WO2011021370A1 - Photocurable resin composition - Google Patents

Abstract

Disclosed is a photocurable resin composition which enables the formation of a dried coating film having excellent finger touch dryness and high sensitivity, also enables the production of a cured article having excellent electroless gold plating resistance, soldering heat resistance, moisture resistance and electrical insulation properties, and is applicable to the formation of cured coating films such as solder resists for printed wiring boards and flexible printed wiring boards advantageously. The photocurable resin composition comprises a photosensitive compound produced using a compound having a structure represented by general formula (I) as a raw material or an oligomer of the photosensitive compound, a carboxyl-group-containing resin, and a photopolymerization initiator. (In the formula, R¹ represents a polyhydric alcohol derivative having a valency of (n+1); m and n independently represent an integer of 1 or greater; l represents 0 or an integer of 1 or greater; R³ represents CH₂, C₂H₄, C₃H₆, C₄H₈, or a substituted or unsubstituted aromatic ring; and R² represents a substituted or unsubstituted aromatic ring.)

Description

Photocurable resin composition

The present invention relates to a photocurable resin composition used as, for example, a solder resist for a printed wiring board.

Alkali development type photosensitive resin compositions are widely used as solder resists for the purpose of protecting circuits such as printed wiring boards. In general, the solder resist is composed of a carboxyl group-containing resin, a polyfunctional acrylate compound, a photopolymerization initiator, a thermosetting resin, and the like.

In such a solder resist, a liquid polyfunctional polyester acrylate is widely used as a polyfunctional acrylate compound mainly from the viewpoint of high sensitivity and development resistance. However, when used in a large amount, the dryness to touch of the dried coating film deteriorates. In the case of exposure by the contact exposure method, the dry coating film requires a touch-drying property (tack-free property), so that the amount of liquid polyfunctional polyester acrylate used is limited.

In contrast, a method using semi-solid polyester acrylates has been proposed (see, for example, Patent Document 1). However, in this case, since the polyester acrylate is semi-solid and bifunctional, there is a problem that the sensitivity is lowered and the developability is lowered because the softening point of the dried coating film is improved.

In general, acrylate compounds are inferior in hydrophobicity and alkali resistance. Solder resists are required to have high solder heat resistance and electrical insulation, but there is a problem that they tend to cause a decrease in reliability, such as a decrease in insulation resistance under high-temperature humidification conditions, and a short circuit between circuits due to ion migration. is there.

Japanese Patent No. 3928620

The present invention has excellent dryness to touch and high sensitivity of the dried coating film, and its cured product is excellent in solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, etc., and photocurable resin composition The purpose is to provide goods.

According to one aspect of the present invention, it is characterized in that it contains a photosensitive compound or an oligomer thereof, a carboxyl group-containing resin, and a photopolymerization initiator that are made from a compound containing a structure represented by the general formula (I). A photocurable resin composition is provided.

(Wherein R ¹ represents an (n + 1) -valent polyhydric alcohol derivative, m and n are each represented by an integer of 1 or more, l is 0 or an integer of 1 or more, and R ³ is CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , any of a substituted or unsubstituted aromatic ring, and R ² represents a substituted or unsubstituted aromatic ring.)

With such a configuration, it is possible to obtain a touch-drying property of a highly sensitive and good dry coating film, and the cured product has excellent electroless gold plating resistance, solder heat resistance, moisture resistance, and electrical insulation. Obtainable.

In the photocurable resin composition of one embodiment of the present invention, the photosensitive compound or oligomer thereof is preferably a photosensitive compound represented by the following general formula (II) or an oligomer thereof.

(Wherein R ⁴ represents an (n + 1 + k) -valent polyhydric alcohol derivative, j, k, m are each represented by an integer of 1 or more, l and n are each represented by 0 or an integer of 1 or more, and R ⁶ And R ⁸ each independently represents CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , a substituted or unsubstituted aromatic ring, and R ⁵ and R ⁷ are each independently substituted or unsubstituted. Represents a substituted aromatic ring, and R ⁹ represents a hydrogen atom or a methyl group.)
By using such a photosensitive compound or an oligomer thereof, a coating film having high sensitivity and excellent touch drying property can be obtained.

In the photosensitive resin of one embodiment of the present invention, the oligomer of the photosensitive compound is obtained by depolymerizing polyester with a polyol having a plurality of hydroxyl groups in one molecule, and further reacting a compound having an ethylenically unsaturated group. It is preferable that it is an oligomer of the photosensitive compound obtained.

As a result, there is no decrease in sensitivity and the touch dryness is improved and the sensitivity is high, and in the cured product, excellent solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, etc. are obtained. Can do.

In the photosensitive resin of one embodiment of the present invention, the polyester is preferably recycled polyethylene terephthalate. Thereby, since the molecular weight of the oligomer precursor of a photosensitive compound can be made small and the viscosity at the time of melting becomes low, the subsequent reaction can be performed under mild reaction conditions and at a high concentration.

In the photosensitive resin of one embodiment of the present invention, the polyol preferably contains trimethylolpropane. Thereby, the storage stability of the oligomer precursor of the photosensitive compound is improved, and the resulting oligomer of the photosensitive compound becomes trifunctional and has high sensitivity.

In the photosensitive resin of one embodiment of the present invention, the compound having an ethylenically unsaturated group is preferably acrylic acid or methacrylic acid. Thereby, the fall of a sensitivity can be suppressed.

In the photocurable resin composition of one embodiment of the present invention, the oligomer of the photosensitive compound preferably has a molecular weight Mn of 700 to 5000.
When the molecular weight Mn is within this range, good dryness to touch can be obtained without adversely affecting the developability.

Further, the photocurable resin composition of one embodiment of the present invention preferably further contains a thermosetting component. By containing a thermosetting component, the heat resistance is further 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 one aspect of the present invention, there is provided a dry film including a dry coating film obtained by applying and drying the above-described photocurable resin composition on a carrier film. By using such a dry film, a dry coating film can be easily formed without applying a photocurable resin composition on a substrate.

Moreover, according to 1 aspect of this invention, the dry coating film formed from the photocurable resin composition mentioned above can be used as hardened | cured material obtained by photocuring by active energy ray irradiation.
Such a cured product can be improved to have excellent electroless gold plating resistance, solder heat resistance, moisture resistance, electrical insulation, and the like.

Furthermore, according to one aspect of the present invention, the dried coating film formed from the above-described photocurable resin composition is used as a printed wiring board having a pattern of a cured product obtained by photocuring by irradiation with active energy rays. be able to. Thereby, a highly reliable printed wiring board can be provided.

In the photocurable resin composition of one embodiment of the present invention, the dry coating film has excellent touch-drying property and high sensitivity, and in the cured product, excellent electroless gold plating resistance, solder heat resistance, moisture resistance Electrical insulation can be obtained, and the reliability of the printed wiring board having a cured product pattern can be improved.

The present inventors use a photocurable resin composition containing a photosensitive compound or an oligomer thereof using a compound containing a structure represented by the general formula (I) as a raw material, a carboxyl group-containing resin and a photopolymerization initiator. As a result, it has been found that the above-described problems can be solved, and the present invention has been completed.

(Wherein R ¹ represents an (m + 1) -valent polyhydric alcohol derivative, m and n are each represented by an integer of 1 or more, 1 is represented by 0 or an integer of 1 or more, and R ² is CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , any of a substituted or unsubstituted aromatic ring, and R ³ represents a substituted or unsubstituted aromatic ring.)

