JP5043775B2 - Flame-retardant photocurable resin composition, dry film and cured product thereof, and printed wiring board using them - Google Patents

Description

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

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

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

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

  In order to achieve the above object, according to the present invention, (A) an organic solvent-soluble phosphorus element-containing polyester, (B) a carboxyl group-containing resin, and (C) a photopolymerization initiator are included. A flammable photocurable resin composition is provided. Preferably, the carboxyl group-containing resin (B) is a carboxyl group-containing polyurethane resin.

  In a suitable aspect, it further contains (D) a photopolymerizable monomer, or further contains (E) a thermosetting resin. The thermosetting resin (E) preferably contains an epoxy resin having a biphenyl skeleton. Such a flame-retardant photocurable resin composition, particularly a flame-retardant photocurable / thermosetting resin composition containing the thermosetting resin (E), can be suitably used as a solder resist.

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

Since the flame-retardant photocurable resin composition of the present invention uses a halogen-free organic solvent-soluble phosphorus element-containing polyester and a carboxyl group-containing resin, the non-halogen composition has low environmental impact and excellent flame retardancy. The cured film is rich in flexibility and can form a cured film having a fine pattern excellent in adhesion to various substrates, solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, and the like.
Therefore, the flame-retardant photocurable resin composition of the present invention can be advantageously applied to the formation of a flame-retardant cured film such as a printed wiring board, particularly an FPC solder resist.

式中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、又は炭化水素基を表し、
Ｒ^３及びＲ^４、はそれぞれ独立に、水素原子、炭化水素基またはヒドロキシ基置換炭化水素基を表し、
ｌ、ｍは０〜４の整数を表す。
前記の有機溶剤可溶性リン元素含有ポリエステルの市販品としては、東洋紡（株）製バイロン（登録商標）２３７、バイロン３３７等が挙げられる。
これらリン元素含有ポリエステルは部分的にジイソシアネートを用いてウレタン結合を導入したポリエステルポリウレタン構造であってもかまわない。例えば、市販されているものとしては、東洋紡（株）製ＵＲ３５７０等が挙げられる。 As described above, the first feature of the flame-retardant photocurable resin composition of the present invention is that a halogen-free organic solvent-soluble phosphorus element-containing polyester (A) is used. In the present specification, the term “halogen-free” means that a halogen compound is not actively used unless it is mixed as an inevitable impurity.
The organic solvent-soluble phosphorus element-containing polyester (A) is used in the production of the polyester to contain a phosphorus-containing carboxylic acid or an esterified product thereof, a phosphoric acid compound, a phosphonic acid compound, a phosphorous acid compound, a phosphonite compound, It is obtained by copolymerizing a phosphorus compound such as a phosphinic acid compound (see, for example, JP 2002-3587 A, JP 2007-204744 A, etc.).
Preferably, it is a phosphorus-containing carboxylic acid represented by the following general formula (I) or an organic solvent-soluble phosphorus element-containing polyester obtained by co-polymerizing an ester compound thereof.

In the formula, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group,
R ³ and R ⁴ each independently represents a hydrogen atom, a hydrocarbon group or a hydroxy group-substituted hydrocarbon group,
l and m represent an integer of 0 to 4;
Examples of commercially available organic solvent-soluble phosphorus element-containing polyesters include Byron (registered trademark) 237 and Byron 337 manufactured by Toyobo Co., Ltd.
These phosphorus element-containing polyesters may have a polyester polyurethane structure in which urethane bonds are partially introduced using diisocyanate. For example, as a commercially available product, UR3570 manufactured by Toyobo Co., Ltd. may be mentioned.

As the organic solvent-soluble phosphorus element-containing polyester (A), various high molecular weight polyester resin compounds that are soluble in various industrial organic solvents can be used, and are not limited to specific ones, but preferably have the following properties.
(1) The weight average molecular weight is generally in the range of 1,000 to 100,000, more preferably 5,000 to 50,000. If the weight average molecular weight is less than 1,000, the tack-free performance of the resulting coating film may be inferior. On the other hand, when the weight average molecular weight exceeds 100,000, the solubility in various organic solvents is lowered, and the developability of the resulting coating film may be remarkably deteriorated.
(2) The phosphorus content in the polyester is generally in the range of 0.3 to 20%, more preferably 1 to 5%. If it is less than 0.3%, sufficient flame retardancy may not be obtained. On the other hand, if it exceeds 20%, the flexibility and electrical properties of the cured film may be remarkably deteriorated.

