JP5854600B2 - Photocurable resin composition - Google Patents

Description

  The present invention is, for example, a photocurable resin composition used as a solder resist of a printed wiring board, a dry film and a cured product obtained therefrom, and a cured film such as a solder resist formed by the dry film or the cured product. The present invention relates to a printed wiring board.

The photocurable resin composition can be finely processed by applying the principle of a photographic method (photolithography). Furthermore, since a cured product having excellent physical properties can be obtained, it is used in electronic devices and printing plates.
The photocurable resin composition includes a solvent development type and an alkali development type. In recent years, an alkali development type that can be developed with a dilute weak alkaline aqueous solution has become mainstream from the viewpoint of environmental measures. For example, alkali-developable photocurable resin compositions are widely used in printed wiring board manufacture, liquid crystal display board manufacture, printing plate making, and the like. As a characteristic required for this, for example, when used as a solder resist in the production of a printed wiring board, the cured product is required to have heat resistance that can withstand processing under high temperature conditions such as soldering.

  In recent years, as electronic devices have become smaller, lighter, more functional, and environmentally friendly, high-density mounting and thinning of printed wiring boards have been promoted. There is also a need to suppress the occurrence of cracks during the cooling and heating cycle. Furthermore, a high resolution is required for a solder resist used for a high-density mounting substrate having a fine pitch pattern for high-density mounting. In order to obtain a high resolution, it is necessary to increase the contrast between the exposed area and the unexposed area. For reducing the brittleness of the cured product, which is expected to improve crack resistance during the thermal cycle, a mixture of bisphenol-type carboxyl group-containing epoxy (meth) acrylate and novolac-type carboxyl group-containing epoxy (meth) acrylate is used. A technique has been proposed (see, for example, Patent Document 1). However, such a method has not yet achieved both high resolution and crack resistance.

  A typical example of a conventional photocurable resin composition is a photocurable resin composition using a carboxyl group-containing epoxy (meth) acrylate resin and a (meth) acrylate monomer together with a photopolymerization initiator. By using the composition having such a configuration, a required pattern is formed through a development process after light irradiation. However, in order to obtain high resolution, there is a problem that it is difficult to balance the photopolymerization initiator and the photoreactive carboxyl group-containing epoxy (meth) acrylate resin or (meth) acrylate monomer. In particular, when exposed in a state where a PET (polyethylene terephthalate) film is attached to a dry coating film of a liquid type and a dry film type, since the PET film is exposed in a state where it exists on the resist surface, it is not subjected to oxygen inhibition, A dark reaction proceeds on the resist surface and halation is likely to occur, and there is a problem that the desired stable resolution cannot be obtained. Therefore, studies have been made to obtain stable resolution by using methoquinone, hydroquinone, phenothiazine and the like as a polymerization inhibitor, but sufficient results have not been obtained.

JP 2000-109541 A (Claims)

The present invention has been made in view of the above-described problems of the prior art, and halation and undercutting may occur even when exposed in a state where a film is applied to a dry coating film of a liquid type or a dry film type. It is an object of the present invention to provide a photocurable resin composition that can obtain high resolution and can suppress the occurrence of cracks during a cooling and heating cycle.
Furthermore, the object of the present invention is to obtain a dry film and a cured product excellent in various properties as described above obtained by using such a photocurable resin composition, and to cure a solder resist or the like with the dry film or the cured product. It is providing the printed wiring board by which a membrane | film | coat is formed.

According to one aspect of the present invention, there is provided a photocurable resin composition comprising a carboxyl group-containing resin, a photopolymerization initiator, a naphthalene derivative and / or naphthoquinone and a derivative thereof. In a preferred embodiment, the naphthalene derivative and / or naphthoquinone and its derivative are compounds having a hydroxyl group.
With such a configuration, high resolution is obtained, and when the cured product is used for a printed wiring board or the like, it is possible to improve the thermal cycle resistance. Here, in the photocurable resin composition of the present invention, the carboxyl group-containing resin preferably has a photosensitive group. By having the photosensitive group, the photocurability of the photocurable resin composition increases, and the sensitivity can be improved.

（式中、Ｒ^１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、若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のアルキル基若しくはフェニル基で置換されていてもよい）を表し、Ｒ^２は、フェニル基（炭素数１〜６のアルキル基、フェニル基若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のアルキル基若しくはフェニル基で置換されていてもよい）を表し、Ｒ^３及びＲ^４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^５及びＲ^６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し、Ｒ^７及びＲ^８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、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、アルキル基若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^７及びＲ^８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。）
このような光重合開始剤を用いることにより、高濃度で顔料を有するレジストにおいても高解像性を得ることが可能となる。 In one embodiment of the photocurable resin composition of the present invention, the photopolymerization initiator is an oxime ester photopolymerization initiator represented by the following general formula (I), represented by the following general formula (II). And a mixture of one or more photopolymerization initiators selected from the group consisting of acylphosphine oxide photopolymerization initiators represented by the following general formula (III): Is preferred.

(In the formula, R ¹ 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). Or 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 benzoyl. Represents a group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group), and R ² is a phenyl group (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, and may have one or more oxygen atoms in the middle of the alkyl chain), carbon number 5 ˜8 cycloalkyl groups, Represents an alkanoyl group or a benzoyl group prime 2-20 (carbon atoms may be substituted with 1-6 alkyl or phenyl group), R ³ and R ⁴ are each independently, a carbon number 1 to 12 R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded, and R ⁷ and R ^8. Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl 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 ⁷ and R ⁸ may represent an R—C (═O) — group (where R is a hydrocarbon group having 1 to 20 carbon atoms).
By using such a photopolymerization initiator, high resolution can be obtained even in a resist having a pigment at a high concentration.

