by Fushimi Pharmaceutical. Among them, phenoxyphosphazene oligomers substituted with alkyl groups or polar groups such as hydroxyl groups and cyano groups have high solubility in carboxyl group-containing resins, and there are no problems such as recrystallization even when added in large amounts. preferable.

  By using a phosphinic acid metal salt, flame retardancy can be improved without impairing the flexibility of the cured coating film. In addition, by using a phosphinic acid metal salt that is excellent in heat resistance, the bleedout of the flame retardant can be suppressed in the hot press during mounting. Commercially available products include EXOLIT OP 930, EXOLIT OP 935 and the like manufactured by Clariant.

  The compounding amount of the phosphorus-containing compound is preferably in the range of 1 to 40 parts by mass, particularly preferably 5 to 30 parts by mass with respect to 100 parts by mass of the (B) carboxyl group-containing resin in terms of solid content. If blended in a large amount exceeding 40 parts by mass, sufficient flame retardancy can be obtained, but bleed out may occur, which is not preferable.

(Coloring agent)
The curable resin composition of the present invention can contain a colorant. 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. Specific examples include those with the following color index numbers (CI; issued by The Society of Dyers and Colorists). However, it is preferable that the colorant does not contain a halogen from the viewpoint of reducing environmental burden and affecting the human body.

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.

Blue colorant:
Blue colorants include phthalocyanine and anthraquinone, and pigments are compounds classified as Pigment, specifically: 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.

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 colorant as described above can be appropriately blended, and the blending amount is not particularly limited. However, in terms of solid content, blending of 10 parts by mass or less is sufficient with respect to 100 parts by mass of the (B) carboxyl group-containing resin. Preferably, it is 0.1-5 mass parts.

(Filler)
The flame retardant curable resin composition of the present invention can be blended with a filler as necessary in order to increase the physical strength and the like of the obtained cured product. As such a filler, known and commonly used inorganic or organic fillers can be used, and barium sulfate, spherical silica and talc are particularly preferably used. Further, for the purpose of imparting flame retardancy, aluminum hydroxide, magnesium hydroxide, boehmite and the like can also be used. Furthermore, NANOCRYL (trade names) XP 0396, XP 0596, XP 0733, XP 0746, XP 0765 manufactured by Hanse-Chemie, in which nano silica is dispersed in a compound having one or more ethylenically unsaturated groups or the above polyfunctional epoxy resin. , XP 0768, XP 0953, XP 0954, XP 1045 (all are product grade names), NANOPOX (trade name) XP 0516, XP 0525, XP 0314 (all are product grade names) manufactured by Hanse-Chemie . These may be used alone or in combination of two or more.

  The blending amount of the filler is preferably 500 parts by mass or less, more preferably 0.1 to 300 parts by mass, and particularly preferably 0 to 100 parts by mass of the (B) carboxyl group-containing resin in terms of solid content. .1 to 150 parts by mass. When the blending amount of the filler exceeds 500 parts by mass, the viscosity of the curable resin composition becomes high and the printability may be lowered, or the cured product may become brittle.

(Binder polymer)
Conventionally known binder polymers can be used in the flame-retardant curable resin composition of the present invention for the purpose of improving the flexibility and dryness of the cured product obtained. As the binder polymer, cellulose-based, polyester-based, and phenoxy resin-based polymers are preferable. Examples of the cellulose-based polymer include cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) series manufactured by Eastman Co., Ltd., a polyester-based polymer byron series manufactured by Toyobo Co., Ltd., and a phenoxy resin-based polymer as bisphenol A, Bisphenol F and phenoxy resins of their hydrogenated compounds are preferred.

  The blending amount of the binder polymer is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, and particularly preferably 5 to 100 parts by mass of the (B) carboxyl group-containing resin in terms of solid content. 30 parts by mass. When the blending amount of the binder polymer exceeds 50 parts by mass, the alkali developability of the curable resin composition is inferior, and the pot life that can be developed may be shortened.