By containing a photosensitive compound or an oligomer thereof using a compound containing a structure represented by the general formula (I) as a raw material, it is possible to obtain a dry coating film having excellent touch dryness without a decrease in sensitivity. And compared with the case where it does not contain such a photosensitive compound or its oligomer, it becomes possible to obtain favorable solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, and the like.
Of the structure represented by the general formula (I), a structure represented by the general formula (II) is particularly preferable.

(Wherein R4 represents an (n + 1 + k) -valent polyhydric alcohol derivative, j, k, m are each represented by an integer of 1 or more, l and n are each represented by 0 or an integer of 1 or more, R ⁶ and R ⁸ represents each independently CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , a substituted or unsubstituted aromatic ring, and R ⁵ and R ⁷ are each independently substituted or unsubstituted. Represents an aromatic ring, and R ⁹ represents a hydrogen atom or a methyl group.)

Thus, by subjecting the general formula (I) to (meth) acrylation, it is possible to obtain a dry coating film having excellent touch dryness without a decrease in sensitivity. And compared with the case where it does not contain such a photosensitive compound or its oligomer, it becomes possible to obtain favorable solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, and the like.

Such a photosensitive compound or oligomer thereof is preferably obtained by depolymerizing polyester with a polyol having a plurality of hydroxyl groups in one molecule and reacting a compound having an ethylenically unsaturated group. Further, the molecular weight (Mn) is preferably 700 to 5,000.

This is presumably because the resulting photosensitive compound or oligomer thereof has semi-solid, aromatic rings, and thus improved development resistance, moisture resistance, and heat resistance. Further, it has been found that when a polyfunctional alcohol such as trimethylolpropane is used as a polyol component having a plurality of hydroxyl groups in one molecule, the characteristics are most exhibited.

That is, when trimethylolpropane is used as the above-described polyol component to be depolymerized, the synthesized photosensitive compound or its oligomer becomes trifunctional, and the sensitivity can be improved. In addition, in a depolymerized product (alcohol) depolymerized with a polyfunctional alcohol such as trimethylolpropane, the crystallinity of the polyester is lowered and white turbidity does not occur. For example, when equimolar trimethylolpropane is used as a repeating unit of polyester (PET), a resinous (non-crystalline) substance having a molecular weight of around 700 and having a solid content of 100% is obtained. This depolymerized product is transparent with no precipitation of crystals even after 3 months. Furthermore, it has a very high solubility in a solvent. Mild conditions are used when a compound having an ethylenically unsaturated group is reacted thereafter. Can be easily synthesized.

On the other hand, when a trifunctional alcohol such as propylene glycol is used without using trimethylolpropane, turbidity does not occur immediately after depolymerization, but crystals are generated and become turbid after standing for several days. And it turned out that the crystal | crystallization does not melt | dissolve in a solvent and the temperature close | similar to 200 degreeC is required for making it melt | dissolve. Such a phenomenon was surprising and unexpected.
Hereinafter, the structure of the photocurable resin composition of this embodiment is demonstrated in detail.
The photosensitive compound or oligomer thereof constituting the photocurable resin composition of the present embodiment,

The raw material is a compound having a structure represented by:

Such a photosensitive compound or an oligomer thereof can be obtained by depolymerizing polyester with a polyol having a plurality of hydroxyl groups in one molecule and further reacting a compound having an ethylenically unsaturated group.

The polyester used here is not particularly limited as long as it is a known polyester. For example, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene. Examples include naphthalate (PBN), polyarylate, liquid crystal polymer, PET bottles, PET films, and other PET products that have been pulverized, and recycled PET that has been recovered from waste and washed. Preferred is recycled PET, which can be washed and pelletized from the market.

Examples of the polyol having a plurality of hydroxyl groups in one molecule include bifunctional polyols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4- Butanediol, neopentyl glycol, spiroglycol, dioxane glycol, adamantanediol, 3-methyl-1,5-pentanediol, methyloctanediol, 1,6-hexanediol, 1,1,4-cyclohexanedimethanol, 2- Methylpropanediol 1,3,3-methylpentanediol 1,5, hexamethylene glycol, octylene glycol, 9-nonanediol 2,4-diethyl-1,5-pentanediol, bisphenol Ethylene oxide modified compound of diol A, propylene oxide modified compound of bisphenol A, ethylene oxide of bisphenol A, propylene oxide copolymer modified compound, copolymer polyether polyol of ethylene oxide and propylene oxide, carbonate diol, hydroxyl group terminal Polyalkanediene diols (elastomers such as 1,4-polyisoprenediol 1,4- and 1,2-polybutadiene diols and their hydrogenates), for example, hydroxyl group-terminated polyalkanediene diols. Examples of commercially available products include Epol (registered trademark) (hydrogenated polyisoprene diol, molecular weight 1,860, average polymerization degree 26, manufactured by Idemitsu Petrochemical Co., Ltd.), PIP (polyisoprene diol, molecular 2,200, average polymerization degree 34, manufactured by Idemitsu Petrochemical Co., Ltd., Polytail (registered trademark) HA (hydrogenated polybutadiene diol, molecular weight 2,200, average polymerization degree 39, manufactured by Mitsubishi Chemical Corporation), R-45HT (polybutane) Diol, molecular weight 2,270, average polymerization degree 42, manufactured by Idemitsu Petrochemical Co., Ltd.).

Examples of the trifunctional or higher functional polyol include glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, adamantanetriol, and the like. These ethylene oxide and propylene oxide modified products are also included.

In addition, examples having an aromatic ring include ethylene oxide and propylene oxide modified products of trifunctional or higher phenol compounds, and examples having a heterocyclic ring include Sake (manufactured by Shikoku Kasei Co., Ltd.). These can be used alone or in combination of two or more.

Among these, trifunctional polyols are preferable because they are non-turbid when obtained as a depolymerized product and have high solubility in a solvent. In particular, those containing trimethylolpropane and its derivatives as essential components are preferred. Moreover, when using combining 2 or more types of polyol, what contains 50 mol% or more of trimethylolpropane and its derivative (s) is especially preferable. The obtained depolymerized product may be molecularly extended with an acid anhydride, dibasic acid, polyisocyanate, or the like.

Also, a depolymerization catalyst can be used to promote depolymerization. Examples of the depolymerization catalyst include monobutyltin hydroxide, dibutyltin oxide, monobutyltin-2-ethylhexanoate, dibutyltin dilaurate, stannous oxide, tin acetate, zinc acetate, manganese acetate, cobalt acetate, and calcium acetate. , Lead acetate, antimony trioxide, tetrabutyl titanate, tetraisopropyl titanate and the like.

The blending amount of these depolymerization catalysts is usually 0.005 to 5 parts by mass, particularly 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of the polyester and polyol mixture.

Although not a depolymerization catalyst, water is a compound that promotes depolymerization. This is present as an impurity in the recycled PET, and causes a decrease in molecular weight when the PET is recycled. Therefore, normally, it should be removed by a very energy consuming process of drying, but this is not necessary in this embodiment. Rather, it is preferable to use recycled PET pellets that are once melted and kneaded in a pellet making machine such as an extrusion molding machine with water added. Since the molecular weight of recycled PET is low, the reaction temperature at the time of depolymerization can be lowered, and since the viscosity at the time of melting is low, a high concentration reaction is possible.

