JP5091353B2 - Photocurable resin composition - Google Patents

Description

  The present invention relates to a photocurable resin composition used as, for example, a solder resist for 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, an alkali development type photocurable resin composition is used in printed wiring board manufacture, liquid crystal display board manufacture, or printing plate making. For example, when used as a solder resist in the production of printed wiring boards, characteristics related to long-term reliability, such as heat resistance that can withstand processing under high temperature conditions such as soldering, as well as water resistance and moisture resistance, are required. It is done.

  In recent years, along with the reduction in size and weight of electronic devices, the increase in functionality, and environmental friendliness, high-density mounting and thinning of printed wiring boards and the like have been promoted. In particular, a solder resist used for a high-density mounting substrate having a fine pitch pattern for high-density mounting, for example, requires high migration resistance and thermal cycle resistance in the cured product. Accordingly, it is required to reduce the moisture absorption and purity of the photocurable resin composition used as the solder resist, that is, to reduce the water absorption rate and the ionic impurities in the resin composition.

  As a photo-curable resin composition that satisfies migration resistance as a cured product and thermal cycle resistance to some extent, a polyfunctional epoxy resin or (meth) acrylate is used to double the resin skeleton among carboxyl group-containing epoxy (meth) acrylates. A photocurable resin composition into which many bonds are introduced is used. With such a configuration, it is considered that the crosslink density can be increased, and heat resistance and dimensional stability can be improved.

However, since the cured product becomes brittle when the crosslink density increases, there is a problem that it is difficult to balance heat resistance and brittleness reduction. Regarding the reduction of brittleness, a technique using a mixture of a bisphenol-type carboxyl group-containing epoxy (meth) acrylate and a novolak-type carboxyl group-containing epoxy (meth) acrylate is disclosed (for example, see Patent Document 1). However, in such a method, emphasis is placed on improving flexibility, and there is a problem that sufficient dimensional stability and water resistance due to temperature change cannot be obtained.
Moreover, in a photocurable resin composition, it is possible to aim at reduction of a water absorption rate by using a polyfunctional curable resin and improving a crosslinking density. However, on the other hand, there is a problem that the cured product becomes hard and brittle, and the heat cycle resistance is lowered.

Japanese Patent Publication No. 2000-109541

  The present invention is a photocurable resin composition capable of suppressing hygroscopicity and capable of improving thermal cycle resistance without impairing migration resistance characteristics when used in a printed wiring board or the like in a cured product thereof. The purpose is to provide.

  According to one aspect of the present invention, there is provided a photocurable resin composition comprising a carboxyl group-containing resin, a photopolymerization initiator, an epoxidized polybutadiene compound, and a styryl group-containing compound.

  With such a configuration, it is possible to suppress hygroscopicity and improve the thermal cycle resistance without impairing the migration resistance when the cured product is used for a printed wiring board or the like.

  The photocurable resin composition of one embodiment of the present invention preferably further contains a mercapto compound. With such a configuration, the adhesion can be improved.

  In the photocurable resin composition of one embodiment 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）Further, in the photocurable resin composition of one embodiment of the present invention, the photopolymerization initiator is an oxime ester photopolymerization initiator represented by the following general formula (I), and an amino represented by the following general formula (II). It is preferably a mixture of an acetophenone photopolymerization initiator and one or more photopolymerization initiators selected from the group consisting of acylphosphine oxide photopolymerization initiators represented by the following general formula (III).

(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 represents a hydrocarbon group having 1 to 20 carbon atoms).

  By using such a photopolymerization initiator, it becomes possible to obtain high resolution in a resist having a pigment at a high concentration.

  Moreover, in the photocurable resin composition of 1 aspect 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 and punching resistance can be improved.

  The photocurable resin composition of one embodiment of the present invention can further contain a colorant. By containing a colorant, it can be suitably used as a solder resist.

  Moreover, according to 1 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.

  In one embodiment of the present invention, the above-described photocurable resin composition or dry film can be used as a cured product obtained by photocuring by active energy ray irradiation.

  In such a cured product, when used for a printed wiring board or the like, it is possible to improve the thermal cycle resistance without impairing the migration resistance.