(Elastomer)
The flame-retardant curable resin composition of the present invention can be blended with an elastomer for the purpose of imparting flexibility to the resulting cured product and improving the brittleness of the cured product. Examples of the elastomer include polyester elastomers, polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyesteramide elastomers, acrylic elastomers, and olefin elastomers. In addition, resins in which some or all of the epoxy groups of epoxy resins having various skeletons are modified with carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can be used. Furthermore, epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers and the like can also be used. One type of elastomer may be used alone, or a mixture of two or more types may be used.

(Adhesion promoter)
In the flame-retardant curable resin composition of the present invention, an adhesion promoter can be used in order to improve the adhesion between layers or the adhesion between the photosensitive resin layer and the substrate. Examples of the adhesion promoter include benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, Examples include 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, and silane coupling agents.

(Antioxidant)
In many polymer materials, once oxidation starts, oxidative degradation occurs one after another in a chain, resulting in functional deterioration of the polymer material. Therefore, the flame retardant curable resin composition of the present invention prevents oxidation. (1) A radical scavenger that invalidates the generated radical and (2) a peroxide that decomposes at least one of the generated peroxide into a harmless substance so that no new radical is generated. Antioxidants such as product decomposing agents can be added. An antioxidant may be used individually by 1 type and may be used in combination of 2 or more type.

(UV absorber)
Since the polymer material absorbs light and thereby decomposes and deteriorates, the flame retardant curable resin composition of the present invention is not limited to the above-mentioned antioxidants in order to take measures against stabilization of ultraviolet rays. Absorbents can be used.
Examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like. An ultraviolet absorber may be used individually by 1 type, and can also be used in combination of 2 or more type. By using together with the above antioxidant, the molded product obtained from the curable resin composition of the present invention can be stabilized.

(Other additives)
The flame retardant curable resin composition of the present invention may further comprise, as necessary, known and commonly used thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, finely divided silica, organic bentonite, and montmorillonite. Known and commonly used thickeners such as silicone-based, fluorine-based, polymer-based antifoaming agents and leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, rust prevention Known and commonly used additives such as an agent can be blended.

  The thermal polymerization inhibitor can be used to prevent unintentional thermal polymerization or temporal polymerization of the flame retardant curable resin composition. Examples of thermal polymerization inhibitors include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil. , Naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4 -Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

(Organic solvent)
Furthermore, the flame retardant curable resin composition of the present invention is an organic solvent for the synthesis of the above (B) carboxyl group-containing resin and the adjustment of the composition, or for the adjustment of the viscosity for application to a substrate or a carrier film. Can be used.

  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, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether is petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such an organic solvent may be used individually by 1 type, and may be used as a 2 or more types of mixture.

  The flame-retardant curable resin composition of the present invention can be preferably used as a solder resist. Moreover, since a flame-retardant film excellent in flame retardancy and flexibility can be obtained, it can be particularly preferably used as a flame-retardant curable resin composition for FPC.

The dry film of the present invention is obtained by applying and drying the flame retardant curable resin composition of the present invention on a film (carrier film), and the carrier film and the flame retardant curing formed on the carrier film. A layer made of a conductive resin composition.
In forming a dry film, the flame retardant curable resin composition of the present invention is diluted with the above organic solvent to an appropriate viscosity, and then a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater. A film can be obtained by applying a uniform thickness on a support with a gravure coater, spray coater or the like, and drying usually 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 or the like can be used, and when the cover film is peeled off, the adhesive strength between the film and the support is more than What is necessary is just to have a smaller adhesive force between the membrane and the cover film.

  The flame-retardant coating film of the present invention is obtained by at least one of thermosetting and photocuring the flame-retardant curable resin composition of the present invention or the dry film of the present invention. Although the specific example of the manufacturing method of the said flame-retardant film is given to the following, it is not limited to this. In the case of the form of the flame-retardant curable resin composition, for example, adjusted to a viscosity suitable for the coating method with the organic solvent, on the substrate, dip coating method, flow coating method, roll coating method, bar coater method, 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 (temporary drying) at a temperature of about 60 to 100 ° C. Moreover, in the case of the said dry film form, it bonds together on a base material using a hot roll laminator etc. (It bonds so that the said flame-retardant curable resin composition layer and a base material may contact). In the case of a dry film having a peelable cover film on the flame retardant curable resin composition layer of the film, after peeling the cover film, the flame retardant curable resin composition layer and the substrate Use a hot roll laminator or the like so that they come into contact with each other.