The molar ratio between the polyester and the polyol in such a depolymerized product (polyester polyol) is defined as A1 for the number of repeating units of the polyester and B1 for the number of moles of the polyol.
Molar ratio (A1) / (B1) = 0.3-5
Is preferred.

When the ratio is less than 0.3, the polyol is excessively contained and the ratio of the aromatic ring derived from the polyester is reduced, so that the dryness to the touch when solder resist is used, the solder heat resistance and the electrical characteristics are improved. Less effective. On the other hand, when the molecular weight is larger than 5, the molecular weight of the depolymerized product is large, and a polyester-derived crystallized product is present. When the compound having an ethylenically unsaturated group is subsequently reacted, it becomes insoluble in the solvent and reacts. Efficiency is reduced. More preferably, it is 0.5 to 4.5.

Examples of the compound having an ethylenically unsaturated group used for the synthesis of the photosensitive compound or the oligomer thereof constituting the photocurable resin composition of the present embodiment include acrylic acid, a dimer of acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a saturated or unsaturated dibasic acid anhydride and (meth) acrylate having one hydroxyl group in one molecule And half ester compounds.

Examples of the (meth) acrylate having a hydroxyl group for producing such a half ester compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di ( Examples thereof include (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, phenylglycidyl (meth) acrylate, and (meth) acrylic acid caprolactone adduct.

Examples of the dibasic acid anhydride for producing the half ester compound include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl Examples include endomethylenetetrahydrophthalic anhydride.

Here, the photosensitive compound represented by the general formula (II) or an oligomer thereof is particularly preferable, and the compound having an ethylenically unsaturated group to be reacted with the depolymerized product is acrylic acid or methacrylic acid. .
These unsaturated group-containing monocarboxylic acids can be used alone or in admixture of two or more.

Further, compounds having isocyanate and ethylenic unsaturation in one molecule may be used, and commercially available products include, for example, Karenz (registered trademark) MOI, Karenz MOI-EG, Karenz AOI, Karenz BEI (both Showa Denko) Etc.). Further, at this time, a product obtained by reacting one end of (meth) acrylate having one hydroxyl group and diisocyanate may be used.

Here, as a method of reacting the depolymerized product with the compound having an ethylenically unsaturated group, a known method can be used. For example, in the case of ethylenically unsaturated group-containing carboxylic acids, it is synthesized by dehydrating condensation with a hydroxyl group of a depolymerized product with an acid catalyst in a solvent, and in the case of an isocyanate compound, it is synthesized by reacting an isocyanate with a hydroxyl group. be able to. At this time, the blending ratio of the depolymerized polyol, the ethylenically unsaturated group-containing carboxylic acid, and the ethylenically unsaturated group-containing isocyanate is 0.5 to 1.2 with respect to the hydroxyl equivalent 1 of the depolymerized product. It is preferable to synthesize with a carboxylic acid equivalent and an isocyanate equivalent. When the carboxylic acid molar equivalent and the isocyanate molar equivalent are less than 0.5 with respect to the hydroxyl molar equivalent 1, the amount of the ethylenically unsaturated group is reduced and the sensitivity is lowered. Moreover, when it is more than 1.2, impurities increase. More preferably, it is 0.8 to 1.1. However, this is not the case when this impurity is removed in a cleaning process or the like. Here, when the carboxylic acid molar equivalent and the isocyanate molar equivalent are less than the hydroxyl equivalent 1, the obtained photosensitive oligomer has an unreacted hydroxyl group, but there is no problem in the characteristics even if some hydroxyl groups are present. .

The blending amount of such a photosensitive compound or oligomer thereof 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 of the photosensitive oligomer is 100 parts by mass or more, the alkali developability is lowered and a development residue is easily generated. On the other hand, in the case of 1 part by mass or less, the image forming ability is impaired. The amount is more preferably 5 to 60 parts by mass, still more preferably 10 to 40 parts by mass.

As the carboxyl group-containing resin, various known carboxyl group-containing resins having a carboxyl group in the molecule for the purpose of imparting alkali developability can be used. In particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is more preferable in terms of photocurability and development resistance. And the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof.

When only a carboxyl group-containing resin having no ethylenically unsaturated double bond is used, in order to make the composition photocurable, a plurality of the photosensitive compound of the present invention or an oligomer thereof or a molecule described later are used. It is necessary to use together a compound having an ethylenically unsaturated group, that is, a photopolymerizable monomer.
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 compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A type A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(4) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( 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. (5) During the synthesis of the resin described in (2) or (4) above, a compound having one hydroxyl group and one or more (meth) acryloyl groups in the molecule such as hydroxyalkyl (meth) acrylate is added, (Meth) acrylic carboxyl group-containing urethane resin.
(6) During the synthesis of the resin described in (2) or (4) above, one isocyanate group and one or more (meth) acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate The carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.
(7) (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
(8) (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin, and a dibasic acid anhydride is added to the resulting hydroxyl group. Added carboxyl group-containing photosensitive resin.
(9) A cyclic ether such as ethylene oxide or a cyclic carbonate such as propylene carbonate is added to a polyfunctional phenolic compound such as novolak, and the resulting hydroxyl group is partially esterified with (meth) acrylic acid, and the remaining hydroxyl group is polybasic acid. A carboxyl group-containing photosensitive resin obtained by reacting an anhydride.
(10) One epoxy group and one or more (meth) acryloyl groups in the molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate are added to the resins (1) to (9) described above. A carboxyl group-containing photosensitive resin obtained by adding a compound having the same.
In addition, (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions below.

Since the carboxyl group-containing resin as described above has a number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution is possible.

The acid value of such a carboxyl group-containing resin is preferably 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, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary. Depending on the case, the exposed portion and the unexposed portion may be dissolved and separated by the developer without distinction, and it becomes difficult to draw a normal resist pattern. More preferably, it is 45 to 120 mg KOH / g.

The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally preferably 2,000 to 150,000. If the weight average molecular weight is less than 2,000, the tack-free performance may be inferior, the moisture resistance of the coated 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 5,000 to 100,000.

The blending amount of such a carboxyl group-containing resin is preferably 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 30 to 50% by mass.
These carboxyl group-containing resins are not limited to those listed, and can be used by mixing one kind or plural kinds.

Examples of the photopolymerization initiator include an oxime ester photopolymerization initiator having a group represented by the following general formula (III), and an α-aminoacetophenone photopolymerization initiator having a group represented by the following general formula (IV). It is preferable to use one or more photopolymerization initiators selected from the group consisting of acylphosphine oxide photopolymerization initiators having a group represented by the following formula (V).

(Wherein R ¹⁰ 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 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 ¹¹ 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 Represents an alkanoyl group or a benzoyl group having 2-20 carbon atoms (carbon atoms may be substituted with an alkyl group or a phenyl group having 1 ~ 6), R ¹² and R ¹³ each independently, a carbon number 1 R ¹⁴ and R ¹⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group having two bonded to each other, R ¹⁶ and R ¹⁵ R ¹⁷ 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. However, one of R ¹⁶ and R ¹⁷ 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 (III) is preferably 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the following formula (VI), Examples include compounds represented by the formula (VII) and compounds represented by the general formula (VIII).