Moreover, in one aspect | mode of the photocurable resin composition of this invention, it is preferable to contain a thermosetting component further. By containing a thermosetting component, while providing heat resistance, the tensile elongation rate of a cured film can be increased and crack resistance can be improved.
Furthermore, in the one aspect | mode of the photocurable resin composition of this invention, a coloring agent can be contained further. By containing a colorant, it can be suitably used as a solder resist.

Moreover, according to the other aspect of this invention, the dry film obtained by apply | coating and drying the photocurable resin composition mentioned above on a film is provided. By using such a dry film, a resist layer can be easily formed without applying a photocurable resin composition on a substrate.
Moreover, in 1 aspect of this invention, the photocurable resin composition or dry film mentioned above can be used as hardened | cured material obtained by carrying out photocuring by active energy ray irradiation.
When such a cured product is used for a printed wiring board or the like, it is possible to improve the heat cycle resistance.

Furthermore, according to the other aspect of this invention, the printed wiring board which has the pattern of the hardened | cured material obtained by photocuring the photocurable resin composition mentioned above or its dry film by active energy ray irradiation is provided. .
In such a printed wiring board, it is possible to improve the heat cycle resistance.

According to the photocurable resin composition of the present invention, since it contains a naphthalene derivative and / or naphthoquinone and its derivative together with a carboxyl group-containing resin and a photopolymerization initiator, a film is applied to a dry coating film of a liquid type and a dry film type. Even when exposed in the affixed state, halation and undercut do not occur and high resolution can be obtained, and the cured product improves the thermal cycle resistance when used for a printed wiring board or the like. It becomes possible.
Therefore, the photocurable resin composition of the present invention can be advantageously applied to the formation of a cured film such as a solder resist of a printed wiring board or a flexible printed wiring board, and can provide a stable resolution and a thermal cycle resistance (TCT). Resistance) and PCT (pressure cooker test) resistance, and other cured films such as solder resists excellent in various properties can be formed, and a highly reliable printed wiring board can be provided.

The present inventors have found that the above-described object can be achieved by a photocurable resin composition containing a carboxyl group-containing resin, a photopolymerization initiator, a naphthalene derivative and / or naphthoquinone and a derivative thereof. The invention has been completed.
In particular, by using a naphthalene derivative and / or naphthoquinone and its derivatives, it is possible to obtain a stable and high resolution without undercut or halation, without generating the starting point of crack generation during a thermal cycle, and crack resistance. Can be improved.
Hereinafter, the photocurable resin composition of the present invention will be described in detail.

  First, as the carboxyl group-containing resin constituting the photocurable resin composition of the present invention, various known carboxyl group-containing resins having a carboxyl group in the molecule are used for the purpose of imparting alkali developability. be able to. In particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is preferable from the viewpoint of photocurability and development resistance. The unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof.

As specific examples of the carboxyl group-containing resin, the following compounds (any of oligomers and polymers) are preferable.
(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 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 ( A carboxyl group-containing photosensitive urethane resin obtained by a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

  (4) During the synthesis of the resin of (2) or (3) described above, 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 photosensitive urethane resin.

  (5) During the synthesis of the resin described in (2) or (3) above, one isocyanate group and one or more (meth) acryl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate A carboxyl group-containing photosensitive urethane resin obtained by adding a compound having a terminal and being terminally (meth) acrylated.

  (6) (Meth) acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin as described later, and phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride are added to the hydroxyl group present in the side chain. A carboxyl group-containing photosensitive resin to which a dibasic acid anhydride such as

  (7) A polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group. Added carboxyl group-containing photosensitive resin.

  (8) A carboxyl group-containing polyester obtained by reacting a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid with a bifunctional oxetane resin as described later, and adding a dibasic acid anhydride to the resulting primary hydroxyl group. resin.

  (9) Reaction product obtained by reacting a compound 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 such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride.

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

  (11) A carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth) acryl groups in one molecule to the above-described resins (1) to (10).

Here, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
These carboxyl group-containing resins are not limited to those listed, and can be used singly or in combination.

  Since such a carboxyl group-containing resin has a number of free 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 preferably in the range of 40 to 200 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, if it exceeds 200 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so the line becomes thinner than necessary, and in some cases, dissolution and peeling occur with the developer without distinguishing between the exposed portion and the unexposed portion, It becomes difficult to draw a normal resist pattern. More preferably, it is the range of 45-120 mgKOH / g.

  Moreover, although the weight average molecular weight of carboxyl group-containing resin changes with resin frame | skeleton, generally 2,000-150,000 are preferable. If 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. More preferably, it is the range of 5,000-100,000.

  The amount of such a carboxyl group-containing resin is preferably in the range of 20 to 60% by mass of the total composition. When the blending amount is less than 20% by mass, the film strength is lowered. On the other hand, when it is more than 60% by mass, the viscosity of the composition becomes high, and the applicability and the like deteriorate. More preferably, it is the range of 30-50 mass%.

（式中、Ｒ^１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、若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のアルキル基若しくはフェニル基で置換されていてもよい）を表し、Ｒ^２は、フェニル基（炭素数１〜６のアルキル基、フェニル基若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のアルキル基若しくはフェニル基で置換されていてもよい）を表し、Ｒ^３及びＲ^４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^５及びＲ^６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し、Ｒ^７及びＲ^８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、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、アルキル基若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^７及びＲ^８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, an oxime ester photopolymerization initiator having a group represented by the following general formula (I), an α-aminoacetophenone photopolymerization initiator having a group represented by the following general formula (II) Or / and by using one or more photopolymerization initiators selected from the group consisting of acylphosphine oxide photopolymerization initiators having a group represented by the following formula (III), It is possible to obtain high resolution even in a resist having the same.