  Thereafter, when photocuring, the coated film of the obtained flame-retardant curable resin composition or the flame-retardant curable resin composition layer of the bonded dry film is exposed (active energy rays). Irradiation). The exposure may be either a contact type (or non-contact type) method of selectively exposing with an active energy ray through a photomask on which a pattern is formed, or a direct pattern exposure method using a laser direct exposure machine. By this exposure, the exposed portion (the portion irradiated by the active energy ray) of the coating film (flame retardant curable resin composition layer) is cured. Next, by developing the unexposed portion with a dilute alkaline aqueous solution (for example, 0.3 to 3% sodium carbonate aqueous solution) to form a resist pattern, the above-mentioned flame retardant coating film having a desired pattern can be obtained. In the case of thermosetting, for example, (C) in the presence of the thermosetting component having the cyclic (thio) ether group as the thermosetting component, the thermosetting is performed by heating to a temperature of about 140 to 180 ° C. By causing the carboxyl group of the (B) carboxyl group-containing resin to react with the thermosetting component having a cyclic (thio) ether group to form a cured coating film, a flame-retardant coating film is obtained. Can do.

  As the substrate, 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, fluorine Copper-clad laminates of all grades (FR-4 etc.) using composite materials such as resin, polyethylene, polyphenylene ether, polyphenylene oxide and cyanate ester, polyimide film, PET film, glass substrate, ceramic substrate, wafer plate, etc. Can be used.

  Volatile drying performed after applying the flame-retardant curable resin composition of the present invention is a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (using a heat source of an air heating method using steam, The method can be carried out using a method in which the hot air in the dryer is brought into countercurrent contact or a method in which the hot air is blown onto the support from a nozzle.

As an exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, and the like may be used as long as the apparatus irradiates ultraviolet rays in a range of 350 to 450 nm. Furthermore, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer) can also be used. As the laser light source of the direct drawing machine, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. The amount of exposure for image formation varies depending on the film thickness and the like, but is generally 20 to 800 mJ / cm ² , preferably 20 to 600 mJ / cm ² .

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

  The printed wiring board of the present invention comprises a flame retardant coating obtained by subjecting the flame retardant curable resin composition of the present invention or the dry film of the present invention to at least one of thermosetting and photocuring. . Although the specific example of the manufacturing method of the said printed wiring board is given to the following, it is not limited to this.

  After forming a coating film of the flame-retardant curable resin composition of the present invention on a printed circuit board on which a circuit is formed, or by laminating the dry film of the present invention to form a flame-retardant curable resin composition layer (After laminating on the printed circuit board on which the circuit is formed, the support is not peeled off), or directly irradiating active energy rays such as laser light as the pattern, or A resist pattern can be formed by selectively exposing with an active energy ray through a photomask on which a pattern has been formed, and developing the unexposed portion with a dilute alkaline aqueous solution (if the dry film is bonded, the support is peeled off after exposure) ,develop). Thereby, a printed wiring board provided with the said flame-retardant film of a desired pattern can be obtained. In addition, in the case of thermosetting, final curing (main curing) is performed only by heat curing, or by heat curing after irradiation with active energy rays or after irradiation with active energy rays to form a cured film (cured product). Can do. Thereby, a printed wiring board provided with the said flame-retardant film can be obtained. The pattern formation is not limited to the photolithography method, and a screen printing method or the like may be used.

  The photopolymerizable resin composition of the present invention and a cured coating film formed from a dry film are suitable as a permanent film for a printed wiring board, and particularly suitable as a solder resist or an interlayer insulating material.