(Wherein R ¹⁸ 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 R ¹⁹ and R ²¹ each independently represents a phenyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom may be substituted). 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). And 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 ²⁰ Are 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 6 may be substituted with 6 alkyl groups or phenyl groups).

(Wherein R ²² , R ²³ and R ²⁸ each independently represents an alkyl group having 1 to 12 carbon atoms, and R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ each independently represents a hydrogen atom or a carbon atom. (Expression 1 represents an alkyl group of 1 to 6, M represents O, S or NH, and m and p each independently represents an integer of 0 to 5).

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

The α-aminoacetophenone photopolymerization initiator having a group represented by the general formula (IV) includes 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, Irgacure 379 (manufactured by Ciba Japan).

Examples of the acylphosphine oxide photopolymerization initiator having a group represented by the general formula (V) 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 Lucillin TPO (manufactured by BASF) and Irgacure 819 (manufactured by Ciba Japan).

The blending amount of such a photopolymerization initiator is preferably 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 0.5 to 15 parts by mass.

In the case of the oxime ester photopolymerization initiator having a group represented by the general formula (III), 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. When the amount is less than 0.01 parts by mass, sufficient sensitivity cannot be obtained. When the amount is more than 20 parts by mass, the deep curability decreases due to light absorption. More preferably, it is 0.01 to 5 parts by mass.

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, and 1,1-dichloroacetophenone.

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

Examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.
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, and 4-benzoyl-4'-propyl diphenyl sulfide.

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 (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-butyl Xyl) ethyl (Quantacure® BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (Esolol manufactured by Van® Dyk) 507) 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 particularly preferable. As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. The dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm is not colored because the maximum absorption wavelength is in the ultraviolet region, and uses not only a colorless and transparent photosensitive composition but also a colored pigment. 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. Among these, a thioxanthone compound and a tertiary amine compound are preferable. In particular, a thioxanthone compound is preferably included from the viewpoint of deep part curability.

The amount of such a thioxanthone compound is preferably 20 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. When the amount exceeds 20 parts by mass, the thick film curability is lowered, leading to an increase in the cost of the product. More preferably, it is 10 parts by mass or less.

The blending amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the blending amount 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 to 10 parts by mass.

For 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.

Examples of such chain transfer agents include chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid, and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol, Chain transfer agents having a hydroxyl group such as mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (Ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cycl Pentane thiol, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzenethiol like.

Further, the polyfunctional mercaptan-based compound is not particularly limited. For example, fat such as hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide, etc. Aromatic thiols such as xylylene dimercaptan and 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate) ), Trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythritol tetrakis (mercaptoacetate), dipentaeri Poly (mercaptoacetate) s of polyhydric alcohols such as litholhexakis (mercaptoacetate); ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate), propylene glycol bis (3 -Mercaptopropionate), glycerin tris (3-mercaptopropionate), trimethylolethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopro Poly (3-mercaptopropionate) s of polyhydric alcohols such as pionate) and dipentaerythritol hexakis (3-mercaptopropionate); 1,4-bis (3-mercaptobutyryloxy) Ii) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3- And poly (mercaptobutyrate) s such as mercaptobutyrate).

Further, examples of the heterocyclic compound having a mercapto group acting as a chain transfer agent include 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 Lerolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto- Examples include 5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, and 2-mercapto-6-hexanolactam.

In particular, as a heterocyclic compound having a mercapto group that is a chain transfer agent that does not impair the developability of the photocurable resin composition, mercaptobenzothiazole, 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 chain transfer agents can be used alone or in combination of two or more.
These photopolymerization initiators, photoinitiator assistants, sensitizers and chain transfer agents can be used alone or as a mixture of two or more.

The total amount of such photopolymerization initiator, photoinitiator assistant, sensitizer and chain transfer agent 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, a thermosetting resin or the like can be added to impart heat resistance. As the thermosetting component used in the present embodiment, known thermosetting resins such as amine resins such as melamine resins and benzoguanamine resins, isocyanate compounds, block isocyanate compounds, cyclocarbonate compounds, oxazine resins, bismaleimide resins, and carbodiimide resins. 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, and 3, A compound having two or more groups of any one or two kinds of 4- or 5-membered cyclic (thio) ether groups, for example, polyfunctional epoxy compounds, polyfunctional oxetane compounds, compounds having a plurality of thioether groups in the molecule Examples thereof include episulfide resins.

Examples of amine resins 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 for example, it can be 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, Same Mx-032, Same Mx-270, Mx-280, Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw-750LM (all manufactured by Sanwa Chemical Co., Ltd.), and the like.

The cyclocarbonate compound is not particularly limited as long as it is a cyclic compound and has a carbonate bond. Examples include alkylene carbonate compounds having a polyfunctional structure.

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.D. E. R. 664 (all manufactured by Dow Chemical Co., Ltd.), Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260 (all manufactured by Ciba Japan), Sumiepoxy (registered trademark) ESA-011, ESA-014, ELA-115, ELA-128 (Both manufactured by Sumitomo Chemical Co., Ltd.), A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all 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), Araldide 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.) Araldide ECN1235, Araldide ECN1273, Araldide ECN1299, Araldide XPY307 (all manufactured by Ciba Japan), EPPN (registered trademark) -201, EOCN (registered trademark) -1025, EOCN-1020, EOCN-104S, RE-306 ( All are manufactured by Nippon Kayaku Co., Ltd.), Sumiepoxy ESCN (registered trademark) -195X, ESCN-220 (all 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 type epoxy resins such as Araldide 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 resins such as jER604 (manufactured by Mitsubishi Chemical), Epototo YH-434 (manufactured by Nippon Steel Chemical Co., Ltd.), Araldide MY720 (manufactured by Ciba Japan), Sumiepoxy ELM (registered trademark) -120 ( Glycidylamine type epoxy resin such as Sumitomo Chemical Co., Ltd .; Araldide CY Hydantoin type epoxy resin such as 350 (manufactured by Ciba Japan); cycloaliphatic epoxy resin such as Celoxide (registered trademark) 2021 (manufactured by Daicel Chemical Industries), Araldide CY175, CY179 (all manufactured by Ciba Japan); YL-933 (Mitsubishi Chemical Corporation), T.M. E. N. Trihydroxyphenylmethane type epoxy resins such as EPPN (registered trademark) -501 and EPPN-502 (all manufactured by Nippon Kayaku Co., Ltd.); 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 (Mitsubishi Chemical Corporation); tetraphenylolethane type epoxy resin such as jERYL-931 (Mitsubishi Chemical Corporation), Araldide 163 (Ciba Japan); Araldide PT810 (Ciba)・ Product made in Japan, TEPIC (product made in Nissan Chemical Industries) Heterocyclic epoxy resins such as Bremermer (registered trademark) DGT (manufactured by NOF Corporation), diglycidyl phthalate resin such as ZX-1063 (manufactured by Nippon Steel Chemical Co., Ltd.), tetraglycidylxylenoylethane resin such as 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) Epoxy resins having a dicyclopentadiene skeleton such as: CP-50S, CP-50M (manufactured by NOF Corporation), glycidyl methacrylate copolymer epoxy resin; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Polybutadiene rubber derivatives (for example, manufactured by Daicel Chemical Industries, Ltd.) B-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.

