WO2010131649A1

WO2010131649A1 - Photosensitive resin composition, dry film and cured product of same, and printed wiring board using these materials

Info

Publication number: WO2010131649A1
Application number: PCT/JP2010/057954
Authority: WO
Inventors: 大地岡本; 聖夫有馬
Original assignee: 太陽インキ製造株式会社
Priority date: 2009-05-12
Filing date: 2010-05-11
Publication date: 2010-11-18
Also published as: CN102422224A; KR20120013982A; CN102422224B; JP2010266518A; KR101362543B1; JP5567290B2

Abstract

Disclosed is an alkali-developable photosensitive resin composition which comprises (A) a resin produced using a recovered polyester as a raw material and (B) a photopolymerization initiator. Preferably, the resin (A) is a polyol, a carboxyl-group-containing resin, or a photosensitive resin having an ethylenically unsaturated group, particularly a polyol produced by depolymerizing a recovered polyester (a) with two or more molecules of a polyol (b) per molecule of the polyester (a), a carboxyl-group-containing resin produced by reacting the recovered polyester (a) with a polybasic acid or an anhydride thereof (c) prior to, simultaneously with or subsequent to the depolymerization, or the like. Preferably, the photosensitive resin composition additionally comprises a carboxyl-group-containing photosensitive resin (C) that is different from the resin (A). Preferably, the photosensitive resin composition additionally comprises a heat-curable component (D), or additionally comprises a coloring agent (E). The photosensitive resin composition or a dry film thereof is advantageously applicable to the formation of a cured coating film such as a solder resist for a printed wiring board or a flexible printed wiring board, or the like.

Description

Photosensitive resin composition, dry film and cured product thereof, and printed wiring board using them

The present invention relates to an alkali-developable photosensitive resin composition containing a resin made from recovered polyester, a dry film and a cured product thereof, and a printed wiring board using them.

In recent years, from the viewpoint of environmental problems, printed wiring boards used for electronic devices have been required to use environmentally friendly materials. For example, due to the social problem of the generation of harmful gases such as dioxins during incineration, flame retardant materials and coloring materials used for prepregs, solder resist films, etc., have been changed from conventional halogen-containing systems such as bromine to non-halogen systems. Conversion is required.
For example, various studies have been made on non-halogenation of a flame retardant material of a printed wiring board composition (see, for example, Patent Document 1). However, due to growing interest in environmental issues, further consideration for the environment is required.

On the other hand, since a printed wiring board is used for an electronic device, insulation is required. In addition, heat resistance is required because an electronic component is attached to the interlayer resin insulation layer of the printed wiring board at a high temperature.
In recent years, with the miniaturization of the pattern of the solder resist film formed on the outermost layer of the printed wiring board, a photolithography method is used for pattern formation. At this time, since the pattern is formed by irradiating active energy rays through the mask pattern, the resin composition for forming the solder resist film is further required to have photocurability. Therefore, among such photosensitive resin compositions, a non-halogen type in consideration of the environment has been proposed (for example, see Patent Document 2).
Thus, in the resin composition for printed wiring boards, both consideration for the environment and maintenance and improvement of characteristics are required.

On the other hand, the amount of PET bottles made from polyester has been rapidly increasing in recent years due to its light weight, transparency, excellent gas barrier properties, and high strength, and the disposal method has become a social problem. Therefore, PET bottles are generally collected separately and recycled, and various studies have been made on recycling PET bottles (see, for example, Patent Documents 3 and 4). However, in the recycling process, there is a problem that the molecular weight of PET decreases due to hydrolysis of ester bonds, and the melt viscosity and mechanical strength of PET decrease. Such a decrease in quality is a factor in inhibiting the recycling of PET bottles. Therefore, at present, recycled PET resin is mainly used only in the field of fibers and industrial materials. However, as the amount of discarded PET bottles increases, a new effective method of using recycled PET resin is sought. ing.

Examples of new methods for reclaiming waste polyester include production of alkyd resins for paints using a depolymerization reaction with glycols (see Patent Document 5), and production of polyester resins for paints using recycled polyesters (Patent Documents 6 and 7). Further, the use of recycled polyester as a raw material for a photocurable urethane resin (see Patent Document 8) has been studied, all of which are intended for use in coating compositions.

WO02 / 006399 Publication (Claims) JP 2000-7974 A (Claims) JP-A-10-287844 (Claims) JP-A-11-114961 (Claims) Japanese Patent No. 3310661 (Claims) Japanese Patent No. 3443409 (Claims) Japanese Patent No. 3256537 (Claims) JP 2004-307779 A (Claims, Examples)

The present invention has been made in view of the prior art as described above, and has high sensitivity, excellent solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, etc., and has an alkali developability in consideration of environmental problems. It aims at providing the photosensitive resin composition.
Furthermore, an object of the present invention is to provide a dry film and a cured product excellent in various properties as described above obtained by using such a photosensitive resin composition, and a cured film such as a solder resist using the dry film and the cured product. It is in providing the printed wiring board formed by.

In order to achieve the above object, according to the present invention, an alkali-developable photosensitive resin comprising (A) a resin made from recovered polyester as a raw material, and (B) a photopolymerization initiator. A composition is provided.
In a preferred embodiment, the resin (A) is a polyol, a carboxyl group-containing resin, or a photosensitive resin having an ethylenically unsaturated group. In particular, (a) the recovered polyester is (b) in one molecule. A polyol obtained by depolymerization with a polyol having two or more hydroxyl groups, or (c) a carboxyl group-containing resin obtained by reacting a polybasic acid or its anhydride before, simultaneously with or after depolymerization, the carboxyl group A (meth) acrylate photosensitive resin obtained by reacting a compound (d) having an ethylenically unsaturated group with a functional group capable of reacting with an acid or alcohol such as (meth) acrylic acid and derivatives thereof, or After the recovered polyester (a) is depolymerized with the polyol (b), an acid or alcohol such as (meth) acrylic acid and its derivatives A (meth) acrylate-based photosensitive resin obtained by reacting a functional group capable of reacting with a compound (d) having an ethylenically unsaturated group, or a polybasic acid or its (meth) acrylate-based photosensitive resin It is preferably a carboxyl group-containing photosensitive resin obtained by reacting the anhydride (c), and further preferably includes a carboxyl group-containing photosensitive resin (C) other than the resin (A).
In a preferred embodiment, it further contains a thermosetting component (D), and preferably further contains a colorant (E). Such a photosensitive resin composition, particularly a photocurable / thermosetting resin composition containing a thermosetting component (D), can be suitably used as a solder resist.