(Synthesis of phosphorus element-containing acrylate resin)
[Synthesis Example 1]
10- (2,3-dicarboxypropyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., M-Acid) 1384 parts by weight, 3-methylpentane 590 parts by weight of a diol and 0.1 parts by weight of tetra-n-butyl titanate as a catalyst were charged into an autoclave and heated at 220 to 235 ° C. for 3 hours, then the pressure was reduced to 5 mmHg over 20 minutes, and the temperature was increased to 250 ° C. The polycondensation reaction was carried out at 250 ° C. for 60 minutes. Thereafter, the obtained reaction product was cooled to room temperature, and 147 g of acrylic acid, 19.22 g of methanesulfonic acid, 0.3 g of methylhydroquinone and 1000 g of toluene were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube. Then, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring. Water produced by the reaction was distilled off as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 58.92 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 529.5 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a phosphorus element-containing acrylate resin solution (varnish) having a solid content of 75% and a phosphorus concentration of 6.3%. Hereinafter, the obtained phosphorus element-containing acrylate resin solution is referred to as A-1.

[Synthesis Example 2]
692 parts by weight of 10- (2,3-dicarboxypropyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., M-Acid), 284 weights of glycidyl methacrylate 418 weight parts of diethylene glycol monomethyl ether acetate was heated and stirred at 100 ° C. to dissolve uniformly. Next, 2.1 parts by weight of triphenylphosphine was charged and reacted at 115 ° C. for 4 hours to obtain a phosphorus element-containing acrylate resin solution (varnish) having a solid content of 65% and a phosphorus concentration of 4.7%. Hereinafter, the obtained phosphorus element-containing acrylate resin solution is referred to as A-2.

(Synthesis or preparation of carboxyl group-containing resin)
[Synthesis Example 3: Synthesis of Resin Corresponding to Carboxyl Group-Containing Resin (5) (B-1)]
In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 2400 g (3 of polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol (manufactured by Asahi Kasei Chemicals, T5650J, number average molecular weight 800) Mol), 603 g (4.5 mol) of dimethylolpropionic acid, and 238 g (2.6 mol) of 2-hydroxyethyl acrylate as a monohydroxyl compound. Next, 1887 g (8.5 mol) of isophorone diisocyanate was added as a polyisocyanate, and the mixture was stopped by heating to 60 ° C. while stirring. When the temperature in the reaction vessel began to decrease, the mixture was heated again and stirred at 80 ° C. The reaction was terminated after confirming that the absorption spectrum of the isocyanate group (2280 cm ⁻¹ ) had disappeared in the infrared absorption spectrum. Carbitol acetate was added so that the solid content was 50% by mass. The acid value of the solid content of the obtained carboxyl group-containing resin was 50 mgKOH / g. Hereinafter, the obtained resin solution (varnish) is referred to as B-1.

[Preparation Example 1: Preparation of resin corresponding to the carboxyl group-containing resin (8) (B-2)]
Uses photosensitive carboxyl group-containing resin (Nippon Kayaku Co., Ltd., ZFR-1401H (solid content 65%, acid value as resin is 98 mgKOH / g)) containing photosensitive group and using bisphenol F type polyfunctional epoxy It was. Hereinafter, the resin solution (varnish) is referred to as B-2.

[Preparation Example 2: Preparation of resin corresponding to the carboxyl group-containing resin (4) (B-3)]
A carboxyl group-containing resin containing a photosensitive group and having a urethane structure [manufactured by Nippon Kayaku Co., Ltd., UXE-3000 (solid content: 65%, acid value as resin: 98 mgKOH / g)] was used. Hereinafter, the resin solution (varnish) is referred to as B-3.

[Preparation Example 3: Preparation of resin corresponding to the carboxyl group-containing resin (7) (B-4)]
Use photosensitive carboxyl group-containing resin (Nippon Kayaku Co., Ltd., ZCR-1601H (solid content 65%, acid value as resin is 98 mgKOH / g)) using photosensitive group-containing biphenyl novolac type polyfunctional epoxy It was. Hereinafter, the resin solution (varnish) is referred to as B-4.

[Comparative Synthesis Example (R-1)]
Orthocresol novolak type epoxy resin (produced by DIC, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) 1070 g (number of glycidyl groups (total number of aromatic rings): 5) 0.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, heated and stirred at 100 ° C., and uniformly dissolved. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. To the obtained reaction solution, 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 4 hours. After cooling, the solid content acid value 89 mgKOH / G, a resin solution having a solid content of 65% was obtained. Hereinafter, the obtained resin solution (varnish) is referred to as R-1.