(In the formula, R ¹ 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). Or 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 benzoyl. Represents a group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group), and R ² is a phenyl group (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, and may have one or more oxygen atoms in the middle of the alkyl chain), carbon number 5 ˜8 cycloalkyl groups, Represents an alkanoyl group or a benzoyl group prime 2-20 (carbon atoms may be substituted with 1-6 alkyl or phenyl group), R ³ and R ⁴ are each independently, a carbon number 1 to 12 R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded, and R ⁷ and R ^8. Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl 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 ⁷ and R ⁸ may represent an R—C (═O) — group (where R is a hydrocarbon group having 1 to 20 carbon atoms).

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

（式中、Ｒ^９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^１０、Ｒ^１２は、それぞれ独立に、フェニル基（炭素数１〜６のアルキル基、フェニル基若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のアルキル基若しくはフェニル基で置換されていてもよい）を表し、Ｒ^１１は、水素原子、フェニル基（炭素数１〜６のアルキル基、フェニル基若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のアルキル基若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 ⁹ 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 carbon atoms. To 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 in the middle of the alkyl chain) Or a phenoxycarbonyl group, and each of R ¹⁰ and R ¹² may be independently substituted with a phenyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom). Good), an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain). 11), 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), and R ¹¹ 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), an alkyl group having 1 to 20 carbon atoms (which is substituted with one or more hydroxyl groups). Or 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 1 carbon atoms). 6 may be substituted with 6 alkyl groups or phenyl groups).

（式中、Ｒ^１３、Ｒ^１４及びＲ^１９は、それぞれ独立に、炭素数１〜１２のアルキル基を表し、Ｒ^１５、Ｒ^１６、Ｒ^１７及びＲ^１８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、ｘ及びｙは、それぞれ独立に０〜５の整数を表す。）

(Wherein R ¹³ , R ¹⁴ and R ¹⁹ each independently represents an alkyl group having 1 to 12 carbon atoms, and R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a carbon atom. (Expression 1 represents an alkyl group of 1 to 6, M represents O, S or NH, and x and y each independently represents an integer of 0 to 5).

  Among the oxime ester photopolymerization initiators, 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the general formula (IV) and a compound represented by the formula (V) are more preferable. Examples of commercially available products include CGI-325 manufactured by BASF Japan, Irgacure (registered trademark) OXE01, Irgacure OXE02, N-1919 manufactured by ADEKA, and the like. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.

  As the α-aminoacetophenone photopolymerization initiator having a group represented by the general formula (II), 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.

  Acylphosphine oxide photopolymerization initiators having a group represented by the general formula (III) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and the like. Examples of commercially available products include Lucilin TPO manufactured by BASF, Irgacure 819 manufactured by BASF Japan, and the like.

  The blending amount of such a photopolymerization initiator is preferably in the range of 0.01 to 30 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the blending amount is less than 0.01 parts by mass, the photocurability on copper is insufficient, and the coating film is peeled off or the coating properties such as chemical resistance are deteriorated. On the other hand, when it exceeds 30 parts by mass, light absorption on the coating film surface of the photopolymerization initiator becomes intense, and the deep curability tends to decrease. More preferably, it is the range of 0.5-15 mass parts.

  In the case of the oxime ester-based photopolymerization initiator having a group represented by the general formula (I), the blending amount is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. More preferably, it is 0.01-5 mass parts.

  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.

  Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

  Examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.

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

  Examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like.

  Examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.

  Examples of the benzophenone compound include benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4′-methyl diphenyl sulfide, 4-benzoyl-4′-ethyl diphenyl sulfide, 4-benzoyl-4′-propyl diphenyl sulfide, and the like. It is done.

  As the tertiary amine compound, an ethanolamine compound, a compound having a dialkylaminobenzene structure, for example, 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4,4′-diethylaminobenzophenone (Hodogaya Chemical Co., Ltd.) Dialkylaminobenzophenones such as EAB); dialkylamino group-containing coumarin compounds such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin); Ethyl dimethylaminobenzoate (Kayacure (registered trademark) EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-dimethylaminobenzoic acid (n-buto Ii) Ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoic acid (Esolol 507 manufactured by Van Dyk) ) And the like. In particular, 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 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.

  Of these compounds, thioxanthone compounds and tertiary amine compounds are preferred. 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

  As a compounding quantity of a thioxanthone compound, 20 mass parts or less are preferable with respect to 100 mass parts of carboxyl group-containing resin. When the compounding quantity of a thioxanthone compound exceeds 20 mass parts, thick film sclerosis | hardenability will fall and it will lead to the cost increase of a product. More preferably, it is 10 parts by mass or less.

  As a compounding quantity of a tertiary amine compound, 0.1-20 mass parts is preferable with respect to 100 mass parts of carboxyl group-containing resin. 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 the amount exceeds 20 parts by mass, light absorption on the surface of the dried 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 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 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

  In the photocurable resin composition of the present invention, known N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole and the like can be used as chain transfer agents in order to improve sensitivity. Specific examples of the chain transfer agent include mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof. These chain transfer agents can be used alone or in combination of two or more.

  The photo-curable resin composition of the present invention uses any naphthalene derivative and / or naphthoquinone and its derivatives, so that any exposure apparatus can be used for exposure in a state where a PET film is attached to a dry film of a liquid type and a dry film type. Even in the case of using halation, halation did not occur, and stable resolution was obtained regardless of the time for peeling the PET film. This is because naphthalene derivatives and / or naphthoquinone and its derivatives are different from general polymerization inhibitors phenothiazine and hydroquinone, and have an effect of slowing the rate of photoreaction under oxygen evasion (that is, under oxygen evasion). This is considered to be because it acts as a polymerization inhibitor) and suppresses the speed of surface curing and cures uniformly in the thickness direction.