Further, according to the present invention, the photosensitive resin composition can be obtained by curing a photocurable dry film obtained by applying and drying the photosensitive resin composition on the film, or the photosensitive resin composition or the dry film. There are also provided a cured product, particularly a cured product obtained by photocuring on copper, and a cured product obtained by photocuring in a pattern.
Furthermore, according to the present invention, there is also provided a printed wiring board having a cured film obtained by photocuring the photosensitive resin composition or dry film in a pattern and then thermally curing.

Since the alkali-developable photosensitive resin composition of the present invention contains (A) a resin made from recovered polyester and (B) a photopolymerization initiator, it can contribute to effective utilization of resources. Further, the depolymerized product obtained by depolymerizing the recovered polyester (a) with the polyol (b) has a high carbon ratio derived from the polyester, and the polybasic acid or its anhydride (c) before, simultaneously with or after the depolymerization. Functional group capable of reacting with acid or alcohol such as (meth) acrylic acid and its derivatives after depolymerizing the recovered polyester (a) with polyol (b) And a (meth) acrylate photosensitive resin obtained by reacting a compound (d) having an ethylenically unsaturated group, or a polybasic acid or an anhydride thereof (c) further added to the (meth) acrylate photosensitive resin. Since it can be suitably used for the synthesis of a carboxyl group-containing photosensitive resin obtained by the reaction, the recycled resin utilization rate is increased and recovered. Terephthalic acid depolymerization product in polyester, can contribute soldering heat resistance of the dry coating film of the photosensitive resin composition, an electroless gold plating resistance, moisture resistance, electrical insulating properties and the like. Furthermore, when it contains the carboxyl group-containing resin or the carboxyl group-containing photosensitive resin, and preferably further contains a carboxyl group-containing photosensitive resin (C) other than these, it is photosensitive and alkali-developable. Further, preferably by further containing a thermosetting resin (D), a cured film having further excellent solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation and the like can be formed.
Therefore, the photosensitive resin composition of the present invention can be advantageously applied to the formation of a cured film such as a solder resist of a printed wiring board or a flexible printed wiring board.

As described above, the characteristic of the photosensitive resin composition of the present invention is that the resin (A) using the recovered polyester as a raw material is used.
According to the research of the present inventors, by containing the resin (A) made from the recovered polyester as a raw material, environmental consideration is realized, and the dicarboxylic acid component in the recovered polyester depolymerized product In particular, in the case of polyethylene terephthalate, the terephthalic acid component contained in the structure was found to contribute to the solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, etc. of the dry coating film of the photosensitive resin composition. . This is an effective means for solving the problem of reduced mechanical strength due to the decrease in molecular weight, which has been regarded as a drawback of the recovered polyester, by using it in a photosensitive resin composition that does not require mechanical strength. .

Hereafter, the structural component of the photosensitive resin composition of this invention is demonstrated in detail.
First, as the resin (A) using the recovered polyester as a raw material, various resins obtained from a depolymerized product obtained by depolymerizing the recovered polyester by a conventionally known method can be used. The resin like this is mentioned.
(A-1) A polyol obtained by depolymerizing the recovered polyester (a) with the polyol (b). (In addition, although the polyol component and dicarboxylic acid component of polyester generate | occur | produce by depolymerization and these mixtures are obtained, it is a mixture with the dicarboxylic acid components mixed.)
(A-2) A carboxyl group-containing resin obtained by reacting a polybasic acid or its anhydride (c) before, simultaneously with or after the depolymerization.
(A-3) Obtained by reacting the polyol (A-1) with a compound (d) having an ethylenically unsaturated group and a functional group capable of reacting with an acid or alcohol such as (meth) acrylic acid and its derivatives. (Meth) acrylate photosensitive resin.
(A-4) A compound (d) having a functional group capable of reacting with an acid or alcohol such as (meth) acrylic acid or a derivative thereof and an ethylenically unsaturated group on the carboxyl group of the carboxyl group-containing resin (A-2) ) A (meth) acrylate-based photosensitive resin obtained by partially or completely reacting (when partially reacted, a carboxyl group-containing photosensitive resin).
(A-5) A carboxyl group-containing photosensitive resin obtained by further reacting the (meth) acrylate photosensitive resin (A-3) with a polybasic acid or its anhydride (c).
(A-6) By polyaddition reaction of a diisocyanate as described later, a polyol compound, and a compound having one hydroxyl group and one or more (meth) acryl groups in a molecule such as hydroxyalkyl (meth) acrylate, In the synthesis of the terminal (meth) acrylated photosensitive urethane resin, the polyol (A-1) obtained by depolymerizing the recovered polyester (a) with the polyol (b) was used as the polyol compound. Photosensitive urethane resin.
(A-7) Obtained by depolymerizing the recovered polyester (a) with a polyol (b) as a polyol compound during the synthesis of a carboxyl group-containing urethane resin or a carboxyl group-containing photosensitive urethane resin as described later. A carboxyl group-containing urethane resin or a carboxyl group-containing photosensitive urethane resin using the polyol (A-1) obtained.
In this specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions such as (meth) acrylic acid and (meth) acrylates. is there.

The recovered polyester (a) can be used as long as it is a conventionally known polyester waste material. Among them, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate. (PBN), polytrimethylene terephthalate (PTT), liquid crystal polymer, etc. Specifically, PET bottles, PET films, and other remanufactured PET products are crushed, recovered from waste and washed PET etc. are mentioned. Preferred is recycled PET, but these can be obtained from the market as washed and pelletized. The shape of the polyester is not particularly limited, and is preferably in the form of pellets and / or flakes. Moreover, although it is not necessary to grind | pulverize finely in powder form, the grind | pulverized thing may be used.

The recovered polyester (a) can be depolymerized by a conventionally known method. Preferably, the recovered polyester (a) is depolymerized with a polyol (b) having two or more hydroxyl groups in one molecule in the presence of a depolymerization catalyst. The method is preferred. In particular, without using a solvent, in a state in which the recovered polyester (a) is dissolved by heating, a liquid polyol (b) is added (in the case of solid, it is dissolved by heating to make it liquid), preferably the presence of a catalyst The reaction is preferably carried out at about 200 to 300 ° C. below.