[Example 8, Reference Examples 1-7 , 9 and Comparative Examples 1-4]
The above resin solution (varnish) is blended in the proportions (parts by mass) shown in Table 1 together with various components shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and curable resin composition A product was prepared. Here, it was 15 micrometers or less when the dispersion degree of each obtained curable resin composition was evaluated by the particle size measurement by the grindometer by Eriksen.

＊１：三菱化学社製 ＹＸ４０００、固形分１００％
＊２：三菱化学社製 ｊＥＲ８２８、固形分１００％
＊３：ダウ・ケミカル社製 Ｄ．Ｅ．Ｎ．４３８ＣＡ９０、固形分９０％：カルビトールアセテート１０％
＊４：ＢＡＳＦジャパン社製 ルシリンＴＰＯ
＊５：ＢＡＳＦジャパン社製 イルガキュアー３８９
＊６：ＢＡＳＦジャパン社製 イルガキュアーＯＸＥ−０２
＊７：大塚化学社製 ＳＰＥ−１００
＊８：新中村化学社製 ＢＰＥ−５００
＊９：日本化薬社製 ＫＡＹＡＲＡＤ ＵＸ−２２０１
＊１０：昭和電工社製 ハイジライトＨ−４２Ｍ
＊１１：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：３
＊１２：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ１４７
＊１３：ジエチレングリコールモノエチルエーテールアセテート

* 1: YX4000 manufactured by Mitsubishi Chemical Corporation, solid content 100%
* 2: jER828 manufactured by Mitsubishi Chemical Corporation, solid content 100%
* 3: Dow Chemical Co., Ltd. E. N. 438CA90, solid content 90%: carbitol acetate 10%
* 4: Lucirin TPO manufactured by BASF Japan
* 5: Irgacure 389 manufactured by BASF Japan
* 6: Irgacure OXE-02 manufactured by BASF Japan
* 7: SPE-100 manufactured by Otsuka Chemical Co., Ltd.
* 8: Shin Nakamura Chemical Co., Ltd. BPE-500
* 9: KAYARAD UX-2201 manufactured by Nippon Kayaku Co., Ltd.
* 10: Showa Denko Hijilite H-42M
* 11: C.I. I. Pigment Blue 15: 3
* 12: C.I. I. Pigment Yellow147
* 13: Diethylene glycol monoethyl ether acetate

[Performance evaluation]
<Optimum exposure amount>
The curable resin compositions of Examples 8 and Reference Examples 1 to 7, 9 and Comparative Examples 1 to 4 were washed with water after drying a circuit pattern substrate with a copper thickness of 35 μm, dried, and then screen printed. It apply | coated to the whole surface and was dried for 30 minutes with the 80 degreeC hot-air circulation type drying furnace (after-drying film thickness 20 micrometers). Exposure is performed through a step tablet (Kodak No. 2) using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and development (30 ° C., 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution) is performed for 60 seconds. The amount of exposure of the step tablet remaining when the step was performed was determined as the optimum exposure amount.

<Flexibility (fold resistance)>
The curable resin compositions of the above Examples 8, Reference Examples 1 to 7, 9 and Comparative Examples 1 to 4 were applied to the entire surface of a 25 μm-thick polyimide film (manufactured by Toray DuPont, Kapton 100H) by screen printing. The film was dried at 80 ° C. for 30 minutes and allowed to cool to room temperature (film thickness after drying: 15 μm). The obtained substrate is exposed to a resist pattern with an optimal exposure amount using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. is sprayed at a pressure of 0.2 MPa. After developing for 60 seconds to obtain a resist pattern, the substrate was cured by heating at 150 ° C. for 60 minutes to obtain an evaluation substrate.
The obtained evaluation substrate was subjected to 180 ° folding by goblet folding several times, and the occurrence of cracks in the coating film was observed visually and with a 200-fold optical microscope until cracks were generated. The number of bendings was measured and the flexibility was evaluated according to the following criteria.
◎: 5 times or more ○: 3-4 times △: 1-2 times ×: 0 times