  Among the naphthalene derivatives and / or naphthoquinones and derivatives thereof used in the present invention, ammonium 1,4-dihydroxy-2-naphthalenesulfonate, 4-methoxy-1-naphthol and the like can be used. As naphthoquinone and its derivatives, 1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, anthrone and the like can be used.

  Examples of commercially available naphthalene derivatives include Kinopower (registered trademark) WSI, Kinopower MNT (all manufactured by Kawasaki Chemical Industry Co., Ltd.), 4-methoxy-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.), and the like.

  Commercial products of naphthoquinone and its derivatives include, for example, Kinopower (registered trademark) NQI, Kinopower LSN, Kinopower ATR (all manufactured by Kawasaki Kasei Co., Ltd.), 1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, and anthrone. (Both manufactured by Tokyo Chemical Industry Co., Ltd.).

  As for the compounding quantity of a naphthalene derivative and / or naphthoquinone and its derivative, 0.01-20 mass parts is preferable with respect to 100 mass parts of carboxyl group-containing resin. If the blending amount of the naphthalene derivative and / or naphthoquinone and its derivative is less than 0.01 parts by mass, the resolution will not be stable, and halation and undercut will occur and high resolution will not be obtained. is there. On the other hand, when the amount exceeds 20 parts by mass, the coating properties such as electroless gold plating resistance deteriorate due to the decrease in photocurability. More preferably, it is the range of 0.05-10 mass parts.

  A thermosetting component can be added to the photocurable resin composition of the present invention in order to impart heat resistance. Examples of thermosetting components used in the present invention include amino resins such as melamine resins, benzoguanamine resins, melamine derivatives, and benzoguanamine derivatives, block isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, and the like. The thermosetting resin can be used. Particularly preferred is a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.

  Such a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule has either one of the three-, four- or five-membered cyclic (thio) ether groups or a plurality of two types of groups in the molecule. Compound, 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, a compound having a plurality of thioether groups in the molecule That is, an episulfide resin etc. are mentioned.

  Examples of the polyfunctional epoxy compound include jER (registered trademark) 828, jER834, jER1001, jER1004 (all manufactured by Mitsubishi Chemical Corporation), Epicron (registered trademark) 840, Epicron 850, Epicron 1050, and Epicron 2055 (all DIC Corporation). Epototo (registered trademark) YD-011, YD-013, YD-127, YD-128 (all manufactured by Nippon Steel Chemical Co., Ltd.), E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.E. E. R. 664 (all manufactured by Dow Chemical Co., Ltd.), Araldite 6071, Araldite 6084, Araldite GY250, Araldite GY260 (all manufactured by BASF Japan), Sumiepoxy ESA-011, ESA-014, ELA-115, ELA-128 (all Sumitomo) Chemical Industry), A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. 664 etc. (all manufactured by Asahi Kasei Kogyo Co., Ltd.); jERYL903 (manufactured by Mitsubishi Chemical), Epicron 152, Epicron 165 (all manufactured by DIC), Epototo YDB-400, YDB-500 (all new) Manufactured by Nippon Steel Chemical Co., Ltd.) E. R. 542 (manufactured by Dow Chemical Company), Araldite 8011 (manufactured by BASF Japan), Sumiepoxy ESB-400, ESB-700 (all manufactured by Sumitomo Chemical Co., Ltd.), A.I. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both manufactured by Asahi Kasei Kogyo Co., Ltd.); jER152, jER154 (both manufactured by Mitsubishi Chemical Co., Ltd.); E. N. 431, D.D. E. N. 438 (all manufactured by Dow Chemical Company), Epicron N-730, Epicron N-770, Epicron N-865 (all manufactured by DIC), Epototo YDCN-701, YDCN-704 (all manufactured by Nippon Steel Chemical Co., Ltd.) Araldite ECN1235, Araldite ECN1273, Araldite ECN1299, Araldite XPY307 (all manufactured by BASF Japan), EPPN-201, EOCN (registered trademark) -1025, EOCN-1020, EOCN-104S, RE-306 (all Nippon Kayaku) Sumiepoxy ESCN-195X, ESCN-220 (both manufactured by Sumitomo Chemical Co., Ltd.), A. E. R. Novolak type epoxy resins such as ECN-235 and ECN-299 (both manufactured by Asahi Kasei Kogyo Co., Ltd.); Epicron 830 (manufactured by DIC), jER807 (manufactured by Mitsubishi Chemical), Epototo YDF-170, YDF-175, YDF-2004 Bisphenol F type epoxy resin such as Araldite XPY306 (manufactured by BASF Japan); Epototo ST-2004, ST-2007, ST-3000 (all manufactured by Nippon Steel Chemical Co., Ltd.), etc. Hydrogenated bisphenol A type epoxy resin: jER604 (manufactured by Mitsubishi Chemical), Epototo YH-434 (manufactured by Nippon Steel Chemical Co., Ltd.), Araldite MY720 (manufactured by BASF Japan), Sumiepoxy ELM-120 (manufactured by Sumitomo Chemical Industries) Glycidylamine type epoxy resin such as Araldite CY-350 Hydantoin type epoxy resins such as BASF Japan); Cycloside (registered trademark) 2021 (manufactured by Daicel Chemical Industries, Ltd.), Araldite CY175, CY179 (both manufactured by BASF Japan), etc .; cycloaliphatic epoxy resins such as YL-933 ( Manufactured by Mitsubishi Chemical Corporation), T.M. E. N. , EPPN (registered trademark) -501, EPPN-502 (all manufactured by Nippon Kayaku Co., Ltd.) and other trihydroxyphenylmethane type epoxy resins; YL-6056, YX-4000, YL-6121 (all manufactured by Mitsubishi Chemical Corporation) Bisylenol type or biphenol type epoxy resins such as bisphenol S type epoxy resins such as EBPS-200 (manufactured by Nippon Kayaku Co., Ltd.), EPX-30 (manufactured by ADEKA), EXA-1514 (manufactured by DIC) Bisphenol A novolac type epoxy resin such as jER157S (manufactured by Mitsubishi Chemical Corporation); tetraphenylolethane type epoxy resin such as jERYL-931 (manufactured by Mitsubishi Chemical Corporation) and Araldite 163 (manufactured by BASF Japan); Araldite PT810 (BASF Japan) ), TEPIC (Nissan Chemical Industry) A heterocyclic epoxy resin such as Blemmer (registered trademark) DGT (manufactured by NOF Corporation); a tetraglycidylxylenoylethane resin such as ZX-1063 (manufactured by Nippon Steel Chemical Co., Ltd.); Naphthalene group-containing epoxy resins such as ESN-190, ESN-360 (all manufactured by Nippon Steel Chemical Co., Ltd.), HP-4032, EXA-4750, EXA-4700 (manufactured by DIC); HP-7200, HP-7200H (DIC) Epoxy resin having a dicyclopentadiene skeleton such as CP-50S, CP-50M (manufactured by NOF Corporation); and a copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives (eg, Daicel Chemical Industries) Ltd. PB-3600, etc.), CTBN modified epoxy resins (e.g., manufactured by Nippon Steel Chemical Co., Ltd. of YR-102, YR-450, etc.) and others as mentioned, is not limited thereto. These epoxy resins can be used alone or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.