Polyfunctional oxetane compounds include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl- 3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolac resin, poly (P-hydroxystyrene), cardo bisphenol S, 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, that is, an episulfide resin include, for example, 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.

Examples of the isocyanate compound include a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a compound having a plurality of blocked isocyanate groups in one molecule, that is, a blocked isocyanate compound. Here, 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. A group is generated.
As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.

Examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene. Examples include range isocyanate and 2,4-tolylene dimer.

Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate.

Examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adduct bodies, burette bodies, and isocyanurate bodies of the isocyanate compounds listed above may be mentioned.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include the polyisocyanate compounds described above.

Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid 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, Mercaptan block agents such as methylthiophenol and ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide block 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 It is.

The blocked isocyanate compound may be commercially available, for example, Sumidur (registered trademark) BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078. TPLS-2117, desmotherm 2170, desmotherm 2265 (all manufactured by Sumitomo Bayer Urethane Co., Ltd.), coronate 2512, coronate 2513, coronate (registered trademark) 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), TPA-B80E, 17B-60PX, E402-B80T (all manufactured by Asahi Kasei Chemicals) and the like. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.
Such a thermosetting component can be used individually by 1 type or in combination of 2 or more types.

In the case of a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, 0.6 to 2.5 equivalents are preferable with respect to 1 equivalent of the carboxyl group of the 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 to 2.0 equivalents.

In the case of a thermosetting resin typified by an isocyanate compound or a melamine derivative, a ratio of 1 to 100 parts by mass is preferable 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 to 70 parts by mass.
When using a thermosetting component having a plurality of cyclic (thio) ether groups in such a molecule, it is preferable to contain a thermosetting catalyst.

Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine.

Examples of commercially available compounds include imidazole compounds such as 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both manufactured by Shikoku Kasei Kogyo Co., Ltd.), and dimethylamine blocked isocyanate compounds such as U- CAT (registered trademark) 3503N, U-CAT3502T (all manufactured by San Apro), bicyclic amidine compounds and salts thereof, DBU, DBN, U-CATSA (registered trademark) 102, U-CAT 5002 (all manufactured by San Apro) ) And the like. In particular, it is not limited to these, as long as it is a thermosetting catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used.

Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine / isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used. It is preferable to use a compound that also functions as an adhesion-imparting agent in combination with a thermosetting catalyst.

The blending amount of these thermosetting catalysts is sufficient in the usual 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. The amount is 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass.

In the photocurable resin composition of the present embodiment, an adhesion promoter can be used in order to improve adhesion between layers or adhesion between the photosensitive resin layer and the substrate. Examples of such adhesion promoters include benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (Axel (registered trademark) M manufactured by Yodogawaguchi Chemical Co., Ltd.) 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzo Examples include triazole, amino group-containing benzotriazole, and silane coupling agent.

The compound having two or more ethylenically unsaturated groups in the molecule used in the photocurable / thermosetting resin composition of the present embodiment is photocured by irradiation with active energy rays, and the ethylenically unsaturated The group-containing carboxylic acid-containing resin is insolubilized or assists insolubilization in an alkaline aqueous solution. As such a compound, known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, and epoxy (meth) acrylate can be used. Specifically, 2-hydroxy Hydroxyalkyl acrylates such as ethyl acrylate and 2-hydroxypropyl acrylate; Diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; N, N-dimethylacrylamide, N-methylolacrylamide, N, Acrylamides such as N-dimethylaminopropyl acrylamide; N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate Aminoalkyl acrylates such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate and the like, or their ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone Polyvalent acrylates such as adducts; polyvalent acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols; glycerin diglycidyl ether, glycerin triglycidyl ether, tri Multivalent acrylates of glycidyl ethers such as methylolpropane triglycidyl ether and triglycidyl isocyanurate; Not limited to polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadiene, polyester polyols and other acrylates and melamine acrylates obtained by directly acrylated or urethane acrylated via diisocyanate, and / or each of the acrylates described above. And methacrylates.

Further, 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. Examples thereof include an epoxy urethane acrylate compound obtained by reacting a half urethane compound. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

The compounding amount of the compound having two or more ethylenically unsaturated groups in the molecule is 5 to 100 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated group-containing carboxylic acid-containing resin (A). is there. 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 alkaline aqueous solution falls, and a coating film becomes weak. More preferably, it is 1 to 70 parts by mass.

The photocurable resin composition of the present embodiment can contain a colorant. As the colorant, for example, 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, 175, 176, 185, 208
Perylene series: Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, 224
Diketopyrrolopyrrole: Pigment Red 254, 255, 264, 270, 272
Condensed azo type: Pigment Red 220, 144, 166, 214, 220, 221, 242
Anthraquinone series: Pigment Red 168, 177, 216, Solvent Red 52, 149, 150, 207
Kinacridone series: Pigment Red 122, 202, 206, 207, 209

Blue colorants include phthalocyanine and anthraquinone, and pigments include Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, and dyes. Solvent Blue 35, 63, 67, 68, 70, 83, 87, 94, 97, 122, 136, etc. can be used. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Similarly, the green colorant includes phthalocyanine, anthraquinone, and perylene, and for example, Pigment Green 7, 36, Solvent Green 3, 5, 20, 28, and the like can be used. 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, 108, 193, 147, 199, 202
Isoindolinone: Pigment Yellow 109, 110, 139, 179, 185
Condensed azo type: Pigment Yellow 93, 94, 95, 128, 155, 166, 180
Benzimidazolone series: Pigment Yellow 120, 151, 154, 156, 175, 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

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

The blending ratio of such a colorant is not particularly limited, but is preferably 10 parts by mass or less, particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. .

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 resin composition of the present invention is protected from oxidation ( 1) Radical scavengers that invalidate the generated radicals and / or (2) Oxidation of peroxide decomposers that decompose the generated peroxides into innocuous substances and prevent the generation of new radicals. An inhibitor can be added.

Antioxidants that act as radical scavengers include, for example, 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) - sebacate, amine compounds such as phenothiazine and the like.

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 292, TINUVIN 292 (Both manufactured by Ciba Japan).

Examples of the antioxidant that acts as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl-3,3′-thiol. And sulfur compounds such as dipropionate.

The peroxide decomposing agent may be commercially available, for example, Adeka Stub TPP (manufactured by ADEKA), Mark AO-412S (manufactured by Adeka Argus Chemical Co., Ltd.), Sumilyzer (registered trademark) TPS (manufactured by Sumitomo Chemical). Etc. These antioxidants can be used alone or in combination of two or more.

Since the polymer material absorbs light, thereby causing degradation and degradation, the photocurable resin composition of the present embodiment absorbs ultraviolet rays in addition to antioxidants in order to take measures against stabilization against ultraviolet rays. Agents can be used.

Examples of the ultraviolet absorber include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and Benzophenone derivatives such as 2,4-dihydroxybenzophenone; 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-tert-butylphenyl-3,5-di- benzoate derivatives such as t-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate; 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2 -(2'-Hydroxy-5'-methylphenyl) enzotria 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butyl) Phenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, etc. Benzotriazole derivatives of: triazine derivatives such as hydroxyphenyltriazine and bis (ethylhexyloxyphenol) methoxyphenyltriazine; cinnamate derivatives such as methyl 2,4-diisopropyl cinnamate, 2 ethylhexyl-p-methoxycinnamate; methyl anthranilate; Anthranilate derivatives such as phenyl anthranilate and benzyl anthranilate Dibenzoylmethane derivatives such as t- butyl methoxydibenzoylmethane 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 the stability of the molded product obtained from the photocurable resin composition of the present embodiment when used in combination with an antioxidant. Can be achieved.