<High temperature press resistance>
The curable resin compositions of the above Examples 8, Reference Examples 1 to 7, 9 and Comparative Examples 1 to 4 were all coated by screen printing on a patterned polyimide film substrate and dried at 80 ° C. for 30 minutes. And allowed to cool to room temperature (film thickness after drying 20 μm). The obtained substrate is exposed to a solder resist pattern at an optimum exposure amount using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. is applied at a spray pressure of 2 kg / cm ² . Development was performed under conditions for 60 seconds to obtain a resist pattern. This substrate was cured by heating at 150 ° C. for 60 minutes. The obtained printed circuit board (evaluation board) was sandwiched between cushion materials and a SUS plate was used to give a load of 20 kgf / cm ² and vacuum pressing was performed at 150 ° C. for 60 minutes. The opening of the substrate after pressing was observed visually and with a 200 × optical microscope to confirm bleed out, and the high temperature press resistance was evaluated according to the following criteria.
○: No bleed-out in the opening.
X: Bleed out at the opening.

<Flame retardance>
The curable resin compositions of the above Examples 8, Reference Examples 1 to 7, 9 and Comparative Examples 1 to 4 were applied to a polyimide film having a thickness of 25 μm and 12.5 μm (manufactured by Toray DuPont, Kapton 100H (25 μm)). The whole surface was applied by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature (film thickness after drying 20 μm). 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. The obtained double-sided substrate is exposed to the entire surface of the solder resist with an optimum exposure amount using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. is sprayed at a pressure of 2 kg / cm ^2. Development was performed for 60 seconds under the above conditions, and thermosetting was performed at 150 ° C. for 60 minutes to obtain an evaluation sample. With respect to the sample for evaluation of flame retardancy, a thin material vertical combustion test based on the UL94 standard was performed as a flame retardancy test. In the evaluation, the flame retardancy test pass was indicated as VTM-0, and the failure was indicated as combustion.
Table 2 summarizes the results of the above evaluation tests.

(Example 17, Reference Examples 10-16, 18 )
Each curable resin composition prepared with the formulation of Example 8 and Reference Examples 1 to 7 and 9 shown in Table 1 excluding the silicone-based antifoaming agent was diluted with methyl ethyl ketone and applied onto a carrier film (PET). Then, it was dried by heating to form a photosensitive resin composition layer having a thickness of 20 μm, and a cover film (PE) was bonded 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 to prepare a test substrate. In the same manner as the test method and the evaluation method described above, an evaluation test of each characteristic was performed. In addition, the dry film by the composition of Reference Example 1 is Reference Example 10, the composition of Reference Example 2 is Reference Example 11, the composition of Reference Example 3 is Reference Example 12, the composition of Reference Example 4 is the composition of Reference Example 13, and the composition of Reference Example 5 The composition of Reference Example 14, Reference Example 6 corresponds to Reference Example 15, the composition of Reference Example 7 corresponds to Reference Example 16, the composition of Example 8 corresponds to Example 17, and the composition of Reference Example 9 corresponds to Reference Example 18. The results are shown in Table 3 below.

From the results shown in Tables 2 and 3, the curable resin compositions of Examples 8 and 17 and Reference Examples 1 to 7 , 9 to 16, and 18 have good flexibility and excellent difficulty. It turns out that it also has flammability. On the other hand, it turned out that the curable resin composition of the comparative example 1 which does not contain the phosphorus containing acrylate resin of this invention is inferior to a flame retardance and flexibility. Moreover, it turned out that the comparative example 2 which replaced (B) carboxyl group containing resin of the reference example 1 with the other carboxyl group containing resin is inferior to the reference example 1 in flexibility. Comparative Example 3 using phenoxyphosphazene instead of the phosphorus-containing acrylate resin of the present invention has good flexibility and flame retardancy but is inferior in high-temperature press resistance, and urethane instead of the phosphorus-containing acrylate resin of the present invention Comparative Example 4 using acrylate was found to have good flexibility but poor flame retardancy. It turned out that the flame-retardant curable resin composition of this invention excellent in said characteristic can be preferably used as a soldering resist for FPC.