  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- In addition to polyfunctional oxetanes such as 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 bisph Nord acids, calixarenes, calix resorcin arenes or etherified products such as the 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 having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. Moreover, episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin by the sulfur atom using the same synthesis method can also be used.

  As for the compounding quantity of the thermosetting component which has a some cyclic | annular (thio) ether group in such a molecule | numerator, 0.6-2.5 equivalent is preferable with respect to 1 equivalent of carboxyl groups of carboxyl group-containing resin. When the blending amount is less than 0.6, a carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electrical insulation and the like are 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, thereby reducing the strength of the coating film. More preferably, it is 0.8-2.0 equivalent.

  Furthermore, examples of other thermosetting components 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, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the 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 these commercially available products include Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, and the like. 202, Same 1156, Same 1158, Same 1123, Same 1170, Same 1174, Same UFR65, Same 300 (all manufactured by Mitsui Cyanamid Co., Ltd.), Nicarak (registered trademark) 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, Examples include the same Mw-100LM, the same Mw-750LM (all manufactured by Sanwa Chemical Co., Ltd.), and the like. Such thermosetting components can be used alone or in combination of two or more.

  In order to improve curability and toughness of the resulting cured product, a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be added to the photocurable resin composition of the present invention. . Examples of such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule include polyisocyanate compounds or blocked isocyanate compounds. The blocked isocyanate group is a group in which the isocyanate group is protected by the reaction with the blocking agent and temporarily inactivated, and the blocking agent is dissociated when heated to a predetermined temperature. Produces.

  As such a polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used.

  Specific examples of the aromatic polyisocyanate include, for example, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, Examples thereof include m-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.

  As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. As an isocyanate compound which can react with a blocking agent, the above-mentioned polyisocyanate compound etc. are mentioned, for example.

  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, lactic acid methyl And alcohol blocking agents such as 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, methylthio Mercaptan blocking agents such as phenol and ethylthiophenol; acid amide blocking agents such as acetic acid amide and benzamide; imide blocking agents such as succinimide and maleic imide; amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine The

  The block isocyanate compound may be commercially available, for example, Sumidur (registered trademark) BL-3175, BL-4165, BL-1100, BL-1265, Desmodur (registered trademark) TPLS-2957, TPLS-2062. , TPLS-2078, TPLS-2117, Desmotherm 2170, Desmotherm 2265 (all manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate (registered trademark) 2512, Coronate 2513, Coronate 2520 (all manufactured by Nippon Polyurethane Industry Co., Ltd.), B-830, B-815, B-846, B-870, B-874, B-882 (all manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T (all manufactured by Asahi Kasei Chemicals Co., Ltd.), etc. Can be mentioned. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent. Such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.

  The compounding amount of such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the blending amount is less than 1 part by mass, sufficient coating film toughness cannot be obtained. On the other hand, when it exceeds 100 mass parts, storage stability falls. More preferably, it is 2-70 mass parts.

  When using the thermosetting component which has a some cyclic | annular (thio) ether group in a 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 trade names of bicyclic amidine compounds and salts thereof) and the like. It is done. 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 a thermosetting catalyst.

  The blending amount of these thermosetting catalysts is sufficient in a normal quantitative ratio. For example, preferably 100 parts by mass of the thermosetting component having a carboxyl group-containing resin or a plurality of cyclic (thio) ether groups in the molecule. It is 0.1-20 mass parts, More preferably, it is 0.5-15.0 mass parts.

  A coloring agent can be mix | blended with the photocurable resin composition of this invention. As the colorant, known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and pigments 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.