  Furthermore, in one embodiment of the present invention, the above-described photocurable resin composition or a dry film thereof can be used as a printed wiring board having a pattern of a cured product obtained by photocuring by irradiation with active energy rays.

  In such a printed wiring board, it becomes possible to improve the thermal cycle resistance without impairing the migration resistance.

  According to one embodiment of the present invention, in a photocurable resin composition, hygroscopicity can be suppressed, and in the cured product, when used for a printed wiring board or the like, the thermal cycle resistance without impairing the migration resistance characteristics. Can be improved.

  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, an epoxidized polybutadiene compound, and a styryl group-containing compound. It came to complete.

  In particular, the use of an epoxidized polybutadiene compound not only provides flexibility to the cured product of this photo-curable resin composition, but also contributes to stress relaxation during over-curing of the coating film and improves thermal cycle resistance. It becomes possible. Moreover, by crosslinking with an epoxy group and a hydroxyl group introduced into the epoxidized polybutadiene compound, the crosslinking density can be improved and the migration resistance can be improved.

  Moreover, it becomes possible by using a styryl group containing compound to provide heat resistance required when using as a solder resist.

Hereinafter, the photocurable resin composition of the present embodiment will be described in detail.
First, as the carboxyl group-containing resin constituting the photocurable resin composition of the present embodiment, various known carboxyl group-containing resins having a carboxyl group in the molecule are used for the purpose of imparting alkali developability. can do. 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 ( 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. (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 the molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal (Meth) acrylated photosensitive carboxyl group-containing urethane resin.
(5) During the synthesis of the above-mentioned resin (2) or (3), an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, etc., one isocyanate group and one or more (meth) acryl groups in the molecule A photosensitive carboxyl group-containing urethane resin obtained by adding a compound having a terminal and being terminally (meth) acrylated.
(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) 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 photosensitive 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) 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.
(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 photosensitive carboxyl group-containing resin obtained by adding a compound having one epoxy group and one or more (meth) acrylic groups in one molecule to the resins (1) to (10) described above.

  Here, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

  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. When the weight average molecular weight is less than 2,000, tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, film thickness may be reduced during development, and resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior. 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 in the entire 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%.

  These carboxyl group-containing resins are not limited to those listed, and can be used singly or in combination.

（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 in the 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 represents a hydrocarbon group having 1 to 20 carbon atoms).

（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）

（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）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.

(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). And 6 may be substituted with an alkyl group or a phenyl group)

(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 Ciba Japan, Irgacure (registered trademark) OXE01, Irgacure OXE02, and N-1919 manufactured by ADEKA. 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 Ciba 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 and Irgacure 819 manufactured by Ciba Japan.

  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 surface of the solder resist coating film 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 for the photocurable resin composition of the present embodiment include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, Examples include benzophenone compounds, xanthone compounds, and tertiary amine compounds.

  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 MABP manufactured by Nippon Soda Co., Ltd.), 4,4′-diethylaminobenzophenone (manufactured by 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-butoxy) Ii) Ethyl (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayakyua DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (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 dry solder resist coating film by the tertiary amine compound becomes intense, 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 embodiment, 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 epoxidized polybutadiene compound used in the photocurable resin composition of the present embodiment not only improves the flexibility of the resulting cured product (cured coating film), but also provides stress relaxation during solder resist overcuring. Used.

  As such an epoxidized butadiene compound, any polybutadiene compound containing an epoxy group can be used without any particular limitation. For example, Epofriend (registered trademark) (produced by Daicel Chemical Industries, Ltd.) obtained by copolymerizing styrene and butadiene and then epoxidizing a double bond in the copolymer with an oxidizing agent such as peracetic acid. Epoxidized product of butadiene and styrene block copolymer). Specifically, for example, Epofriend A1005 (butadiene / styrene weight ratio, 60/40, epoxy equivalent 1800 to 2100), Epofriend A1010 (butadiene / styrene weight ratio, 60/40, epoxy equivalent 950 to 1050), Epofriend Friend A1020 (butadiene / styrene weight ratio 60/40, epoxy equivalent 480 to 540) and the like. Epolide (registered trademark) PB3600 (manufactured by Daicel Chemical Industries), Ricon657 (manufactured by Sartomer), and the like can be mentioned. These epoxidized polybutadiene compounds can be used alone or as a mixture of two or more.