In the photocurable resin composition of the present embodiment, a filler can be blended as necessary in order to increase the physical strength of the coating film. As such a filler, for example, known inorganic or organic fillers can be used, but barium sulfate, spherical silica and talc are particularly 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 amount of such 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 is increased, and the coating and moldability are lowered, or the cured product is brittle. More preferably, the content is 0.1 to 60% by mass.

Furthermore, the photocurable resin composition of the present embodiment 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 organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, and butyl carbitol. , Glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene Esters such as glycol butyl ether acetate; methyl lactate, ethyl lactate, Esters such as butyl acid, ethyl acetate, and butyl acetate; Alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum such as petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha Examples thereof include system solvents. Such organic solvents are used alone or as a mixture of two or more.

In the photocurable resin composition of the present embodiment, a binder polymer can be used for the purpose of further improving dryness to touch and improving handling properties, if necessary. Examples of such binder polymers include polyester polymers, polyurethane polymers, polyester urethane polymers, polyamide polymers, polyester amide polymers, acrylic polymers, cellulose polymers, polylactic acid polymers, phenoxy polymers, and the like. Can be used. These binder polymers can be used alone or as a mixture of two or more.

The photocurable resin composition of this embodiment can use an elastomer for the purpose of imparting flexibility, improving the brittleness of the cured product, etc., if necessary. For example, a polyester-based elastomer, Polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyesteramide elastomers, acrylic elastomers, and olefin elastomers can be used. In addition, resins in which some or all of the epoxy groups of epoxy resins having various skeletons are modified with carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can be used. Furthermore, epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers and the like can also be used. These elastomers can be used alone or as a mixture of two or more.

In addition, a polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization of the polymerizable compound contained in the curable resin composition in the present embodiment.

Examples of such thermal polymerization inhibitors include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride. Phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, Examples include picric acid, 4-toluidine, methylene blue, copper and an organic chelating agent reaction product, methyl salicylate, and phenothiazine, a nitroso compound, a chelate of a nitroso compound and Al, and the like.

The photocurable resin composition of the present embodiment can further contain a thixotropic agent such as finely divided silica, organic bentonite, montmorillonite, hydrotalcite, etc., if necessary. Organic bentonite and hydrotalcite are preferred as the thixotropic agent over time, and hydrotalcite is particularly excellent in electrical characteristics. In addition, known additives such as silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, rust preventives, etc. Can be blended.

After the photocurable resin composition of the present embodiment configured as described above is prepared with a predetermined composition, it is adjusted to a viscosity suitable for a coating method with an organic solvent, for example, on a base material, a dip coating method, The film 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 is evaporated and dried to form a dry coating film.

Volatile drying after coating can be done by using hot air circulation drying oven, IR furnace, hot plate, convection oven, etc. Can be carried out at a temperature of about 60 to 100 ° C. using a method of spraying on a support.

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

The dry coating film is a layer obtained by applying and drying a photocurable resin composition on a carrier film or a cover film. For such a dry coating film, the photocurable resin composition of the present embodiment 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 it is preferable that the adhesive force with the solder resist layer is smaller than that of the carrier film.

When such a dry film is used, if a cover film is used, it is peeled off, and the dry coating film and the base material are overlapped and bonded together using a laminator or the like to form a dry coating film on the base material. The In addition, what is necessary is just to peel a carrier film before or after the exposure mentioned later.

At this time, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluorine / polyethylene / PPO are used as the base material on which the dry coating film is formed.・ Uses materials such as copper clad laminates for high frequency circuits using cyanate esters, etc., all grades (FR-4 etc.) copper clad laminates, other polyimide films, PET films, glass substrates, ceramic substrates, A wafer board etc. can be mentioned.

Further, exposure is selectively performed with an active energy ray or directly with 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 laser light having a wavelength of 350 to 410 nm. By setting the 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. The exposure amount varies depending on the film thickness and the like, but is generally 5 to 200 mJ / cm ² , preferably 5 to 100 mJ / cm ² , more preferably 5 to 50 mJ / cm ² .

As the direct drawing apparatus, for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any apparatus may be used as long as it oscillates laser light having a wavelength of 350 to 410 nm.

Then, by exposing in this way, the exposed portion (the portion irradiated with the active energy ray) is cured, and the unexposed portion 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, the developing method can be a dipping method, a shower method, a spray method, a brush method, or the like. In addition to sodium carbonate, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines can be used as the developer.

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

[Photosensitive Compound Synthesis Example 1]
192 parts of PET flake (Mitsubishi Chemical Corporation: Novavex (trade name)) was charged in a 500 ml four-necked round-bottom separable lasco equipped with a stirrer, a nitrogen introduction tube, and a cooling tube, and the atmosphere in the flask was changed to 300 ° C. Soaked in a salt bath heated to When the PET flakes were dissolved, stirring was started and 0.65 part of dibutyltin oxide was added.

Next, 134 parts of trimethylolpropane previously heated and dissolved at 130 ° C. was added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Then, the salt bath was replaced with an oil bath that had been heated to 240 ° C. in advance, and the temperature in the flask was kept at 220 ° C. (± 10 ° C.) for 5 hours. The reaction product was transparent yellow and soft viscous at room temperature.

To 100 parts of the obtained reaction product, 37 parts of toluene and 74 parts of methyl isobutyl ketone were introduced and mixed. Next, 65 parts of acrylic acid, 1.94 parts of paratoluenesulfonic acid, and 0.26 part of paramethoxyphenol were added and reacted at 110 ° C. for 100 hours, and cooled to room temperature. The acid value of the obtained reaction solution was measured, and an acid equivalent alkaline aqueous solution was added to the flask and stirred to neutralize. Next, 50 parts of brine was added and stirred.

Thereafter, the solution was transferred to a separating funnel, the aqueous phase was discarded, and the oil phase was washed twice with 100 parts of a 5 wt% NaCl solution. After washing, the solvent was distilled off with an evaporator to obtain a reaction product having a nonvolatile content of 100%. The obtained reaction product was a brown transparent soft liquid at room temperature. This is called A-1 resin.

[Photosensitive compound synthesis example 2]
After charging 39 parts of PET flakes (Mitsubishi Chemical Corporation: Novavex (trade name)) into a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen introduction tube, and a cooling tube, the inside of the flask was made into a nitrogen atmosphere, and then 300 ° C. Soaked in a salt bath heated to When the PET flakes were dissolved, stirring was started and 0.40 part of dibutyltin oxide was added.

Next, 161 parts of DURANOL (registered trademark) T5650J (manufactured by Asahi Kasei Chemicals Corporation) preheated at 130 ° C. was added little by little while taking care not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Then, the salt bath was replaced with an oil bath that had been heated to 240 ° C. in advance, and the temperature in the flask was kept at 220 ° C. (± 10 ° C.) for 5 hours. The reaction product was transparent yellow and soft viscous at room temperature.