The amount of the organic solvent-soluble phosphorus element-containing polyester (A) is 0.5 to 50% by mass, preferably 1 to 20% by mass in the entire composition.
When less than the said range, sufficient flame retardance of the cured film obtained is not acquired, and a favorable result is not acquired also in flexibility. On the other hand, when the amount is more than the above range, the tack-free performance of the coating film is lowered or the viscosity of the composition is increased, which is not preferable.

Various organic solvents for industrial use used in organic solvent-soluble phosphorus element-containing polyester (A) include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, and aliphatic hydrocarbons. And petroleum solvents. 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 is used alone or as a mixture of two or more, and more preferably does not accelerate hydrolysis of the high molecular weight polyester resin compound.

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

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

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

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

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

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

式中、Ｒ^５及びＲ^６は、それぞれ独立に、炭素数１〜１０の直鎖状又は分岐状のアルキル基、炭素数１〜１０の直鎖状又は分岐状のアルコキシ基、シクロヘキシル基、シクロペンチル基、アリール基、又はハロゲン原子、アルキル基もしくはアルコキシ基で置換されたアリール基を表し、但し、Ｒ^５及びＲ^６の一方は、Ｒ−Ｃ（＝Ｏ）−基（ここでＲは、炭素数１〜２０の炭化水素基）を表してもよい。 As the photopolymerization initiator (C) used in the present invention, known and commonly used compounds can be used.
Particularly preferred photopolymerization initiators include phosphorus element-containing photopolymerization initiators, and acylphosphine oxide photopolymerization initiators having a group represented by the following general formula (II-1) can be suitably used.

In the formula, R ⁵ and R ⁶ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a cyclohexyl group, or cyclopentyl. A group, an aryl group, or an aryl group substituted with a halogen atom, an alkyl group or an alkoxy group, provided that one of R ⁵ and R ⁶ is an R—C (═O) — group (where R is a carbon (Hydrocarbon group of 1 to 20).

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

式中、Ｒ^５は前記と同様の意味を有し、Ｒ^７は、Ｒ^５とは独立に、炭素数１〜１０の直鎖状又は分岐状のアルキル基、シクロヘキシル基、シクロペンチル基、アリール基、又はハロゲン原子、アルキル基で置換されたアリール基を表し、Ｒ−Ｃ（＝Ｏ）−基（ここでＲは、炭素数１〜２０の炭化水素基）を表してもよい。 Another preferable phosphorus element-containing photopolymerization initiator is an initiator represented by the following general formula (II-2), and a commercially available product is Lucilin TPO-L manufactured by BASF.

In the formula, R ⁵ has the same meaning as described above, and R ⁷ is, independently of R ⁵ , a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, or an aryl group. Or an aryl group substituted with a halogen atom or an alkyl group, and an R—C (═O) — group (where R is a hydrocarbon group having 1 to 20 carbon atoms).

  The compounding quantity of such a phosphorus element containing photoinitiator can be selected from the range of 1-80 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (B), Preferably it is 2-50 mass parts. .

式中、Ｒ^８は、水素原子、フェニル基（炭素数１〜６のアルキル基、フェニル基、もしくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基もしくはフェニル基で置換されていてもよい）を表し、
Ｒ^９は、フェニル基（炭素数１〜６のアルキル基、フェニル基もしくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基もしくはフェニル基で置換されていてもよい）を表し、
Ｒ^１０及びＲ^１１は、それぞれ独立に、炭素数１〜１２のアルキル基又はアリールアルキル基を表し、
Ｒ^１２及びＲ^１３は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、又は２つが結合した環状アルキルエーテル基を表す。 The photopolymerization initiator that can be added in addition to the phosphorus element-containing photopolymerization initiator includes an oxime ester photopolymerization initiator having a group represented by the following general formula (III), represented by the following general formula (IV): There are α-aminoacetophenone photopolymerization initiators having the following groups.