The ratio of the recovered polyester (a) to the polyol (b) is such that the ratio of the number of moles of repeating units (a1) of the polyester to the number of moles of polyol (b1) is (a1) / (b1) = 0.5 to 3, preferably in the range of 0.8-2. When the ratio is less than 0.5, the polyol is excessively contained, the ratio of the aromatic ring derived from the polyester is decreased, and the effect of improving heat resistance and chemical resistance is decreased, which is not preferable. On the other hand, when the ratio is greater than 3, the depolymerized product is crystallized in most cases and is insoluble in the solvent, which is not preferable.

The polyol (b) having two or more hydroxyl groups in one molecule can be any bifunctional or higher polyol, and is not limited to a specific one. Bifunctional polyols include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, spiro glycol, dioxane glycol, adamantane Diol, 3-methyl-1,5-pentanediol, methyloctanediol, 1,6-hexanediol, 1,1,4-cyclohexanedimethanol, 2-methylpropanediol 1,3, 3-methylpentanediol 1, 5, ethylene oxide modification of bifunctional phenols such as hexamethylene glycol, octylene glycol, 9-nonanediol, 2,4-diethyl-1,5-pentanediol, bisphenol A A compound, a propylene oxide-modified compound of a bifunctional phenol such as bisphenol A, an ethylene oxide of a bifunctional phenol such as bisphenol A, a propylene oxide copolymer-modified compound, a copolymer polyether polyol of ethylene oxide and propylene oxide, a carbonate diol, Polyester diols, adamantane diols, polyether diols, polyester diols, hydroxyl-terminated polyalkanediene diols, such as 1,4-polyisoprenediol, 1,4- and 1,2-polybutadiene diols and their hydrogenated products Elastomers). As a commercially available product, for example, as an example of a commercially available product of the above hydroxyl group-terminated polyalkanedienediol, Epaul (manufactured by Idemitsu Petrochemical Co., Ltd., hydrogenated polyisoprene diol, molecular weight 1,860, average polymerization degree 26), PIP ( Idemitsu Petrochemical Co., Ltd., polyisoprene diol, molecular weight 2,200, average polymerization degree 34), polytail HA (Mitsubishi Chemical Corporation, hydrogenated polybutadiene diol, molecular weight 2,200, average polymerization degree 39), R-45HT (Idemitsu) And petrochemicals, polybutanediol, molecular weight 2,270, average polymerization degree 42), and the like. Examples of the tri- or higher functional polyol include glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, adamantanetriol, and more. Ethylene oxide or propylene oxide modified products are also included. Examples of the polyol having an aromatic ring include ethylene oxide or propylene oxide modified products of trifunctional or higher functional phenol compounds, and examples having a heterocyclic ring include Sake manufactured by Shikoku Kasei Kogyo Co., Ltd. These polyols can be used alone or in combination of two or more. Among these, when using a long-chain diol such as carbonate diol or a trifunctional polyol typified by trimethylolpropane, an amorphous semi-solid fluid material that does not become turbid when depolymerized. Is preferable, and the solubility in a solvent is further increased. Therefore, among the above polyols, it is particularly preferable to use a polycarbonate diol, trimethylolpropane and / or a derivative thereof or a polyol containing 50 mol% or more thereof.

In order to promote the depolymerization, a depolymerization catalyst can be used. 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 amount of these depolymerization catalysts used is usually 0.005 to 5 parts by mass, preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of the recovered polyester (a) and polyol (b). The range of is appropriate. Although not a depolymerization catalyst, water is a compound that promotes depolymerization. This is present as an impurity in, for example, recycled PET, and causes a decrease in molecular weight when PET is recycled. Therefore, it is usually necessary to remove it by a very energy-consuming process such as drying. is there. However, in the application of the present invention, it is not necessary. Rather, the use of recycled PET pellets once melted and kneaded in a pellet manufacturing machine such as an extruder with water added has a lower molecular weight of the recycled PET. Since the reaction temperature at the time of superposition | polymerization can be lowered | hung and the viscosity at the time of a fusion | melting is low, it is preferable at the point that reaction can be performed with high concentration.

The polyol (A-1) obtained by depolymerizing the recovered polyester (a) with the polyol (b) can be used as it is, and as described above, the polybasic acid or its anhydride By adding the product (c) before, simultaneously with, or after the depolymerization, the molecular weight can be increased and used as the carboxyl group-containing resin (A-2). As the reaction, a normal esterification reaction can be applied, but the methods described in Patent Documents 5 to 8 may be used.

As the polybasic acid or its anhydride (c), a conventionally known polybasic acid or its anhydride can be used. Specific examples include phthalic anhydride, isophthalic acid, terephthalic acid, tetrabromophthalic anhydride, methyl hymic anhydride, tetrachlorophthalic anhydride and other aromatic polycarboxylic acids and their acid anhydrides, hexahydrophthalic anhydride , Alicyclic carboxylic acids such as tetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and their anhydrides, maleic anhydride, fumaric acid, succinic anhydride, adipic acid, sebacine Examples thereof include aliphatic polyvalent carboxylic acids such as acid and azelaic acid and trifunctional or higher functional carboxylic acids such as acid anhydride, pyromellitic anhydride, trimellitic anhydride, and methylcyclohexenedicarboxylic acid anhydride.

The polyol (A-1) and the carboxyl group-containing resin (A-2) obtained by the above method further have a functional group capable of reacting with an acid or alcohol such as (meth) acrylic acid or an acrylic acid derivative and an ethylenic group. An ethylenically unsaturated group may be introduced in the compound (d) having a saturated group to obtain a (meth) acrylate photosensitive resin (A-3, A-4). This reaction is usually carried out at 80 to 120 ° C. for 2 to 10 hours in the presence or absence of an organic solvent, which will be described later, with the addition of an acid catalyst and a polymerization inhibitor. The synthesis can be carried out at normal pressure or under pressure, and the reaction temperature can be lowered under pressure. It should be noted that there is no problem in characteristics even if an unreacted hydroxyl group derived from the depolymerized product is present in the obtained photosensitive resin.

Examples of the functional group capable of reacting with the acid or alcohol include a carboxyl group, an isocyanate group, and a hydroxyl group.
The compound (d) having a carboxyl group and an ethylenically unsaturated group may be any unsaturated monocarboxylic acid having one carboxyl group and one or more ethylenically unsaturated groups in one molecule, and is particularly limited. Not. Specific examples include acrylic acid, dimer of acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, (meth) Examples include adducts of caprolactone with acrylic acid, and half ester compounds of saturated or unsaturated dibasic acid anhydrides and (meth) acrylates having one hydroxyl group in one molecule. Examples of (meth) acrylates having a hydroxyl group for producing a half ester compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, Examples include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and phenylglycidyl (meth) acrylate. 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, methylendomethylenetetrahydro And phthalic anhydride. Particularly preferred here are acrylic acid and methacrylic acid. These unsaturated monocarboxylic acids can be used alone or in admixture of two or more.