Examples of the red colorant include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, quinacridone, etc. (CI: The Society of Dyers and Colorists) number is given.
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 colorants include phthalocyanine and anthraquinone, and pigment types include Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, and Pigment Blue 15 : 6, Pigment Blue 16, Pigment Blue 60, dye system is 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 these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

  Similarly, green colorants include phthalocyanine, anthraquinone, and perylene, such as Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. it can. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

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, for the purpose of adjusting the color tone, a colorant such as purple, orange, brown, or black may be added. Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, Pigment Orange 1, Pigment Orange 5, Pigment Orange 13, Pigment Orange 14, Pigment Orange 16, Pigment Orange 17 , Pigment Orange 24, Pigment Orange 34, Pigment Orange 36, Pigment Orange 38, Pigment Orange 40, Pigment Orange 43, Pigment Orange 46, Pigment Orange 49, Pigment Orange 51, Pigment Orange 61, Pigment Orange 63, Pigment Orange 64, Pigment Examples include Orange 71, Pigment Orange 73, Pigment Brown 23, Pigment Brown 25, Pigment Black 1, and Pigment Black 7.

  The blending ratio of such a colorant is not particularly limited, but is preferably 10 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. When it exceeds 10 mass parts, deep part sclerosis | hardenability may deteriorate remarkably. More preferably, it is 0.1-5 mass parts.

The compound having a plurality of ethylenically unsaturated groups in the molecule used in the photocurable resin composition of the present invention is photocured by irradiation with active energy rays, and an ethylenically unsaturated group-containing carboxyl group-containing resin is obtained. It helps insolubilize or insolubilize in dilute alkaline aqueous solution.
Examples of such compounds include glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, and the like. Polyhydric acrylates such as polyhydric alcohols or their ethylene oxide adducts or propylene oxide adducts; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether Le, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or each methacrylates and the like corresponding to the acrylate.

  Furthermore, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. The epoxy urethane acrylate compound etc. which made the half urethane compound react are mentioned. Such an epoxy acrylate resin can improve the photocurability without deteriorating the touch drying property of the coating film.

  As for the compounding quantity of the compound which has several ethylenically unsaturated groups in such a molecule | numerator, 5-100 mass parts is preferable with respect to 100 mass parts of carboxyl group-containing resin. When the blending amount is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays. On the other hand, when it exceeds 100 mass parts, the solubility with respect to dilute alkaline aqueous solution falls, and a coating film becomes weak. More preferably, it is 1-70 mass parts.

  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, known inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica, hydrotalcite and talc are preferably used. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can be used as extender pigment fillers. The blending amount of the filler is preferably 75% by mass or less of the total amount of the composition. When the blending amount of the filler exceeds 75% by mass of the total amount of the composition, the viscosity of the insulating composition becomes high, the coating and moldability are lowered, and the cured product becomes brittle. More preferably, it is 0.1-60 mass%.

Furthermore, the photocurable resin composition of the present invention may use an organic solvent for the synthesis of a carboxyl group-containing resin, the preparation of the composition, or the viscosity adjustment for application to a substrate or a carrier film. it can.
Examples of such an organic solvent 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, propanol Ethylene glycol, or propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.

  The photo-curable resin composition of the present invention may further include a known thickener such as a known thermal polymerization inhibitor, fine silica, organic bentonite, and montmorillonite, a silicone-based, a fluorine-based, a polymer-based, etc., if necessary. Known additives such as antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, antioxidants, rust inhibitors, and the like can be blended.

  The thermal polymerization inhibitor can be used for preventing thermal polymerization or polymerization with time of the polymerizable compound. Examples of the thermal polymerization inhibitor 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, phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

  In the photocurable resin composition of the present invention, an adhesion promoter can be used in order to improve adhesion between layers or adhesion between the formed resin insulation layer and the substrate. Examples of such adhesion promoters include, for example, benzimidazole, benzoxazole, benzothiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione. , Triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent and the like.

  After the photocurable resin composition of the present invention configured as described above is prepared to a predetermined composition, it is adjusted to a viscosity suitable for a coating method with an organic solvent, for example, on a substrate, a dip coating method, a flow The coating method is a coating method, a roll coating method, a bar coater method, a screen printing method, a curtain coating method, or the like.

  And the organic solvent contained in a composition is volatilized and dried (temporary drying) at the temperature of about 60-100 degreeC, and a tack-free coating film (resin insulating layer) is formed. At this time, the volatile drying is performed by using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (using a method having a heat source of an air heating method using steam in a countercurrent contact with hot air in the dryer) A method of spraying on a support).

Moreover, you may form a resin insulating layer by forming a dry film with a photocurable resin composition and bonding this on a base material.
The dry film has, for example, a structure in which a carrier film such as polyethylene terephthalate, a resin insulating layer such as a solder resist layer, and a peelable cover film used as necessary are laminated in this order.

  A resin insulation layer is a layer obtained by apply | coating and drying a photocurable resin composition to a carrier film or a cover film. For such a resin insulation layer, the photo-curable resin composition of the present invention is uniformly applied to a carrier film with a thickness of 10 to 150 μm using a blade coater, a lip coater, a comma coater, a film coater, etc., and dried. Formed. And a dry film is formed by laminating | stacking a cover film further as needed. At this time, the carrier film may be laminated after the photocurable resin composition is applied to the cover film and dried.

As the carrier film, for example, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm is used.
As the cover film, a polyethylene film, a polypropylene film, or the like can be used, but a cover film having a smaller adhesive force than the solder resist layer is preferable.

  If such a dry film is used and the cover film is used, after peeling off the cover film, the resin insulation layer and the base material are stacked and bonded together using a laminator or the like, so that the resin insulation layer is formed on the base material. It is formed. In addition, what is necessary is just to peel a carrier film before or after the exposure mentioned later.