To 100 parts of the resulting reaction product, 37 parts of toluene and 74 parts of methyl isobutyl ketone were introduced and mixed. Next, 14.5 parts of acrylic acid, 0.43 part of paratoluenesulfonic acid, and 0.06 part of paramethoxyphenol were added, reacted at 110 ° C. for 10 hours, and cooled to room temperature. The acid value of the obtained reaction solution was measured, and an acid equivalent alkaline aqueous solution was added to the flask and stirred to neutralize.

Next, 50 g of saline was added and stirred. Thereafter, the solution was transferred to a separating funnel, the aqueous phase was discarded, and the oil phase was washed twice with 100 parts of a 5 wt% NaCl solution. After washing, the solvent was distilled off with an evaporator to obtain a reaction product having a nonvolatile content of 100%. The obtained reaction product was a brown transparent soft liquid at room temperature. This is referred to as A-2 resin.

[Photosensitive Compound Synthesis Example 3]
Charge 192 parts of PET flakes (Mitsubishi Chemical's Novavex (trade name)) to a 500 ml four-necked round bottom separable lasco fitted with a stirrer, nitrogen inlet tube, and cooling tube. It was immersed in a heated salt bath. When the PET flakes were dissolved, stirring was started and 0.65 part of dibutyltin oxide was added.

Next, 67 parts of trimethylolpropane and 127 parts of dipentaerythritol, which were preliminarily heated and dissolved at 130 ° C., were added little by little while taking care not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Then, the salt bath was replaced with an oil bath that had been heated to 240 ° C. in advance, and the temperature in the flask was kept at 220 ° C. (± 10 ° C.) for 5 hours. The reaction product was transparent yellow and soft viscous at room temperature.

Into 100 parts of the obtained reaction product, 109 parts of toluene, 138 parts of cyclohexanone, 40 parts of dimethyl sulfoxide, and 13 parts of water were introduced and mixed. Next, 84 parts of acrylic acid, 9.9 parts of paratoluenesulfonic acid monohydrate, and 0.31 part of paramethoxyphenol were added and reacted at 110 ° C. for 10 hours and cooled to room temperature. The acid value of the obtained reaction solution was measured, and an acid equivalent alkaline aqueous solution was added to the flask and stirred to neutralize.

Next, 50 parts of saline was added and stirred. Thereafter, the solution was transferred to a separating funnel, the aqueous phase was discarded, and the oil phase was washed twice with 100 parts of a 5 wt% NaCl solution. After washing, the solvent was distilled off with an evaporator to obtain a reaction product having a nonvolatile content of 100%. The obtained reaction product was a brown transparent soft liquid at room temperature. This is called A-3 resin.

[Photosensitive Compound Synthesis Example 4]
A 500 ml four-necked round bottom separable flask equipped with a stirrer, a nitrogen introducing tube, and a cooling tube was charged with 192 parts of recycled PET flakes having an IV value of 0.6 to 0.7. It was immersed in a salt bath heated to 0 ° C. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added.

Next, 134 parts of trimethylolpropane previously heated and dissolved at 130 ° C. was added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Then, the salt bath was replaced with an oil bath that had been heated to 240 ° C. in advance, and the temperature in the flask was kept at 220 ° C. (± 10 ° C.) for 5 hours. The reaction product was transparent yellow and soft viscous at room temperature.

To 100 parts of the obtained reaction product, 37 parts of toluene and 74 parts of methyl isobutyl ketone were introduced and mixed. Next, 65 parts of acrylic acid, 1.94 parts of paratoluenesulfonic acid, and 0.26 part of paramethoxyphenol were added and reacted at 110 ° C. for 10 hours, and cooled to room temperature. The acid value of the obtained reaction solution was measured, and an acid equivalent alkaline aqueous solution was added to the flask and stirred to neutralize.

Next, 50 parts of saline was added and stirred. Thereafter, the solution was transferred to a separating funnel, the aqueous phase was discarded, and the oil phase was washed twice with 100 parts of a 5 wt% NaCl solution. After washing, the solvent was distilled off with an evaporator to obtain a reaction product having a nonvolatile content of 100%. The obtained reaction product was a brown transparent soft liquid at room temperature. This is called A-4 resin

[Photosensitive Compound Synthesis Example 5]
192 parts of PET flake (manufactured by Mitsubishi Chemical Corporation: Novavex (trade name)) was charged in a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen introduction tube, and a cooling tube, and the atmosphere in the flask was changed to 300 ° C. Soaked in a salt bath heated to When the PET flakes were dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Next, 134 parts (1.0 mol) of trimethylolpropane previously heated and dissolved at 130 ° C. was added little by little while taking care not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased.

Next, the salt bath was replaced with an oil bath that had been heated to 240 ° C. in advance, and the temperature inside the flask was kept at 220 ° C. (± 10 ° C.) for 5 hours. The reaction product was transparent yellow and soft viscous at room temperature. This polyol resin is referred to as PET-TMP resin (a).

Next, 66.6 parts of isophorone diisocyanate and 80 parts of carbitol acetate are charged into another four-necked flask, to which 37.6 parts of 2-hydroxyethyl acrylate, 0.05 part of dibutyltin laurate, p-methoxy is added. A carbitol acetate solution mixed with 20 parts of phenol 0.03 part carbitol acetate was added dropwise at 35 ° C. over 2 hours. Subsequently, it was made to react at 80 degreeC for 2 hours.

After completion of the reaction, the temperature was lowered to 40 ° C., and a carbitol acetate solution containing 33 parts of PET-TMP resin (a), 0.1 part of dibutyltin laurate and 50 parts of carbitol acetate was slowly poured, and then 80 ° C. For 3 hours to obtain an ethylene terephthalate type urethane acrylate having a nonvolatile content of 80%. This is referred to as A-5 resin.

[Photosensitive Compound Synthesis Example 6]
Into a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen introducing tube and a cooling tube were charged 326 parts of the PET-TMP resin (a) heated to 230 ° C., and 146 parts of adipic acid were immediately added. Esterification was performed in a nitrogen stream at 210 ° C. to 220 ° C. for 3 hours, and finally, a reduced pressure treatment of 20 to 25 Torr was performed for 30 minutes to obtain a soft polyester resin at room temperature.

To 100 parts of the obtained reaction product, 37 parts of toluene and 74 parts of methyl isobutyl ketone were introduced and mixed. Next, 65 parts of isocyanate ethyl methacrylate (made by Showa Denko KK: trade name MOI), 0.1 part of dibutyltin dilaurate and 0.01 part of methylparabenzoquinone were added and kept at 70 ° C. to 75 ° C. for 3 hours, resulting in infrared absorption. It was observed that the isocyanate group had disappeared completely. This is called A-6 resin.

Using the resin solutions of each synthesis example, the various components shown in Table 1 are blended in the proportions (parts by mass) shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and photosensitive for solder resist. A functional resin composition was prepared. Here, when the dispersion degree of the obtained photosensitive resin composition was evaluated by particle size measurement using a grindometer manufactured by Eriksen Co., it was 15 μm or less.