( Reference Example 19, Comparative Example 5)
The above resin solution (varnish) is blended in the proportions (mass parts) shown in Table 4 together with various components shown in Table 4, premixed with a stirrer, kneaded with a three-roll mill, and curable resin composition A product was prepared. Here, it was 15 micrometers or less when the dispersion degree of each obtained curable resin composition was evaluated by the particle size measurement by the grindometer by Eriksen.

＊１：日本化薬社製 ＮＣ−３０００−Ｌ（ビフェニルノボラック構造を有するエポキシ樹脂）の固形分７５％、カルビトールアセテート２５％で調整したワニス
＊２：三菱化学社製 ＹＸ４０００、固形分１００％
＊３：ＢＡＳＦジャパン社製 ルシリンＴＰＯ
＊４：ＢＡＳＦジャパン社製 イルガキュアーＯＸＥ−０２
＊５：新中村化学社製 ＢＰＥ−５００
＊６：昭和電工社製 ハイジライトＨ−４２Ｍ
＊７：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：３
＊８：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ１４７
＊９：ジエチレングリコールモノエチルエーテールアセテート

* 1: Varnish prepared with NC-3000-L (epoxy resin having a biphenyl novolac structure) manufactured by Nippon Kayaku Co., Ltd. with 75% solid content and 25% carbitol acetate * 2: YX4000 manufactured by Mitsubishi Chemical Corporation, 100% solid content
* 3: Lucirin TPO manufactured by BASF Japan
* 4: Irgacure OXE-02 manufactured by BASF Japan
* 5: Shin-Nakamura Chemical BPE-500
* 6: Heidilite H-42M manufactured by Showa Denko
* 7: C.I. I. Pigment Blue 15: 3
* 8: C.I. I. Pigment Yellow147
* 9: Diethylene glycol monoethyl ether acetate

[Performance evaluation]
About the curable resin composition of each said reference example 19 and the comparative example 5, optimal exposure amount, flexibility (folding resistance), high temperature press tolerance, and a flame retardance were evaluated by the same method as the above.

<Low warpage>
An evaluation sample obtained by manufacturing in the same manner as the evaluation substrate for flexibility (folding resistance) was cut into a side of 50 mm × 50 mm, and the average value was obtained by measuring four-sided warpage. Evaluated.
○: The warp is less than 4 mm.
(Triangle | delta): The curvature is 4 mm or more and less than 8 mm.
X: The warp is 8 mm or more.
The results of the above evaluation tests are summarized in Table 5.

( Reference Example 20, Comparative Example 6)
Each curable resin composition prepared by blending Reference Example 19 and Comparative Example 5 shown in Table 4 with the silicone antifoam removed is diluted with methyl ethyl ketone, coated on a carrier film (PET), and dried by heating. Then, a photosensitive resin composition layer having a thickness of 20 μm was formed, and a cover film (PE) was bonded 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 to prepare a test substrate. In the same manner as the test method and the evaluation method described above, an evaluation test of each characteristic was performed. The dry film having the composition of Reference Example 19 corresponds to Reference Example 20 and the dry film having the composition of Comparative Example 5 corresponds to Comparative Example 6, respectively. The results are shown in Table 6 below.

From the results shown in Tables 5 and 6 above, in the case of the curable resin compositions of Reference Examples 19 and 20, it has good flexibility and low warpage, and also has excellent flame retardancy. I understand.

[ Reference Examples 19 and 21 and Comparative Examples 7 and 8]
The above resin solution (varnish) was blended in the proportions (parts by mass) shown in Table 7 together with various components shown in Table 7, premixed with a stirrer, kneaded with a three-roll mill, Reference Example 21 and The curable resin compositions of Comparative Examples 7 and 8 were prepared. Here, it was 15 micrometers or less when the dispersion degree of each obtained curable resin composition was evaluated by the particle size measurement by the grindometer by Eriksen. The following evaluation tests were performed for each curable resin composition and the curable resin composition of Reference Example 19 described above.