The compound (d) having an isocyanate group and an ethylenically unsaturated group is not particularly limited as long as it is an isocyanate compound having one isocyanate group and one or more ethylenically unsaturated groups in one molecule. Specific examples include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxyethoxyethyl isocyanate, bis (acryloxymethyl) ethyl isocyanate, and modified products thereof. Furthermore, a half urethane compound of a compound having one hydroxyl group and one or more ethylenically unsaturated groups in one molecule and a diisocyanate such as isophorone diisocyanate, toluylene diisocyanate, tetramethylxylene diisocyanate, hexamethylene diisocyanate, etc. Can be used. These isocyanate compounds having an ethylenically unsaturated group can be used alone or in combination of two or more.

The compound (d) having a hydroxyl group and an ethylenically unsaturated group is not particularly limited as long as it is a compound having one hydroxyl group and one or more ethylenically unsaturated groups in one molecule. Specific examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta ( Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate, and these can be used alone or in combination of two or more.

Further, the (meth) acrylate-based photosensitive resin (A-3) obtained as described above is further reacted with a polybasic acid or its anhydride (c) to obtain a carboxyl group-containing photosensitive resin (A-5). ). In this reaction, the amount of polybasic acid or anhydride (c) used is generally 0.1 to 1.0 mol, preferably 1 mol to 1 mol of the hydroxyl group of the photosensitive resin (A-3). The added amount is such that the acid value of the resulting carboxyl group-containing photocurable resin is about 20 to 200 mgKOH / g, more preferably 40 to 120 mgKOH / g.

The addition reaction of the polybasic acid or its anhydride (c) to the photosensitive resin (A-3) can be carried out in the presence or absence of an organic solvent as described below, and hydroquinone, methylhydroquinone, hydroquinone as necessary. The reaction is usually carried out at about 50 to 150 ° C. in the presence of a polymerization inhibitor such as monomethyl ether, catechol or pyrogallol. If necessary, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, a phosphorus compound such as triphenylphosphine, naphthenic acid, laurin Metal salts of organic acids such as lithium, chromium, zirconium, potassium, and sodium such as acid, stearic acid, oleic acid, and octoenoic acid may be added as a catalyst. These catalysts can be used alone or in admixture of two or more.

Next, the photopolymerization initiator (B) has an oxime ester photopolymerization initiator (B1) having a group represented by the following general formula (I) and a group represented by the following general formula (II). One or more selected from the group consisting of an α-aminoacetophenone photopolymerization initiator (B2) and / or an acylphosphine oxide photopolymerization initiator (B3) having a group represented by the following formula (III) It is preferable to use a photopolymerization initiator.

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

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

In the formula, R ⁹ is a hydrogen atom, halogen atom, alkyl group having 1 to 12 carbon atoms, cyclopentyl group, cyclohexyl group, phenyl group, benzyl group, benzoyl group, alkanoyl group having 2 to 12 carbon atoms, or 2 to 2 carbon atoms. 12 alkoxycarbonyl groups (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, and one or more oxygen atoms are placed in the middle of the alkyl chain. Which may have), or a phenoxycarbonyl group,
R ¹⁰ and R ¹² are each independently a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R ¹¹ is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (substituted with one or more hydroxyl groups). And may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having a carbon number). Optionally substituted with 1 to 6 alkyl groups or phenyl groups.

In the formula, R ¹³ , R ¹⁴ and R ¹⁹ each independently represents an alkyl group having 1 to 12 carbon atoms,
R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
M represents O, S or NH;
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 general formula (IV) and a compound represented by the formula (V) are more preferable. Examples of commercially available products include CGI-325 manufactured by Ciba Japan, Irgacure (registered trademark) OXE01, Irgacure OXE02, and N-1919 manufactured by ADEKA. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.

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

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

The blending amount of such a photopolymerization initiator (B) is 100 parts by weight of the carboxyl group-containing resin (A, C) (the total amount when two or more carboxyl group-containing resins are used, the same applies hereinafter). The range of 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass is appropriate. When the blending amount of the photopolymerization initiator (B) is less than 0.01 part by mass, the photocurability on copper is insufficient, and the coating film peels off or the coating properties such as chemical resistance deteriorate. Therefore, it is not preferable. On the other hand, if it exceeds 30 parts by mass, light absorption on the surface of the solder resist coating film of the photopolymerization initiator (B) becomes violent and the deep curability tends to decrease, which is not preferable.
In the case of the oxime ester photopolymerization initiator having a group represented by the formula (I), the blending amount is preferably 0.01 with respect to 100 parts by mass of the carboxyl group-containing resin (A, C). The range of -20 parts by mass, more preferably 0.01-5 parts by mass is desirable.

Other photopolymerization initiators, photoinitiator assistants and sensitizers that can be suitably used in the photosensitive resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenone compounds. , Xanthone compounds, and tertiary amine compounds.

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

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

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

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

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

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

The amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A, C). It is a ratio. When the amount of the tertiary amine compound is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained. On the other hand, when the amount exceeds 20 parts by mass, light absorption on the surface of the dry solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease.

In the photosensitive resin composition of the present invention, known and commonly used N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole and the like can be blended as chain transfer agents in order to improve sensitivity. Specific examples of chain transfer agents include, for example, 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 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2 -(Ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclo Ntanchioru, 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, 4,4'-dimercaptodiphenyl sulfide, 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 tet Poly (mercaptoacetate) polyhydric alcohols such as kiss (mercaptoacetate) and dipentaerythritol hexakis (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), penta Poly (3-mercaptopropionate) polyhydric alcohols such as erythritol tetrakis (3-mercaptopropionate) and dipentaerythritol hexakis (3-mercaptopropionate) 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, And poly (mercaptobutyrate) s such as 5H) -trione and pentaerythritol tetrakis (3-mertapbutyrate).