* 1: Dipentaerythritol hexaacrylate (DPHA: Nippon Kayaku Co., Ltd.)
* 2: TMPTA
* 3: Corresponds to explanation (6) of R-2000 (solid content 65%) (made by DIC) carboxyl group-containing resin
* 4: ZFR-1401H (65% solid content) (Nippon Kayaku Co., Ltd.) Corresponds to carboxyl group containing (7)
* 5: UXE-3000 (solid content 65%) (Nippon Kayaku Co., Ltd.) Corresponds to explanation (3) of carboxylic acid resin
* 6: UE-9210 (65% solid content) (manufactured by DIC) An acid-modified epoxy acrylate with an increased photoreactive group by further reacting glycidyl methacrylate with carboxylic acid in the explanation of carboxyl group-containing resin (6)
* 7: Cyclomer (registered trademark) P (ACA) Z250 (solid content 45%) (manufactured by Daicel Chemical Industries, Ltd.) Corresponds to explanation (1) of carboxyl group-containing resin
* 8: Irgacure OXE02 (Ciba Japan)
* 9: Nikaluck MW-100LM (Sanwa Chemical Co., Ltd.)
* 10: Phenol novolac type epoxy resin (DEN438: manufactured by Dow Chemical Company)
* 11: Melamine
* 12: CIPigment Blue 15: 3
* 13: CIPigment Yellow 147
* 14: Barium sulfate (B-30: Sakai Chemical)
* 15: Dipropylene glycol monomethyl ether

Performance evaluation:
<Optimum exposure amount>
The photo-curable resin composition shown in Table 1 was applied to the entire surface of a circuit pattern substrate having a copper thickness of 35 μm after polishing with buffalo, washed with water, and dried by a screen printing method in a hot air circulation drying oven at 80 ° C. Dry for 60 minutes.

After drying, exposure is performed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and development (30 ° C., 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution) is performed at 60. When the pattern of the step tablet remaining when it was performed in seconds was 7 steps, the optimum exposure amount was set.

<Dry touch dryness>
The photocurable resin compositions of Examples and Comparative Examples shown in Table 1 were applied on the entire surface of the patterned copper foil substrate by screen printing and dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. It was left to cool. A PET film was pressed against this substrate, and then the sticking state of the film when the negative film was peeled off was evaluated.
(Double-circle): When peeling a film, there is no resistance and a trace is not left in a coating film.
○: When the film is peeled off, there is no resistance, but the coating film has a slight mark.
(Triangle | delta): When peeling a film, there exists resistance slightly and the coating film has a trace.
X: When the film is peeled off, there is resistance and the coating film is clearly marked.

<Resolution>
The photocurable resin compositions of the examples and comparative examples shown in Table 1 were subjected to screen printing by washing a circuit pattern substrate having a line / space of 300/300 μm and a copper thickness of 35 μm after buffing, drying, and drying. It was applied and dried for 30 minutes in a hot air circulating drying oven at 80 ° C. After drying, exposure was performed using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp).

As the exposure pattern, a glass dry plate for drawing a 20/30/40/50/60/70/80/90/100 μm line in the space portion was used. At this time, the active energy ray was irradiated so that it might become the optimal exposure amount of a photocurable resin composition. After the exposure, development was performed with a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. to draw a pattern, and a cured product was obtained by heat curing at 150 ° C. for 60 minutes.
The minimum residual line of the cured product of the obtained photocurable resin composition for solder resist was determined using an optical microscope adjusted to 200 times (resolution).

Characteristic test:
The compositions of Examples and Comparative Examples listed in Table 1 were applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Thereafter, a solder resist pattern is exposed at an optimum exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp) on this substrate, 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.

<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. After evaluating the presence or absence, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.
A: No soaking or peeling is observed.
○: Slight penetration is confirmed after plating, but does not peel off after tape peeling.
Δ: Slight penetration after plating and peeling after tape peel.
X: There is peeling after plating.

<Alkali resistance>
The evaluation substrate was immersed in an aqueous 10 wt% NaOH solution at 40 ° C. for 30 minutes, and soaking and dissolution of the coating film were confirmed. Further, peeling by tape peeling was confirmed. Judgment criteria are as follows.
A: There is no infiltration, dissolution, peeling, and no change in surface gloss.
○: Dyeing, melting and peeling do not occur, but gloss changes.
Δ: Slight infiltration, dissolution, or peeling
X: Dyeing, dissolution, or peeling is largely confirmed.

Dry film evaluation:
Evaluation substrates were prepared for the photosensitive resin compositions of Example 1 and Comparative Example 1 by the method shown below and evaluated in the same manner.
<Dry film production>
Each of the photosensitive resin compositions of Example 1 and Comparative Example 1 was appropriately diluted with methyl ethyl ketone, and then, using an applicator, a PET film (FB-50: 16 μm manufactured by Toray Industries Inc.) so that the film thickness after drying was 30 μm. And dried at 40-100 ° C. to obtain a dry film.

<Board fabrication>
After the circuit-formed substrate was buffed, the dry film produced by the above method was subjected to a pressurization degree of 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.
The evaluation results are shown in Table 2.

As shown in Table 2, in Examples 1 to 12, compositions having excellent dryness to touch while maintaining the same sensitivity as in Comparative Examples 1 and 2 were obtained.
In particular, when PET is depolymerized with trimethylolpropane and a photosensitive group is introduced (Examples 1 to 7, 10 to 12), it is excellent in electroless gold plating resistance and alkali resistance, and is an alkali developable photocurable resin. It turns out that it is useful as a composition.

Claims (8)

1. A photocurable resin composition comprising a photosensitive compound or an oligomer thereof, a carboxyl group-containing resin, and a photopolymerization initiator, each of which includes a compound having a structure represented by the following general formula (I) as a raw material.
   

   

   (Wherein R ¹ represents an (n + 1) -valent polyhydric alcohol derivative, m and n are each represented by an integer of 1 or more, l is represented by 0 or an integer of 1 or more, and R ³ is CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , any of a substituted or unsubstituted aromatic ring, and R ² represents a substituted or unsubstituted aromatic ring)
2. The photocurable resin composition according to claim 1, wherein the photosensitive compound or the oligomer thereof includes a structure represented by the following general formula (II).
   

   

   (Wherein R ⁴ represents an (n + 1 + k) -valent polyhydric alcohol derivative, j, k, m are each represented by an integer of 1 or more, l and n are each represented by 0 or an integer of 1 or more, R ⁶ and R ⁸ independently represents CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , or an aromatic ring, and R ⁵ and R ⁷ each independently represents a substituted or unsubstituted aromatic ring. R ⁹ represents a hydrogen atom or a methyl group)
3. The photosensitive compound or the oligomer thereof is obtained by depolymerizing polyester with a polyol having a plurality of hydroxyl groups in one molecule, and further reacting with a compound having an ethylenically unsaturated group. The photocurable resin composition according to claim 2.
4. 4. The photocurable resin composition according to claim 3, wherein the polyester is recycled polyethylene terephthalate.
5. 4. The photocurable resin composition according to claim 3, wherein the polyol contains trimethylolpropane.
6. A dry film comprising a dry coating film obtained by applying and drying the photocurable resin composition according to any one of claims 1 to 5 on a film.
7. A dry film obtained by applying and drying the photocurable resin composition according to claim 1 or 2 on a substrate, or applying and drying the photocurable resin composition on a film. A cured product obtained by laminating and photocuring the dried coating film formed on the substrate by irradiation with active energy rays.
8. A dry film obtained by applying and drying the photocurable resin composition according to claim 1 or 2 on a substrate, or applying and drying the photocurable resin composition on a film. A printed wiring board having a pattern of a cured product obtained by laminating and photocuring a dried coating film formed on the substrate by irradiation with active energy rays.