  As a compounding quantity of such an epoxidized butadiene compound, 3-100 mass parts is preferable with respect to 100 mass parts of carboxyl group-containing resin. When the blending amount is less than 3 parts by mass, it becomes difficult to obtain sufficient flexibility and stress relaxation. On the other hand, when it exceeds 100 parts by mass, the developability of the composition is lowered, and it is difficult to obtain good resolution. More preferably, it is 10-60 mass parts.

  The styryl group-containing compound used in the present embodiment is used for imparting heat resistance. Such a styryl group-containing compound may be synthesized by a conventional method, or a commercially available product may be used. Examples of methods for synthesizing styryl group-containing compounds include, for example, reaction of mono- and polyfunctional phenols with halogenated methylstyrene, functional groups that can react with epoxy groups (for example, amino groups, hydroxyl groups, carboxyl groups, etc.). The reaction of the mono- and polyfunctional compound which has and vinylbenzyl glycidyl ether is mentioned. Specifically, for example, vinyl naphthalene, divinyl naphthalene, divinyl biphenyl, polyvinyl benzyl ether compound obtained by reaction of polyphenol and vinyl benzyl halide, oligophenylene ether compound of terminal styrene (OPE-2St manufactured by Mitsubishi Gas Chemical Company), Examples thereof include compounds obtained by reaction of bisphenol A and vinylbenzyl halide (Lipoxy (registered trademark) BPV-1X manufactured by Showa Polymer Co., Ltd.). A styryl compound can be used individually by 1 type or in combination of 2 or more types.

  As a compounding quantity of such a styryl group containing compound, 1-50 mass parts is preferable with respect to 100 mass parts of carboxyl group-containing resin. When the blending amount is less than 1 part by mass, it becomes difficult to obtain sufficient heat resistance. On the other hand, when it exceeds 50 parts by mass, the developability of the composition is lowered and it is difficult to obtain good resolution. More preferably, it is 1-10 mass parts.

  The photocurable resin composition of the present embodiment includes a mercapto that acts as an additional reagent, a chain transfer agent, and / or an adhesion imparting agent for the purpose of improving the curability of the photosensitive resin composition and the adhesion of the resulting cured film. Compounds can be added.

  Examples of mercapto compounds include chain transfer agents having a hydroxyl group such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopro Pionate, methyl-3-mercaptopropionate, 2,2- (ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol , Cyclopentanethiol, cyclohexanethiol, thioglycerol, 4,4-thiobisbenzenethiol and the like.

  Examples of these commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP, and TEMPIC (all manufactured by Sakai Chemical Industry Co., Ltd.), Karenz MT-PE1, Karenz MT-BD1, and Karenz (registered trademark) -NR1 (all manufactured by Showa Denko KK) and the like.

  Furthermore, as a mercapto compound having a heterocyclic ring, for example, mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto-4-ethyl- 4-butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4-butyrolactam, N-methyl 2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) ethyl-2-mercapto -4-butyrolactam, 2-mercapto-5-valerolactone, 2-me Capto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto-5-valerolactam N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, 2-mercaptobenzothiazole, 2-mercapto-5-methylthio-thiadiazole, 2-mercapto-6-hexanolactam, 2,4,6 Trimercapto-s-triazine (Dysnet F from Sankyo Kasei), 2-dibutylamino-4,6-dimercapto-s-triazine (Disnet DB from Sankyo Kasei), and 2-anilino-4,6- And dimercapto-s-triazine (Dysnet (registered trademark) AF manufactured by Sankyo Kasei Co., Ltd.).

  In particular, as a mercapto compound having a heterocyclic ring that does not impair the developability of the photocurable resin composition, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (Axel M manufactured by Kawaguchi Chemical Industry Co., Ltd.) 3-mercapto-4-methyl-4H-1,2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, and 1-phenyl-5-mercapto-1H-tetrazole are preferred. These mercapto compounds can be used alone or in combination of two or more.