In the formula, R ⁸ represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R ⁹ is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups). Well, it may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having 1 to 6 carbon atoms) Which may be substituted with an alkyl group or a phenyl group of
R ¹⁰ and R ¹¹ each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group,
R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded.

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

式中、Ｒ^１４は、水素原子、ハロゲン原子、炭素数１〜１２のアルキル基、シクロペンチル基、シクロヘキシル基、フェニル基、ベンジル基、ベンゾイル基、炭素数２〜１２のアルカノイル基、炭素数２〜１２のアルコキシカルボニル基（アルコキシル基を構成するアルキル基の炭素数が２以上の場合、アルキル基は１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、又はフェノキシカルボニル基を表し、
Ｒ^１５、Ｒ^１７は、それぞれ独立に、フェニル基（炭素数１〜６のアルキル基、フェニル基もしくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基もしくはフェニル基で置換されていてもよい）を表し、
Ｒ^１６は、水素原子、フェニル基（炭素数１〜６のアルキル基、フェニル基もしくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基もしくはフェニル基で置換されていてもよい）を表す。

In the formula, R ¹⁴ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, or 2 to 2 carbon atoms. 12 alkoxycarbonyl groups (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, and one or more oxygen atoms are placed in the middle of the alkyl chain. Which may have), or a phenoxycarbonyl group,
R ¹⁵ and R ¹⁷ are each independently a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R ¹⁶ is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (substituted with one or more hydroxyl groups). And may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having a carbon number). 1-6 alkyl groups or phenyl groups optionally substituted).

式中、Ｒ^１８、Ｒ^１９及びＲ^２４は、それぞれ独立に、炭素数１〜１２のアルキル基を表し、
Ｒ^２０、Ｒ^２１、Ｒ^２２及びＲ^２３は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表し、
Ｍは、Ｏ、Ｓ又はＮＨを表し、
ｎ及びｐは、それぞれ独立に０〜５の整数を表す。

In formula, R <^18> , R <^19> and R < ²⁴ > represent a C1-C12 alkyl group each independently,
R ²⁰ , R ²¹ , R ²² and R ²³ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
M represents O, S or NH;
n and p each independently represent an integer of 0 to 5.

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

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

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

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

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

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

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

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

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

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

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

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

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

式中、Ｒ^２５はアクリレート残基であり、Ｒ^２６とＲ^２７は水素もしくはハロゲン以外の有機基であるアクリレート誘導体である。このようなリン含有化合物変性アクリレートは、一般に、９，１０−ジヒドロー９−オキサ−１０−フォスファフェナンスレン−１０−オキサイドと慣用公知の多官能アクリレートとのマイケル付加反応により合成することができる。 Among the (meth) acrylate monomers, a phosphorus element-containing acrylate is preferable from the viewpoint of flame retardancy. For example, phosphate polyfunctional acrylates typified by trisacryloyloxyethyl phosphate, or specifically phosphorus-containing compound-modified acrylates represented by the following general formula (VIII) can be mentioned.

In the formula, R ²⁵ is an acrylate residue, and R ²⁶ and R ²⁷ are acrylate derivatives which are organic groups other than hydrogen or halogen. Such phosphorus-containing compound-modified acrylates can generally be synthesized by a Michael addition reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with a conventionally known polyfunctional acrylate. .

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

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

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

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

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

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

式中、Ｒ^２８、Ｒ^２９及びＲ^３０は、それぞれ独立に、ハロゲン原子以外の置換基を示す。
上記一般式（IX）表される化合物の市販品としてはＨＣＡ、ＳＡＮＫＯ−２２０、Ｍ−ＥＳＴＥＲ、ＨＣＡ−ＨＱ等がある。 The photocurable resin composition of the present invention can further contain a phosphorus-containing compound as a flame retardant auxiliary. As the phosphorus-containing compound, those conventionally known as organic phosphorus flame retardants may be used, and examples include phosphoric acid esters and condensed phosphoric acid esters, cyclic phosphazene compounds, phosphazene oligomers, and compounds represented by the following general formula (IX).