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 which is a chain transfer agent that does not impair the developability of the photosensitive 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 may be in a range of 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin (A, C). preferable. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

Further, the photosensitive composition of the present invention is added with a conventionally known carboxyl group-containing photosensitive resin (C) for the purpose of imparting alkali developability and for the purpose of improving the photosensitivity, heat resistance and electrical characteristics. Also good. In particular, the ethylenically unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof. As specific examples of the carboxyl group-containing photosensitive resin (C), resins listed below (any of oligomers and polymers) may be 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. A carboxyl group-containing photosensitive resin obtained by reacting a compound having one or more ethylenically unsaturated groups and one epoxy group in a molecule.
(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, polyethers Of 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 During the synthesis, a compound having one hydroxyl group and one or more (meth) acryl groups in a molecule such as hydroxyalkyl (meth) acrylate is added. (Meth) acrylated carboxyl group-containing photosensitive urethane resin.
(3) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.
(4) During the synthesis of the resin of (3) above, a compound having one hydroxyl group and one or more (meth) acrylic groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and terminal (meth) acrylated Carboxyl group-containing photosensitive urethane resin.
(5) During the synthesis of the resin of the above (2) or (3), one isocyanate group and one or more (meth) acryl groups are introduced into the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. A carboxyl group-containing photosensitive urethane resin obtained by adding a compound having a terminal (meth) acrylate.
(6) Carboxyl group-containing photosensitivity in which (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin as described later and a dibasic acid anhydride is added to the hydroxyl group present in the side chain. Resin.
(7) A polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group. Added carboxyl group-containing photosensitive resin.
(8) A cyclic ether such as ethylene oxide or a cyclic carbonate such as propylene carbonate is added to a polyfunctional phenol compound such as novolak, and the resulting hydroxyl group is partially esterified with (meth) acrylic acid, and a polybasic acid is added to the remaining hydroxyl group. A carboxyl group-containing photosensitive resin obtained by reacting an anhydride.
(9) A carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth) acrylic groups in one molecule to the resins (1) to (8).

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

The weight-average molecular weight of the carboxyl group-containing photosensitive resin (C) varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. preferable. When the weight average molecular weight is less than 2,000, tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, film thickness may be reduced during development, and resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.

The amount of such a carboxyl group-containing photosensitive resin (C) is 0 to 50% by mass, preferably 10 to 40% by mass in the total composition. When the amount of the carboxyl group-containing photosensitive resin (C) is more than the above range, the amount of the desired recycled polyester is extremely small, which is not preferable.
These carboxyl group-containing photosensitive resins (C) are not limited to those listed above, and can be used singly or in combination. Further, for the purpose of improving alkali developability, other conventionally known carboxyl group-containing resins may be used.

In the photosensitive resin composition of the present invention, a thermosetting resin can be blended to impart heat resistance. Examples of thermosetting components used in the present invention include amine resins such as melamine resins and benzoguanamine resins, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives, bismaleimides, and oxazine compounds. , Known thermosetting resins such as oxazoline compounds and carbodiimide resins can be used. Particularly preferred is a thermosetting component (D) having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.

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

As the polyfunctional epoxy compound (D-1), for example, jER828, jER834, jER1001, jER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, manufactured by Tohto Kasei Co., Ltd. Epototo YD-011, YD-013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Japan's Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo A . E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., Dow Chemical D. E. R. 542, Araldide 8011 manufactured by Ciba Japan, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd. E. R. 711, A.I. E. R. 714 (both trade names) brominated epoxy resin; jER152, jER154 manufactured by Japan Epoxy Resin, D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd. Araldide XPY307, Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo Co., Ltd. A. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Japan Epoxy Resin, Epotote YDF-170, YDF-175, YDF-175 manufactured by Toto Kasei 2004, Bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Japan Co., Ltd. (all trade names); Hydrogenated bisphenol such as Epototo ST-2004, ST-2007, ST-3000 (trade names) manufactured by Tohto Kasei Co., Ltd. Type A epoxy resin: jER604 manufactured by Japan Epoxy Resin, Epototo YH-434 manufactured by Tohto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Japan, Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. ) Glycidylamine type epoxy resin; Hydantoin type epoxy resin such as Araldide CY-350 (trade name) manufactured by Bread; Celoxide 2021 manufactured by Daicel Chemical Industries, and alicyclic epoxy such as Araldide CY175 and CY179 manufactured by Ciba Japan Resin; YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Japan Epoxy Resin YL-6056, YX-4000, YL-6121 (all trade names), etc. Bisphenol S type epoxy resins such as xylenol type or biphenol type epoxy resins or mixtures thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by DIC Co., Ltd .; Bisphenol A novolac type epoxy resin such as Epoxy Resin's jER157S (trade name); Tetraphenylolethane type such as Japan Epoxy Resin's jERYL-931, Ciba Japan's Araldide 163, etc. (all trade names) Epoxy resin; Aral made by Ciba Japan Heterocyclic epoxy resins such as id PT810, TEPIC manufactured by Nissan Chemical Industries, Ltd. (all trade names); diglycidyl phthalate resins such as Bremer DGT manufactured by NOF Corporation; tetraglycidyl xyleno such as ZX-1063 manufactured by Tohto Kasei Co., Ltd. Irethane resin; Naphthalene group-containing epoxy resins such as ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, and EXA-4700 manufactured by DIC; HP-7200 and HP-7200H manufactured by DIC Epoxy resins having a dicyclopentadiene skeleton such as CP-50S and CP-50M glycidyl methacrylate copolymer epoxy resins manufactured by Nippon Oil &Fats; Copolymer epoxy resins of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene Rubber derivatives (eg Iseru Chemical Co. PB-3600, etc.), CTBN modified epoxy resin (e.g., Tohto Kasei Co. YR-102, YR-450, etc.) and others as mentioned, is not limited thereto. These epoxy resins can be used alone or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.

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

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

The amount of the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is preferably 0 with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A, C). A suitable range is from 6 to 2.5 equivalents, more preferably from 0.8 to 2.0 equivalents. When the blending amount of the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is less than 0.6, carboxyl groups remain in the solder resist film, resulting in heat resistance, alkali resistance, electricity This is not preferable because the insulating property is lowered. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.

Also, a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule can be added as a thermosetting component. Such a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound, or two or more in one molecule. And a compound having a blocked isocyanate group, that is, a blocked isocyanate compound.

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

The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.
As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As this isocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.

Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid Alcohol-based blocking agents such as chill and ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetoaldoxime, acetoxime, methylethyl 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 done.

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

The compounding amount of the compound having two or more isocyanate groups or blocked isocyanate groups in one molecule as described above is 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A, C), More preferably, a ratio of 2 to 70 parts by mass is appropriate. When the amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 mass parts, storage stability falls and it is not preferable.