  A thermosetting component can be added to the photocurable resin composition of the present embodiment in order to impart heat resistance. Examples of thermosetting components used in this embodiment include amino resins such as melamine resins, benzoguanamine resins, melamine derivatives, and benzoguanamine derivatives, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, and episulfide resins. A known thermosetting resin can be used. Particularly preferred is a thermosetting component having two or more 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. 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) 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 Ciba 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 Co., Ltd.), Araldite 8011 (manufactured by Ciba Japan), Sumiepoxy ESB-400, ESB-700 (both 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 Ciba Japan), EPPN-201, EOCN (registered trademark) -1025, EOCN-1020, EOCN-104S, RE-306 (all Nipponized) Yakuhin Co., Ltd.), Sumiepoxy ESCN-195X, ESCN-220 (both manufactured by Sumitomo Chemical Co., Ltd.), A.I. 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 epoxy resins such as Araldite XPY306 (manufactured by Ciba Japan); Epototo ST-2004, ST-2007, ST-3000 (all manufactured by Nippon Steel Chemical Co., Ltd.) Hydrogenated bisphenol A type epoxy resin such as jER604 (Mitsubishi Chemical Co., Ltd.), Epototo YH-434 (Nippon Steel Chemical Co., Ltd.), Araldite MY720 (Ciba Japan Co., Ltd.), Sumiepoxy ELM-120 (Sumitomo Chemical Co., Ltd.) Glycidylamine type epoxy resins such as Araldite CY-350 Hydantoin-type epoxy resins such as Japan); Cycloside (registered trademark) 2021 (manufactured by Daicel Chemical Industries, Ltd.), Araldite CY175, CY179 (all manufactured by Ciba Japan), and the like; YL-933 (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); tetraphenylolethane type epoxy resin such as jERYL-931 (manufactured by Mitsubishi Chemical), Araldite 163 (manufactured by Ciba Japan); Araldite PT810 (Ciba)・ Made by Japan), TEPIC (made by Nissan Chemical Industries) A heterocyclic epoxy resin; diglycidyl phthalate resin such as Blemmer (registered trademark) DGT (manufactured by NOF Corporation); tetraglycidyl xylenoylethane resin such as ZX-1063 (manufactured by Nippon Steel Chemical Co., Ltd.); ESN-190 , ESN-360 (all manufactured by Nippon Steel Chemical Co., Ltd.), HP-4032, EXA-4750, EXA-4700 (manufactured by DIC), etc .; naphthalene group-containing epoxy resins; HP-7200, HP-7200H (manufactured by DIC), etc. Epoxy resins having a dicyclopentadiene skeleton; glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M (manufactured by NOF Corporation); further, a copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Polybutadiene rubber derivatives (for example, PB manufactured by Daicel Chemical Industries, Ltd.) -3600), CTBN-modified epoxy resins (for example, YR-102, YR-450, etc., manufactured by Nippon Steel Chemical Co., Ltd.), etc., are 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, amino resins, such as a melamine derivative and a benzoguanamine derivative, are mentioned as a thermosetting component. For example, there are methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds and methylol urea compounds. Furthermore, the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound and alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. In particular, a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.

  As these commercial products, for example, Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, Same 1156, Same 1158, Same 1123, Same 1170, Same 1174, Same UFR65, Same 300 (all made 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 may be added to the photocurable resin composition of the present embodiment. it can. 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 alone or in combination of two or more.

  The compounding amount of the 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 mass parts.

  The photocurable resin composition of this embodiment can mix | blend a coloring agent. 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. (Numbers issued by The Society of Dyers and Colorists).
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: 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: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185
Condensed Azo: 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 embodiment is photocured by irradiation with active energy rays, and an ethylenically unsaturated group-containing carboxyl group-containing resin is obtained. Insolubilizes or helps insolubilize in a 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 photocurability without deteriorating the touch drying property.

  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 embodiment 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 embodiment uses 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. Can do.

  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.

  In many polymer materials, once oxidation starts, oxidative degradation occurs successively in a chain, resulting in a decrease in the function of the polymer material. Therefore, the photocurable thermosetting resin composition of this embodiment is oxidized. To prevent (1) radical scavengers that invalidate the generated radicals and / or (2) peroxide decomposers that decompose the generated peroxides into harmless substances and prevent the generation of new radicals. Antioxidants such as can be added.

  Examples of the antioxidant acting as a radical scavenger include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2 -Methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2 , 4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′-di-t-butyl-4-hydroxybenzyl)- Phenolic compounds such as S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6,6-tetramethyl-4 -Piperidyl) -amine compounds such as sebacate and phenothiazine.