  At this time, as a base material on which a coating film is formed or a dry film is laminated, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, It uses materials such as copper clad laminates for high frequency circuits using fluorine, polyethylene, PPO, cyanate ester, etc., and all grades (FR-4 etc.) copper clad laminates, other polyimide films, PET films, glass A substrate, a ceramic substrate, a wafer plate, etc. can be mentioned.

  Further, the pattern is exposed by an active energy beam or directly by a laser direct exposure machine through a photomask having a pattern formed by a contact method (or non-contact method).

  As an exposure machine used for active energy ray irradiation, a direct drawing device (for example, a laser direct imaging device that draws an image directly with a laser using CAD data from a computer), an exposure device equipped with a metal halide lamp, and an (ultra) high-pressure mercury lamp It is possible to use an exposure machine mounted, an exposure machine equipped with a mercury short arc lamp, or a direct drawing apparatus using an ultraviolet lamp such as a (super) high pressure mercury lamp.

As the active energy ray, it is preferable to use a laser beam having a wavelength in the range of 350 to 410 nm. By setting the maximum wavelength within this range, radicals can be efficiently generated from the photoinitiator. If a laser beam in this range is used, 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, a device manufactured by Nippon Orbotech or Pentax can be used, and any device that oscillates laser light with a wavelength of 350 to 410 nm may be used.

  And by exposing in this way, an exposed part (part irradiated with the active energy ray) is hardened, and an unexposed part is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3 wt% sodium carbonate aqueous solution). Thus, a cured product (pattern) is formed.

  At this time, as a developing method, a dipping method, a shower method, a spray method, a brush method, or the like can be used. Further, as the developer, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used.

  Further, when a thermosetting component is added, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxyl group-containing resin and, for example, a plurality of cyclic ether groups and / or cyclic groups in the molecule A thermosetting component having a thioether group reacts to form a cured product (pattern) excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.

  Thus, in the photocurable resin composition of the present invention, in the cured product containing a carboxyl group-containing resin, a photopolymerization initiator, a naphthalene derivative and / or naphthoquinone and a derivative thereof, an electronic component It is possible to satisfy the resolution required when used for the above, and to obtain the reliability such as the resistance to the thermal cycle. And it becomes possible by using such hardened | cured material for a printed wiring board etc. to obtain high reliability.

  The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following description, “parts” and “%” are based on mass unless otherwise specified.

Examples 1-11 and Comparative Examples 1-3
The various components and ratios (parts by mass) shown in Table 1 were blended, premixed with a stirrer, and then kneaded with a three-roll mill to prepare a photosensitive resin composition for a solder resist. Here, it was 15 micrometers or less when the dispersion degree of the obtained photosensitive resin composition was evaluated by the particle size measurement by the grindometer by an Erichsen company.

Performance evaluation:
<Optimum exposure amount>
A circuit pattern substrate having a copper thickness of 35 μm was polished with buffalo, washed with water and dried, and then the photosensitive resin composition of each example and comparative example was applied to the entire surface by a screen printing method, and a hot air circulation drying oven at 80 ° C. And dried for 60 minutes. After drying, using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), exposure is performed through a step tablet (Kodak No. 2), and development (30 ° C., 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution) is performed. When it was performed in 60 seconds, the optimal exposure amount was obtained when the remaining step tablet pattern had 7 steps.

<Developability>
The photosensitive resin composition of each Example and Comparative Example was applied on a solid copper substrate by a screen printing method so that the film thickness after drying was about 25 μm, and 30 minutes in a hot air circulation drying oven at 80 ° C. Dried. After drying, development was performed with a 1 wt% Na ₂ CO ₃ aqueous solution, and the time until the dried coating film was removed was measured with a stopwatch.

Characterization:
<Production of liquid type substrate>
The photosensitive resin composition of each Example and Comparative Example was applied on the entire surface of the patterned copper foil substrate so that the film thickness after drying by screen printing was 20 μm, dried at 80 ° C. for 30 minutes, and room temperature. It was left to cool. A PET film (FB-50: 16 μm, manufactured by Toray Industries, Inc.) was attached to the obtained substrate, and the degree of pressure was 0.8 MPa, 70 ° C. using a vacuum laminator (MVLP (registered trademark) -500, manufactured by Meiki Seisakusho). Heat lamination was performed for 1 minute under a vacuum degree of 133.3 Pa to obtain a substrate (unexposed substrate) having an unexposed solder resist layer. Using this exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp) on this substrate, the solder resist pattern was exposed at an optimum exposure amount, and the PET film affixed after 10 minutes was peeled off. Thereafter, a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa to obtain a resist pattern. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.

<Dry film type substrate production>
After appropriately diluting the photosensitive resin compositions of each Example and Comparative Example with methyl ethyl ketone, respectively, using an applicator, a PET film (FB-50: 16 μm manufactured by Toray Industries Inc.) was used so that the film thickness after drying was 20 μm. It was applied and dried at 80 ° C. for 30 minutes to obtain a dry film. After buffing the circuit-formed substrate, the resulting dry film was vacuumed using a vacuum laminator (MVLP (registered trademark) -500 manufactured by Meiki Seisakusho): 0.8 MPa, 70 ° C., 1 minute, vacuum Degree: 133.3 Pa was laminated by heating to obtain a substrate (unexposed substrate) having an unexposed solder resist layer. The solder resist pattern was exposed to this substrate with an optimum exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and the PET film was peeled off after 10 minutes. Thereafter, a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa to obtain a resist pattern. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.