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

Examples of these commercially available products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx -290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw -750LM (above, manufactured by Sanwa Chemical Co., Ltd.). The said thermosetting component can be used individually or in combination of 2 or more types.

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

The blending amount of these thermosetting catalysts is sufficient in the usual quantitative ratio, and is preferably 0.1 to 100 parts by weight with respect to 100 parts by mass of the carboxyl group-containing resin (A, C) or thermosetting component (D), for example. 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.

In the photosensitive resin composition of the present invention, an adhesion promoter can be used in order to improve adhesion between layers or adhesion between the photosensitive resin layer and the substrate. Specific examples include, for example, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2- Thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent, etc. is there.

In the photosensitive resin composition of the present invention, the above-described photosensitive resins (A-3 to A-7) and carboxyl group-containing photosensitive resins (C) can be used. The compound (F) having an ethylenically unsaturated group can be used. The role of these photosensitive compounds is that they are photocured by irradiation with active energy rays to obtain a carboxyl group-containing resin (A-2) or photosensitive resin (A-3 to A-7) obtained from the recovered polyester, and the above-mentioned The carboxyl group-containing photosensitive resin (C) is insolubilized or assists insolubilization in an alkaline aqueous solution. Examples of such compounds include glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, and the like. Polyhydric acrylates such as polyhydric alcohols or their ethylene oxide adducts or propylene oxide adducts; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycy Ethers, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or the like each methacrylates corresponding to the acrylates.

Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, 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 (F) 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 carboxyl group-containing resin (A, C). Preferably, a ratio of 1 to 70 parts by mass is appropriate. 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, which is not preferable. On the other hand, when the amount exceeds 100 parts by mass, the solubility in an alkaline aqueous solution is lowered, and the coating film becomes brittle.

The photosensitive resin composition of the present invention can contain a colorant (E). As the colorant, conventionally known colorants such as red (E-1), blue (E-2), green (E-3), yellow (E-4) can be used, and pigments, dyes, Any of 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.

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

Blue colorant (E-2):
Blue colorants include phthalocyanine and anthraquinone, and pigments include compounds classified as Pigment, specifically: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60.
The dye systems include Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

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

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

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

The mixing ratio of the colorant (E) as described above is not particularly limited, but is preferably 0 to 10 parts by mass, particularly preferably 0. 0 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A, C). A ratio of 1 to 5 parts by mass is sufficient.

Generally, in many polymer materials, once oxidation starts, oxidative degradation successively occurs one after another, resulting in a decrease in the function of the polymer material. Therefore, the photosensitive resin composition of the present invention prevents oxidation. (1) A radical scavenger that invalidates the generated radicals and / or (2) a peroxide decomposer that decomposes the generated peroxide into harmless substances and prevents the generation of new radicals. An antioxidant can be added.

Specific examples of the antioxidant that acts as a radical scavenger include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p- Cresol, 2,2-methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3, 5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′-di-t-butyl-4) Phenolic compounds such as -hydroxybenzyl) -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, and the like amine compounds such as phenothiazine.

The radical scavenger may be commercially available, for example, ADK STAB 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 (above, manufactured by Asahi Denka Co., Ltd., trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above, TINUVIN 5100 Japan) Product name).

Specific 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 ′. -Sulfur compounds such as thiodipropionate.

The peroxide decomposing agent may be a commercially available one, for example, ADK STAB TPP (trade name, manufactured by Asahi Denka Co., Ltd.), Mark AO-412S (trade name, manufactured by Adeka Argus Chemical Co., Ltd.), Sumilizer TPS (Sumitomo Chemical) Company name, product name).
Said antioxidant can be used individually by 1 type or in combination of 2 or more types.

In general, since the polymer material absorbs light and thereby decomposes and deteriorates, the photosensitive resin composition of the present invention includes, in addition to the above antioxidant, in order to take a countermeasure against stabilization against ultraviolet rays. UV absorbers can be used.

Examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like. Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone. Is mentioned. Specific examples of benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t. -Butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate. Specific examples of the benzotriazole derivative include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole and the like. Specific examples of the triazine derivative include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.

Ultraviolet absorbers may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (above, manufactured by Ciba Japan, trade name) and the like.
Said ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types, By using together with the said antioxidant, the molding obtained from the photosensitive resin composition of this invention can be stabilized. I can plan.

In the photosensitive resin composition of the present invention, a filler can be blended as necessary in order to increase the physical strength of the coating film. As such a filler, known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica and talc are preferably used. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can be used as extender pigment fillers. The blending amount of the filler is preferably 75% by weight or less, more preferably 0.1 to 60% by weight of the total amount of the composition. If the blending amount of the filler exceeds 75% by weight of the total amount of the composition, the viscosity of the insulating composition becomes high, the coating and moldability are lowered, and the cured product becomes brittle.

Furthermore, the photosensitive resin composition of the present invention uses an organic solvent for the synthesis of the carboxyl group-containing resin (B) and the preparation of the composition, or for adjusting the viscosity for application to a substrate or a carrier film. be able to.
Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether is petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.

The photosensitive resin composition of the present invention may further include, as necessary, known and commonly used thermal polymerization inhibitors, known and commonly used thickeners such as finely divided silica, organic bentonite, and montmorillonite, silicones, fluorines, and polymers. The known antifoaming agent and / or leveling agent, imidazole-based, thiazole-based, triazole-based silane coupling agents, antirust agents, and the like can be blended.

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

The photosensitive resin composition of the present invention is adjusted to a viscosity suitable for the coating method with, for example, the organic solvent, and on the substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. and performing volatile drying (temporary drying) at a temperature of about 60 to 100 ° C. Moreover, a resin insulation layer can be formed by apply | coating the said composition on a carrier film, and making it dry and winding up as a film together on a base material. Thereafter, by a contact method (or non-contact method), exposure is selectively performed with an active energy ray through a photomask having a pattern formed thereon or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3). A resist pattern is formed by development with a 3 wt% sodium carbonate aqueous solution). Further, in the case of the composition containing the thermosetting component (D), the carboxyl group of the carboxyl group-containing resin (A, C) is obtained by heating and curing at a temperature of about 140 to 180 ° C., for example. And a thermosetting component (D) having two or more cyclic ether groups and / or cyclic thioether groups in the molecule react with each other, such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. A cured coating film having excellent characteristics can be formed. Even when the thermosetting component (D) is not contained, the heat treatment causes the ethylenically unsaturated bond of the photocurable component remaining in an unreacted state at the time of exposure to undergo thermal radical polymerization, resulting in coating film characteristics. Therefore, heat treatment (thermosetting) may be performed depending on the purpose and application.