  The radical scavenger may be commercially available, for example, ADK STAB (registered trademark) AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (all manufactured by ADEKA), IRGANOX (registered trademark) 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN (registered trademark) 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 152, 2 TINUVIN 5100 (both manufactured by Ciba Japan Co., Ltd.) and the like.

  Examples of the antioxidant acting as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3′-thiodipro Sulfur compounds such as pionate can be mentioned.

  The peroxide decomposing agent may be commercially available, for example, Adeka Stub TPP (manufactured by ADEKA), Mark AO-412S (manufactured by Adeka Argus Chemical), Sumilyzer (registered trademark) TPS (manufactured by Sumitomo Chemical), Is mentioned. Such antioxidant can be used individually by 1 type or in combination of 2 or more types.

  Since the polymer material absorbs light and thereby causes degradation / degradation, the photocurable resin composition of the present invention includes an ultraviolet absorber in addition to the antioxidant in order to take a countermeasure against stabilization against ultraviolet rays. Can be used.

  Examples of such ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like.

  Examples of the benzophenone derivative include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and 2 , 4-dihydroxybenzophenone and the like.

  Examples of the benzoate derivative include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl- Examples include 4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate.

  Examples of the benzotriazole derivatives include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) enzotriazole, 2- (2′- Hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, Examples include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole.

  Examples of the triazine derivative include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.

  Ultraviolet absorbers may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460. , TINUVIN 479 (both manufactured by Ciba Japan). Such ultraviolet absorbers can be used singly or in combination of two or more, and in combination with an antioxidant, the molded product obtained from the photocurable resin composition of the present embodiment can be used. Stabilization can be achieved.

  The photo-curable resin composition of the present embodiment further includes a known thickener such as a known thermal polymerization inhibitor, finely divided silica, organic bentonite, and montmorillonite, silicone-based, fluorine-based, polymer-based, etc. The known antifoaming agent and / or leveling agent, 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 to prevent 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 embodiment, an adhesion promoter can be used in order to improve the adhesion between layers or the 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 embodiment 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, It is applied by a method such as a flow coating method, a roll coating method, a bar coater method, a screen printing method, or a curtain coating method.

  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 from 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. Such a resin insulation layer is obtained by uniformly applying the photocurable resin composition of the present embodiment 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, and the like, and then drying. 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 All grades (FR-4, etc.) of copper clad laminates, such as copper clad laminates for high frequency circuits using fluorine, polyethylene, PPO, cyanate esters, etc., other polyimide films, PET films, A glass substrate, a ceramic substrate, a wafer board, 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.

  As described above, when the photocurable resin composition contains a carboxyl group-containing resin, a photopolymerization initiator, an epoxidized polybutadiene compound, and a styryl group-containing compound, the cured product is used for an electronic component or the like. Reliability such as heat cycle resistance can be obtained without impairing required heat resistance and migration resistance characteristics. 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.

Example of Synthesis of Carboxyl Group-Containing Resin (A-1) To an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device and a stirring device, a novolac type cresol resin (trade name “Shonol CRG951” manufactured by Showa Polymer Co., Ltd., OH equivalent: 119.4) 119.4 g, 1.19 g of potassium hydroxide and 119.4 g of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating.

Next, 63.8 g of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.

  293.0 g of the obtained novolak-type cresol resin alkylene oxide reaction solution, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer, a thermometer and an air blowing tube. The reaction vessel was charged with air at a rate of 10 ml / min and reacted at 110 ° C. for 12 hours while stirring. As the water produced by the reaction, 12.6 g of water was distilled as an azeotrope with toluene.

  Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution.

  Next, 332.5 g of the obtained novolac acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours. A carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained. Hereinafter, this reaction solution is called varnish A-1.

Example of Synthesis of Carboxyl Group-Containing Resin (A-2) Orthocresol novolac epoxy resin (600 g, diethylene glycol monoethyl ether acetate [DIC Corporation, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) 1070 g (number of glycidyl groups (total number of aromatic rings): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, and the mixture was heated and stirred at 100 ° C. to be uniformly dissolved.

  Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. To the obtained reaction solution, 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 4 hours. After cooling, the solid content acid value 89 mgKOH / G, a resin solution having a solid content of 65% was obtained. This is designated as resin solution A-2.

備考
＊１：ZFR−1124（日本化薬社製）
＊２：ZCR−1601H（日本化薬社製）
＊３：２-メチル-１-(４-メチルチオフェニル)-２-モルフォリノプロパン-１-オン（チバ・ジャパン社製）
＊４： エタノン,１−[９−エチル−６−(２−メチルベンゾイル)−９Ｈ−カルバゾール
−３−イル]１,１−(Ｏ-アセチルオキシム)(チバ・ジャパン社製)
＊５：エポキシ化ポリブタジエン 分子量：3000、エポキシ当量：200（ダイセル化学工業社製）
＊６：リポキシBPV-1X（昭和高分子社製）
＊７：末端スチレンのオリゴフェニレンエーテル化合物（三菱ガス化学社製）
＊８：２−メルカプトベンゾチアゾール（川口化学工業社製）
＊９：1,4-ビス(3-メルカプトブチリルオキシ)ブタン（昭和電工社製）
＊１０：2,4,6-トリメルカプト-s-トリアジン(三協化成社製)
＊１１：フェノールノボラック型エポキシ樹脂(ダウケミカル社製)
＊１２：ビキシレノール型エポキシ樹脂(三菱化学社製)
＊１３：ブロックイソシアネート(旭化成ケミカルズ社製)
＊１４：メチル化メラミン樹脂（三和ケミカル社製）
＊１５：酸化防止剤（チバ・ジャパン社製）
＊１６：ジペンタエリスリトールヘキサアクリレート(日本化薬社製)
＊１７：B-30（堺化学社製）
＊１８：C.I.Pigment Blue 15:3
＊１９：C.I.Pigment Ｙellow 147
＊２０：ジプロピレングリコールモノメチルエーテルExamples 1-12 and Comparative Examples 1-3
Using the resin solution of each synthesis example, blended in various components and proportions (parts by mass) shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and photosensitive resin composition for solder resist Was prepared. 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.

Remarks * 1: ZFR-1124 (Nippon Kayaku Co., Ltd.)
* 2: ZCR-1601H (Nippon Kayaku Co., Ltd.)
* 3: 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (manufactured by Ciba Japan)
* 4: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] 1,1- (O-acetyloxime) (manufactured by Ciba Japan)
* 5: Epoxidized polybutadiene Molecular weight: 3000, Epoxy equivalent: 200 (manufactured by Daicel Chemical Industries)
* 6: Lipoxy BPV-1X (Showa Polymer Co., Ltd.)
* 7: Oligophenylene ether compound of terminal styrene (Mitsubishi Gas Chemical Co., Ltd.)
* 8: 2-mercaptobenzothiazole (manufactured by Kawaguchi Chemical Industry Co., Ltd.)
* 9: 1,4-bis (3-mercaptobutyryloxy) butane (Showa Denko)
* 10: 2,4,6-trimercapto-s-triazine (manufactured by Sankyo Kasei)
* 11: Phenol novolac epoxy resin (Dow Chemical Co.)
* 12: Bixylenol epoxy resin (Mitsubishi Chemical Corporation)
* 13: Block isocyanate (Asahi Kasei Chemicals)
* 14: Methylated melamine resin (Sanwa Chemical Co., Ltd.)
* 15: Antioxidant (Ciba Japan)
* 16: Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.)
* 17: B-30 (manufactured by Sakai Chemical)
* 18: CIPigment Blue 15: 3
* 19: CIPigment Yellow 147
* 20: Dipropylene glycol monomethyl ether

Performance evaluation:
<Optimum exposure amount>
The photocurable / thermosetting resin compositions of the examples and comparative examples were coated on the entire surface by screen printing after applying a circuit board with a copper thickness of 35 μm after buffing, washing with water and drying, and heated at 80 ° C. Dry in a circulating drying oven 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 photocurable / thermosetting resin composition of each example and comparative example was applied to a copper solid substrate by a screen printing method so as to have a thickness of about 25 μm after drying, and then heated at 80 ° C. in a hot air circulation drying oven. Dry for 30 minutes. 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.