In the formula, R ²⁸ , R ²⁹ and R ³⁰ each independently represent a substituent other than a halogen atom.
Commercially available products of the compound represented by the general formula (IX) include HCA, SANKO-220, M-ESTER, HCA-HQ and the like.

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

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

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

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

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

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

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

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

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

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

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

Furthermore, the photocurable resin composition of the present invention uses an organic solvent for the synthesis of the carboxyl group-containing resin (B), the preparation of the composition, or the viscosity adjustment for application to a substrate or a carrier film. can do.
Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, 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 organic solvents are used alone or as a mixture of two or more.

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

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

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

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

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

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

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

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

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

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

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

Examples 1 to 3, Comparative Examples 1 and 2
Each component shown in Table 1 was blended in the proportions (parts by mass) shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and a photocurable / thermosetting resin composition for a solder resist. Prepared. Here, when the degree of dispersion of the obtained photocurable / thermosetting resin composition was evaluated by particle size measurement using a grindometer manufactured by Eriksen, it was 15 μm or less.

Performance evaluation:
<Optimum exposure amount>
The photocurable / thermosetting resin compositions of the above Examples and Comparative Examples were applied to the entire surface by screen printing after applying a circuit board having a copper thickness of 35 μm to buffing, washing with water and drying. For 30 minutes in a hot air circulation drying oven. After drying, 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) When the pattern of the step tablet remaining when performing for 60 seconds was 6 steps, the optimum exposure amount was set.

Characteristic test:
The compositions of the above Examples and Comparative Examples are applied onto the patterned polyimide film substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. The substrate is exposed to a solder 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 applied under a spray pressure of 0.2 MPa. Development was performed for 2 seconds to obtain a resist pattern. This substrate was cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.

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

<Electroless gold plating resistance>
Using a commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 3 μm and gold 0.03 μm, and the presence or absence of peeling of the resist layer or plating penetration is confirmed by tape peeling. After the evaluation, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.
A: No soaking or peeling is observed.
○: Slight penetration is confirmed after plating, but does not peel off after tape peeling.
Δ: Slight penetration after plating and peeling after tape peel.
X: There is peeling after plating.

<Electrical characteristics>
Using an IPC B-25 comb-type electrode B coupon instead of a copper foil substrate, an evaluation board was prepared under the above conditions, and a bias voltage of DC 100 V was applied to the comb-type electrode, and 85 ° C., 85% R.D. H. The presence or absence of migration after 1,000 hours was confirmed in a constant temperature and humidity chamber. The judgment criteria are as follows.
○: No change is observed Δ: Only a slight change ×: Migration occurs

<Acid resistance>
The evaluation substrate was immersed in a 10 vol% H ₂ SO ₄ aqueous solution at room temperature for 30 minutes, and soaking and dissolution of the coating film were confirmed. Further, peeling due to tape peeling was confirmed. Judgment criteria are as follows.
○: No soaking, melting or peeling.
Δ: Slight penetration, dissolution or peeling is confirmed.
X: Significant infiltration, dissolution or peeling.

<Flame retardance>
The composition of each Example and Comparative Example is applied to a 25-um thick polyimide film (Kapton 100H) by screen printing, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature. Further, the entire back surface was similarly applied by screen printing, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature to obtain a double-side coated substrate. Using this exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, the entire surface of the solder resist is exposed to this substrate at an optimum exposure amount, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. is applied under a spray pressure of 0.2 MPa. Development was performed for 1 second, and thermosetting was performed at 150 ° C. for 60 minutes to obtain an evaluation sample. This flame retardant evaluation sample was subjected to a thin material vertical combustion test based on the UL94 standard. Evaluation was expressed as VTM-0 or VTM-1 based on the UL94 standard.

<Flexibility>
The compositions of each Example and Comparative Example were applied to a 25 μm polyimide film (Kapton 100H) by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature to obtain a single-side coated substrate. Using this exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, the entire surface of the solder resist is exposed to this substrate at an optimum exposure amount, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. is applied under a spray pressure of 0.2 MPa. Second development was performed, and thermosetting was performed at 150 ° C. for 60 minutes. The solder resist of the obtained sample is turned outside, and 180 ° bending by goat folding is repeated several times, and the crack occurrence state in the coating film at that time is observed visually and with an optical microscope with a magnification of 200, and no crack is generated. The number of times was evaluated.