Examples of the base material include printed circuit boards and flexible printed circuit boards that are pre-formed with a circuit, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin. , Glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, copper-clad laminates of all grades (FR-4 etc.) using polyimide, polyethylene, PPO, cyanate ester, etc., polyimide film, PET A film, a glass substrate, a ceramic substrate, a wafer plate, or the like can be used.

Volatile drying performed after applying the photosensitive resin composition of the present invention is performed in a dryer using a hot air circulation drying oven, an IR oven, a hot plate, a convection oven or the like (equipped with a heat source of an air heating method using steam). It is possible to use a method in which hot air is brought into countercurrent contact and a method in which a hot air is blown onto a support.

After applying the photosensitive resin composition of the present invention and evaporating and drying as follows, the obtained coating film is exposed (irradiated with active energy rays). In the coating film, the exposed portion (the portion irradiated by the active energy ray) is cured.
As the exposure apparatus used for the active energy ray irradiation, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer), an exposure apparatus equipped with a metal halide lamp, and an (ultra) high pressure mercury lamp. , 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, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. The exposure amount varies depending on the film thickness and the like, but can be generally in the range of 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 maximum wavelength of 350 to 410 nm. .

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

The photosensitive resin composition of the present invention is in the form of a dry film having a solder resist layer formed by previously applying and drying a solder resist on a film of polyethylene terephthalate or the like, in addition to the method of directly applying to the substrate in a liquid state. It can also be used. The case where the photosensitive resin composition of this invention is used as a dry film is shown below.

The dry film has a structure in which a carrier film, a solder resist layer, and a peelable cover film used as necessary are laminated in this order. The solder resist layer is a layer obtained by applying and drying an alkali-developable photosensitive resin composition on a carrier film or a cover film. After forming a solder resist layer on the carrier film, a cover film is laminated thereon, or a solder resist layer is formed on the cover film, and this laminate is laminated on the carrier film to obtain a dry film.

As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm is used.
The solder resist layer is formed by uniformly applying an alkali-developable photosensitive resin composition to a carrier film or cover film with a thickness of 10 to 150 μm using a blade coater, lip coater, comma coater, film coater, and the like, and then drying. .
As the cover film, a polyethylene film, a polypropylene film, or the like can be used, but a cover film having a smaller adhesive force than the solder resist layer is preferable.

To produce a protective film (permanent protective film) on a printed wiring board using a dry film, peel off the cover film, layer the solder resist layer and the substrate on which the circuit is formed, and bond them together using a laminator, etc. A solder resist layer is formed on the formed substrate. If the formed solder resist layer is exposed, developed, and heat cured in the same manner as described above, a cured coating film can be formed. The carrier film may be peeled off either before exposure or after exposure.

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

Example of polyol synthesis After charging 192 parts of recycled PET flakes with an IV value of 0.6 to 0.7 into a 500 ml four-necked round bottom separable lasco equipped with a stirrer, nitrogen inlet tube, and cooling tube, the flask was filled with a nitrogen atmosphere. And immersed in a salt bath heated to 300 ° C. When PET was 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 was previously heated to 240 ° C., 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. Hereinafter, this polyol resin is referred to as PET-TMP resin (a).

Synthesis Example of Carboxyl Group-Containing Resin A 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen introduction tube, and a cooling tube, 163 parts of the PET-TMP resin (a) obtained in the above synthesis example, and tetrahydrophthalic anhydride 60.8 parts was charged and the atmosphere in the flask was changed to a nitrogen atmosphere, and then immersed in an oil bath heated to 125 ° C. ± 5 ° C. The reaction was allowed to stir for 3 hours. The reaction product thus obtained had an acid value of 103 mgKOH / g, was yellow transparent at room temperature, and was solid. 35 parts of carbitol acetate was added to 100 parts of the reaction product and stirred to obtain a carboxyl group-containing resin solution having a nonvolatile content of 65%. Hereinafter, this is referred to as A-1 varnish.

Example of synthesis of carboxyl group-containing photosensitive resin Charged 192 parts of recycled PET flakes with an IV value of 0.6 to 0.7 in a 500 ml four-necked round bottom separable lasco equipped with a stirrer, nitrogen inlet tube, and cooling tube. After making the nitrogen atmosphere, it was immersed in a salt bath heated to 300 ° C. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Subsequently, 134 parts of trimethylolpropane previously heated to 130 ° C. and dissolved were 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. Next, the salt bath was replaced with an oil bath that was previously heated to 240 ° C., and the temperature in the flask was kept at 220 ° C. ± 10 ° C. for 5 hours. The reaction product was transparent yellow and soft tones at room temperature. To 100 parts of the obtained reaction product, 37 parts of toluene and 74 parts of methyl isobutyl ketone (hereinafter abbreviated as MIBK) were introduced and mixed. Next, 43 parts of acrylic acid, 1.94 parts of paratoluenesulfonic acid, and 0.26 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 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. After distilling off, 1.07 parts of triphenylphosphine, 0.07 part of paramethoxyphenol and 70 parts of carbitol acetate were added and dissolved uniformly, and then 54.3 parts of tetrahydrophthalic anhydride was added, The mixture was reacted for a time to obtain a carboxyl group-containing photosensitive resin solution having a solid content acid value of 107 mgKOH / g and a double bond equivalent (g weight of resin per mol of unsaturated groups) of 260. Hereinafter, this carboxyl group-containing photosensitive resin solution is referred to as A-2 varnish.

Synthesis example 1 of photosensitive compound
Charged 192 parts of recycled PET flakes with an IV value of 0.6 to 0.7 to a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. It was immersed in a heated salt bath. 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. Next, the salt bath was replaced with an oil bath that was previously heated to 240 ° C., 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 MIBK 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 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 referred to as A-3 resin.

Synthesis example 2 of photosensitive compound
A 500 ml four-necked flask equipped with a stirrer, air inlet tube and cooling tube is charged with 66.6 parts of isophorone diisocyanate and 80 parts of carbitol acetate, and 37.6 parts of 2-hydroxyethyl acrylate and dibutyltin laurate. A carbitol acetate solution in which 0.05 part, 0.03 part of p-methoxyphenol and 20 parts of carbitol acetate were mixed was added dropwise at 35 ° C. over 2 hours, and reacted at 80 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and a carbitol acetate solution containing 33 parts of the PET-TMP resin (a), 0.1 part of dibutyltin laurate, and 50 parts of carbitol acetate was slowly poured. The mixture was reacted at 0 ° C. for 3 hours to obtain an ethylene terephthalate type urethane acrylate having a nonvolatile content of 80%. This is called A-4 varnish.