Characteristic test:
The composition of each example and comparative example was applied onto 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 allowed to cool to room temperature. did. Using this exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), this substrate is exposed to a solder resist pattern 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 2 kg / cm ² . Development was performed for 60 seconds 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.

<Electroless gold plating resistance>
Using 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 or plating penetration by tape peel After evaluating the presence or absence, 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.

<Insulation after humidification test (HAST)>
A solder resist was applied to a substrate on which comb-type electrodes (line / space = 50 μm / 50 μm) were formed, exposed and developed, and then thermally cured to prepare an evaluation substrate. This evaluation substrate was placed in a high-temperature and high-humidity tank at 130 ° C. and a humidity of 85%, charged with a voltage of 5 V, and subjected to HAST (Highly Accelerated Stress Test) for 192 hours. And the electrical insulation after HAST was measured.

<TCT resistance>
A solder resist 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 on 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. The appearance at 600 cycles, 800 cycles and 1000 cycles was observed.
◎: No abnormality at 1000 cycles ○: No abnormality at 800 cycles, crack generation at 1000 cycles Δ: No abnormality at 600 cycles, crack generation at 800 cycles ×: Crack generation at 600 cycles

<PCT resistance>
The evaluation substrate on which the solder resist cured coating film was formed was PCT (Pressure Cooker Test) for 168, 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). Went. And the state of the coating film after PCT was evaluated. Judgment criteria are as follows.
◎: No swelling, peeling, discoloration, or dissolution 192 hours ○: No swelling, peeling, discoloration, or dissolution of 168 hours Δ: Some swelling, peeling, discoloration, or dissolution ×: Expansion, peeling, discoloration, Many elutions

Dry film evaluation:
Evaluation substrates were prepared for the resin compositions of Example 2 and Comparative Example 1 by the method shown below, and evaluated in the same manner.

<Dry film production>
Each of the resin compositions of Example 2 and Comparative Example 1 was appropriately diluted with methyl ethyl ketone, and then applied to a PET film (FB-50: 16 μm manufactured by Toray Industries, Inc.) using an applicator so that the film thickness after drying was 20 μm. And dried at 80 ° C. for 30 minutes to obtain a dry film.

<Board fabrication>
After buffing the circuit-formed substrate, the dry film was pressed with a vacuum laminator (MVLP (registered trademark) -500 manufactured by Meiki Seisakusho), pressure: 0.8 MPa, 70 ° C., 1 minute, vacuum: Heat lamination was carried out under the condition of 133.3 Pa to obtain a substrate (unexposed substrate) having an unexposed solder resist layer.

The evaluation results are shown in Table 2.

  As shown in Table 2, in the case of Examples 1 to 9 using an epoxidized polybutadiene compound, good HAST, TCT resistance and PCT resistance without lowering the photocuring property as compared with Comparative Examples 1 to 3 It can be seen that In particular, in Examples (Examples 1, 2, 6 to 12) containing A-1 as a carboxyl group-containing resin, it is found that the insulation reliability is excellent and useful as a solder resist.

  On the other hand, in the case of the comparative example which does not use the epoxidized polybutadiene compound, it can be seen that the TCT resistance and the PCT resistance are inferior, and the obtained cured product is brittle. Furthermore, in Comparative Example 1 in which the compound having a styryl group was not used, TCT resistance and PCT resistance were inferior, sensitivity was inferior, and electrical characteristics were lowered.

Claims (5)

  A photocurable resin composition comprising a carboxyl group-containing resin, a photopolymerization initiator, an epoxidized polybutadiene compound, and a styryl group-containing compound.   The photocurable resin composition according to claim 1, comprising a mercapto compound.   A dry film obtained by applying and drying the photocurable resin composition according to claim 1 on a film.   A dry coating film obtained by applying and drying the photocurable resin composition according to claim 1 or 2 on a substrate, or a dry film obtained by applying and drying the photocurable resin composition on a film. A cured product obtained by photocuring a coating film obtained by laminating on a material by irradiation with active energy rays.   A dry coating film obtained by applying and drying the photocurable resin composition according to claim 1 or 2 on a substrate, or a dry film obtained by applying and drying the photocurable resin composition on a film. A printed wiring board comprising a cured product pattern obtained by photocuring a coating film obtained by laminating on a material by irradiation with active energy rays.