[Performance evaluation]
<Low warpage>
In the same manner as above, the polyimide film thickness is 2 conditions (Kapton 100H (25 μm), Kapton 50H (12.5 μm), both manufactured by Toray DuPont), and the exposure amount is 2 conditions (100 mJ / cm ² , 400 mJ / cm Evaluation was made under a total of 4 conditions of ² ).

  The results of the evaluation test are summarized in Table 7. The numerical value described in the evaluation of the low warpage indicates an average value of the four corners.

＊１：未実施
＊２：昭和電工社製 ＨＦＡ−６０６５Ｅ（リン含有多官能アクリレート）（固形分６７．５％、ジエチレングリコールモノエチルエーテルアセテート３２．５％）
＊３：日本化薬社製 ＮＣ−３０００−Ｌ（ビフェニルノボラック構造を有するエポキシ樹脂）の固形分７５％、カルビトールアセテート２５％で調整したワニス
＊４：三菱化学社製 ＹＸ４０００、固形分１００％
＊５：ＢＡＳＦジャパン社製 ルシリンＴＰＯ
＊６：ＢＡＳＦジャパン社製 イルガキュアーＯＸＥ−０２
＊７：新中村化学社製 ＢＰＥ−５００
＊８：昭和電工社製 ハイジライトＨ−４２Ｍ
＊９：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：３
＊１０：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ１４７
＊１１：ジエチレングリコールモノエチルエーテールアセテート

* 1: Not implemented * 2: HFA-6065E (phosphorus-containing polyfunctional acrylate) (solid content 67.5%, diethylene glycol monoethyl ether acetate 32.5%) manufactured by Showa Denko KK
* 3: Varnish adjusted with 75% solid content of NC-3000-L (epoxy resin having biphenyl novolac structure) manufactured by Nippon Kayaku Co., Ltd. and 25% carbitol acetate * 4: YX4000 manufactured by Mitsubishi Chemical Corporation, 100% solid content
* 5: Lucirin TPO manufactured by BASF Japan
* 6: Irgacure OXE-02 manufactured by BASF Japan
* 7: Shin-Nakamura Chemical Co., Ltd. BPE-500
* 8: Showa Denko Hijilite H-42M
* 9: C.I. I. Pigment Blue 15: 3
* 10: C.I. I. Pigment Yellow147
* 11: Diethylene glycol monoethyl ether acetate

From the results shown in Table 7, it was found that the curable resin compositions of Reference Examples 19 and 21 showed good low warpage. On the other hand, it was found that the curable resin compositions of Comparative Examples 7 and 8 containing other phosphorus element-containing acrylate resins (A) instead of the phosphorus element-containing acrylate resins were inferior in low warpage.

Claims (5)

(A) At least any one of phosphorus element-containing dicarboxylic acid represented by the following general formula (1) and its anhydride

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, m and n each independently represents an integer of 0 to 4; (Indicates that two carboxyl groups may form an acid anhydride.)
And a phosphorus element-containing compound (meta) that is a reaction product of a carboxylic acid or a (meth) acrylate compound having a functional group that reacts with the carboxylic acid or the carboxylic acid anhydride of at least one of the phosphorus element-containing dicarboxylic acid and its anhydride ) Acrylate resin,
(B) Structure derived from bisphenol A type epoxy resin, the structure derived from bisphenol F type epoxy resin, the structure derived from the biphenol type epoxy resin, the structure derived from biphenol novolak type epoxy resin, the structure and biphenyl novolak type from bixylenol type epoxy resin A carboxyl group-containing resin having one or more partial structures selected from the group consisting of structures derived from epoxy resins, and
At least any one carboxyl group-containing resin (C) thermosetting component selected from carboxyl group-containing urethane resins, and
(D) a photopolymerization initiator,
A flame retardant curable resin composition comprising: The flame-retardant curable resin composition according to claim 1, which is used for forming a solder resist. A dry film comprising a layer formed by applying and drying the flame-retardant curable resin composition according to claim 1 or 2 on a film. A cured product of a layer formed by applying and drying the flame retardant curable resin composition according to claim 1 or 2 on the film and the flame retardant curable resin composition of the dry film according to claim 3. A flame retardant coating characterized by being. A printed wiring board comprising the flame-retardant coating according to claim 4 .