Examples 1 to 11 and Comparative Examples 1 and 2
Using the resin solutions of the above synthesis examples, blended in the proportions (parts by mass) shown in Table 1 together with various components shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and used for solder resist A photocurable thermosetting resin composition was prepared. Here, it was 15 micrometers or less when the dispersion degree of the obtained photocurable thermosetting resin composition was evaluated by the particle size measurement by the grindometer by Eriksen.

Performance evaluation:
<Recycled PET content>
In the photocurable thermosetting resin compositions of the examples and comparative examples, the content of the recycled PET resin relative to the total organic matter in the cured coating film was calculated.

<Optimum exposure amount>
The photocurable thermosetting resin compositions of the examples and comparative examples were coated on the entire surface by screen printing after the circuit pattern substrate having a copper thickness of 35 μm was buffed, washed with water, dried, and heated at 80 ° C. It was dried for 60 minutes in a circulation drying oven. 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 at the second time was 7 steps, the optimum exposure amount was set.

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

<Dry touch dryness>
Each surface of the photocurable thermosetting resin composition shown in Table 1 was applied onto a patterned copper foil substrate by screen printing, dried in a hot air circulating drying oven at 80 ° C. for 30 minutes, and allowed to cool to room temperature. . 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>
A circuit pattern substrate having a line / space of 300/300 μm and a copper thickness of 35 μm was applied to the photocurable / thermosetting resin compositions of Examples and Comparative Examples by buffing, washing with water, drying and then applying by screen printing. And dried for 30 minutes in a hot air circulation drying oven at 80 ° C. After drying, exposure was performed using an exposure apparatus equipped with a high-pressure mercury lamp. For the exposure pattern, a negative was used to draw a 20/30/40/50/60/70/80/90/100 μm line in the space. The active energy ray was irradiated so that the exposure amount became the optimal exposure amount of the photosensitive resin composition. After the exposure, a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa, and cured at 150 ° C. for 60 minutes to obtain a cured coating film. It determined using the optical microscope which adjusted the minimum residual line of the cured coating film of the obtained photosensitive resin composition for solder resists 200 times, and made this resolution.

Characteristic test:
The compositions of the above Examples and Comparative Examples are applied onto the patterned copper foil substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. This substrate is exposed to a solder resist pattern at an optimal exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and developed with a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. for 60 seconds under a spray pressure of 0.2 MPa. And a resist pattern was obtained. 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 commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 0.5 μm and gold 0.03 μm, and the tape peeling causes the presence or absence of resist layer peeling or plating penetration. 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 a 10 wt% NaOH aqueous solution at room temperature for 30 minutes, and soaking, dissolution of the coating film, and peeling by tape beer were confirmed. The judgment criteria are as follows.
○: No soaking, melting or peeling.
Δ: Slight penetration, dissolution or peeling is confirmed.
X: Significant infiltration, dissolution or peeling.

<Dry film production>
Each of the photosensitive resin compositions for solder resists of Example 1 and Comparative Example 1 was appropriately diluted with methyl ethyl ketone, and then, using an applicator, a PET film (Toray FB-50: manufactured by Toray Industries, Inc.) so that the film thickness after drying was 30 μm. 16 μm) and dried at 40 to 100 ° C. to obtain a dry film.

<Board fabrication>
After the circuit-formed substrate is buffed, the dry film produced by the above method is pressurized using a vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho): 0.8 MPa, 70 ° C., 1 minute, degree of vacuum The substrate (unexposed substrate) having an unexposed solder resist layer was obtained by heat lamination under the condition of 133.3 Pa. Each of the obtained substrates was tested in the same manner as in the above evaluation method for optimum exposure, developability, resolution, solder heat resistance, gold plating resistance, and alkali resistance.
The evaluation results are shown in Table 2.

As is clear from the results shown in Table 2 above, a polyol obtained by depolymerizing PET with a polyol (trimethylolpropane), a carboxyl group-containing resin obtained by modifying the polyol with a polybasic acid anhydride, or An alkali-developable composition using a photosensitive urethane resin (urethane acrylate) obtained by using the above-described polyol as a polyol component in the synthesis of a photosensitive resin into which a photosensitive group has been introduced or a urethane resin has heat resistance, Excellent electroless gold plating, alkali resistance, and developability. Furthermore, by recycling from waste plastics, the load on the environment can be reduced, and as an alkali developable photosensitive resin composition, especially as a solder resist It was found useful.

The photosensitive resin composition of the present invention or its dry film can be advantageously applied to the formation of a cured film such as a solder resist of a printed wiring board or a flexible printed wiring board.

Claims

(A) An alkali-developable photosensitive resin composition comprising a recovered polyester as a raw material and (B) a photopolymerization initiator.
The photosensitive resin composition according to claim 1, wherein the resin (A) is a polyol.
The photosensitive resin composition according to claim 1, wherein the resin (A) is a carboxyl group-containing resin.
The photosensitive resin composition according to claim 1, wherein the resin (A) is a photosensitive resin having an ethylenically unsaturated group.
The resin (A) is a carboxyl group-containing resin obtained by (a) depolymerizing the recovered polyester with (b) polyol, and (c) reacting a polybasic acid or anhydride thereof. The photosensitive resin composition according to claim 1.
The photosensitive resin composition according to claim 1, further comprising a carboxyl group-containing photosensitive resin (C) other than the resin (A).
The photosensitive resin composition according to claim 1, which is a photocurable thermosetting resin composition further containing a thermosetting component (D).
The photosensitive resin composition according to claim 1, which is further for a solder resist containing a colorant (E).
A photocurable dry film obtained by applying and drying the photosensitive resin composition according to any one of claims 1 to 8 on a film.
A photocurable dry film obtained by applying and drying the photosensitive resin composition according to any one of claims 1 to 8 or the photosensitive resin composition on a film is photocured. The cured product obtained.
A photosensitive resin composition according to any one of claims 1 to 8 or a photocurable dry film obtained by applying and drying the photosensitive resin composition on a film is light-patterned. A cured product obtained by curing.
A photosensitive resin composition according to any one of claims 1 to 8 or a photocurable dry film obtained by applying and drying the photosensitive resin composition on a film is light-patterned. A printed wiring board having a cured film obtained by curing after curing.