上記表２に示されるように、本発明の有機溶剤可溶性リン元素含有ポリエステルを含有する光硬化性・熱硬化性樹脂組成物を用いた実施例１〜３の場合、得られた硬化皮膜は、難燃性及び可撓性に優れ、またはんだ耐熱性、耐無電解金めっき性、電気特性、耐酸性にも優れていたが、有機溶剤可溶性リン元素含有ポリエステルを含有しない光硬化性・熱硬化性樹脂組成物を用いた比較例２の場合、難燃性を有さなかった。一方、有機溶剤可溶性リン元素含有ポリエステルに代えて通常のリン含有難燃剤を含有する光硬化性・熱硬化性樹脂組成物を用いた比較例１の場合、難燃性に問題はなかったが、可撓性が悪く、またはんだ耐熱性や電気特性も充分ではなかった。 The results of each evaluation test are summarized in Table 2.

As shown in Table 2 above, in the case of Examples 1 to 3 using the photocurable and thermosetting resin composition containing the organic solvent-soluble phosphorus element-containing polyester of the present invention, the obtained cured film was: Excellent flame retardancy and flexibility, heat resistance, electroless gold plating resistance, electrical properties, and acid resistance, but does not contain organic solvent-soluble phosphorus element-containing polyester. In the case of Comparative Example 2 using the porous resin composition, it did not have flame retardancy. On the other hand, in the case of Comparative Example 1 using a photocurable thermosetting resin composition containing a normal phosphorus-containing flame retardant instead of the organic solvent-soluble phosphorus element-containing polyester, there was no problem in flame retardancy, The flexibility was poor or the heat resistance and electrical properties were not sufficient.

Example 4
A photocurable / thermosetting resin composition prepared with the same formulation as in Example 1 was diluted with methyl ethyl ketone, applied onto a carrier film, and dried by heating to form a resin composition layer having a thickness of 20 μm. It was dried for 30 minutes with a hot air drier at 0 ° C. Further, a cover film was laminated thereon to obtain a dry film. Thereafter, the cover film was peeled off and bonded to the patterned polyimide substrate using a laminator. This substrate was exposed to the solder resist pattern with an optimum exposure amount using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and the carrier film was peeled off, followed by spraying a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. Development was performed at 0.2 MPa for 60 seconds to obtain a substrate on which a resist pattern was formed. Thereafter, heat curing was performed for 60 minutes in a hot air dryer at 150 ° C. to prepare a test substrate. About the test board | substrate which has the obtained cured film, the evaluation test of each characteristic was done like the test method and evaluation method which were mentioned above.
The handling property of the obtained dry film was satisfactory, and the characteristics of the obtained dry film were almost the same as the results of Example 1.

Claims (9)

  A flame retardant photocurable resin composition comprising (A) an organic solvent-soluble phosphorus element-containing polyester, (B) a carboxyl group-containing resin, and (C) a photopolymerization initiator.   Furthermore, (D) a photopolymerizable monomer is contained, The flame-retardant photocurable resin composition of Claim 1 characterized by the above-mentioned.   The flame retardant photocurable resin composition according to claim 1, further comprising (E) a thermosetting resin.   The flame retardant photocurable resin composition according to claim 3, wherein the thermosetting resin (E) contains an epoxy resin having a biphenyl skeleton.   The flame retardant photocurable resin composition according to any one of claims 1 to 4, wherein the carboxyl group-containing resin (B) is a carboxyl group-containing polyurethane resin.   It is a solder resist, The flame-retardant photocurable resin composition as described in any one of Claims 1 thru | or 5.   The flame-retardant photocurable dry film obtained by apply | coating and drying the flame-retardant photocurable resin composition as described in any one of Claims 1 thru | or 6 on a carrier film.   A flame retardant cured product obtained by curing the flame retardant photocurable resin composition according to any one of claims 1 to 6 or the dry film according to claim 7.   A print comprising a flame retardant cured film obtained by curing the flame retardant photocurable resin composition according to any one of claims 1 to 6 or the dry film according to claim 7. Wiring board.