<Resolution stability>
The photosensitive resin compositions of Example 1 and Comparative Example 1 were coated on the entire surface of a patterned copper foil substrate so that the film thickness after drying by screen printing was 20 μm, and a hot-air circulating drying oven at 80 ° C. For 30 minutes. Exposure is performed at 100 mJ / cm ² using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and the time for peeling the PET film is 5 to 60 minutes. Thereafter, development is performed with a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. for 60 seconds to form a pattern, and UV irradiation is performed in a UV conveyor furnace under the condition of an integrated exposure amount of 1000 mJ / cm ² , and then at 150 ° C. for 60 minutes. A cured coating film was obtained by thermosetting. The bottom of the opening having a design opening value of 80 μm in the cured coating film of the obtained photosensitive resin composition for solder resist was measured. Judgment criteria are as follows.
G: The opening bottom having an opening design value of 80 μm is 60 μm or more and 80 μm or less, and there is no occurrence of undercut and halation.
H: Halation occurs. The bottom of the opening is 40 μm or more and less than 60 μm.
A: Undercut occurs. The opening bottom is larger than 80 μm and not larger than 100 μm.

<Resolution>
An evaluation substrate was fabricated under the above-described substrate fabrication conditions. The bottom of the opening having a design opening value of 80 μm in the cured coating film of the obtained photosensitive resin composition for solder resist was measured. Judgment criteria are as follows.
G: The opening bottom having an opening design value of 80 μm is 60 μm or more and 80 μm or less, and there is no occurrence of undercut and halation.
H: Halation occurs. The bottom of the opening is 40 μm or more and less than 60 μm.
A: Undercut occurs. The opening bottom is larger than 80 μm and not larger than 100 μm.

<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.
A: Peeling is not observed even after 10 seconds of immersion for 6 or more times.
○: No peeling is observed even if the immersion for 10 seconds is repeated 3 times or more.
(Triangle | delta): It peels for a while when immersion for 10 seconds is repeated 3 times or more.
X: The resist layer swells and peels off within 3 times for 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 0.5 μm and gold 0.03 μm, and the presence or absence of peeling of the resist layer and the penetration of the plating solution by tape peel After evaluating the presence or absence of the resist layer, the presence or absence of peeling of the resist layer was evaluated. 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.

<TCT resistance>
A photosensitive resin composition was applied to a substrate on which a 2 mm copper line pattern was formed, exposed and developed, and then thermally cured to produce an evaluation substrate in which a 3 mm square resist pattern was formed on the copper line. . This evaluation board | substrate was put into the thermal cycle machine with which a temperature cycle is performed between -65 degreeC and 150 degreeC, and TCT (Thermal Cycle Test) was performed. And the external appearance at the time of 600 cycles, 800 cycles, and 1000 cycles was observed.
A: No abnormality at 1000 cycles.
○: No abnormality at 800 cycles, cracks occurred at 1000 cycles.
Δ: No abnormality at 600 cycles, crack occurred at 800 cycles.
X: Cracks occurred at 600 cycles.

<PCT resistance>
The evaluation substrate on which the solder resist cured coating film was formed was subjected to PCT (Pressure Cooker Test) for 168 hours and 192 hours under the conditions of 121 ° C., saturation, and 0.2 MPa using a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by ESPEC Corporation). ) And the state of the coating film after PCT was evaluated. Judgment criteria are as follows.
A: No swelling, peeling, discoloration or elution from 192 hours.
○: No swelling, peeling, discoloration, or elution from 168 hours.
Δ: Some swelling, peeling, discoloration, and elution.
X: Swelling, peeling, discoloration, and elution are often observed.

The evaluation results of the resolution stability (post-exposure stability) are shown in Table 2, and the evaluation results of other characteristics are shown in Table 3.

  As shown in Table 2, in the case of Example 1 using a naphthalene derivative and / or naphthoquinone and its derivative, good resolution was obtained regardless of the time for peeling the PET film as compared with Comparative Example 1. It turns out that it is obtained.

As shown in Table 3, in the case of Examples 1 to 11 using a naphthalene derivative and / or naphthoquinone and its derivative, better resolution, TCT resistance and PCT resistance compared to Comparative Examples 1 to 3 It can be seen that is obtained.
On the other hand, in contrast to Example 3, in the case of Comparative Example 2 in which a naphthalene derivative and / or naphthoquinone and its derivative were not used, any characteristic was observed when the PET film was peeled off 10 minutes after exposure. Also in the test, the coating film was peeled off, and the solder heat resistance, electroless gold plating resistance, TCT resistance and PCT resistance were inferior. In contrast to Example 1, in the case of Comparative Example 1 in which a naphthalene derivative and / or naphthoquinone and its derivative are not used and in Comparative Example 3 in which phenothiazine is used instead, TCT resistance is similarly inferior, and PCT resistance is inferior. Is marked with ◯, but the resolution was not stable, halation occurred, and peeling occurred in PCT after 168 hours.

Claims (4)

A carboxyl group-containing resin, a photopolymerization initiator, at least one of 4-methoxy-1-naphthol, 9-oxoanthracene, 2-hydroxy-1,4-naphthoquinone, and 1,4-naphthoquinone, and a molecule A photocurable resin composition comprising a thermosetting component having at least one of a plurality of cyclic ether groups and cyclic thioether groups therein. A dry film obtained by applying and drying the photocurable resin composition according to claim 1 on a film. A dry film obtained by applying and drying the photocurable resin composition according to claim 1 on a substrate, or a dry film obtained by applying and drying the photocurable resin composition on a film as a substrate. A cured product of a coating film obtained by laminating. A dry film obtained by applying and drying the photocurable resin composition according to claim 1 on a substrate, or a dry film obtained by applying and drying the photocurable resin composition on a film as a substrate. printed wiring board characterized by having a pattern of a cured product of the coating film obtained by laminating.