Photosensitive composition, multilayer structure, cured object, and electronic component

Abstract

[Problem] To provide a photosensitive composition having excellent resolution and heat resistance. [Solution] This photosensitive composition contains a (A) carboxylic acid-containing resin, a (B) photoinitiator, a (C) photosensitive monomer, and a (D) coloring agent. The (A) carboxylic acid-containing resin contains at least one resin selected from (A1) carboxylic acid-containing photosensitive resins in which a phenolic compound is used as a starting material, (A2) carboxylic acid-containing photosensitive resins having a urethane skeleton, (A3) carboxylic acid-containing copolymerized photosensitive resins, and (A4) carboxylic acid-containing photosensitive resins in which an epoxy compound is used as a starting material. The (D) coloring agent contains a quinophthalone compound represented by formula (1).

Description

Photosensitive composition, laminated structure, cured product, and electronic component

[0001] The present invention relates to a photosensitive composition. The present invention also relates to a laminate structure, a cured product, and an electronic component using the photosensitive composition.

[0002] In recent years, there has been an increasing demand for electronic devices such as mobile phones and personal computers to be more compact through higher density packaging and to process large volumes of information at high speed. Accordingly, solder resists used in electronic components such as printed wiring boards are also required to have higher performance in terms of various properties such as resolution and heat resistance.

[0003] Photosensitive compositions used in solder resists and the like typically contain a colorant, and it is common to use a mixture of a blue colorant and a yellow colorant instead of the conventional green colorant (see, for example, Patent Document 1). Furthermore, taking into consideration resolution, deep curing, and the like, it is preferable to use a colorant that has low absorption in the exposure wavelength region (near 365 nm). Quinophthalone-based yellow colorants, for example, are known as such colorants. Furthermore, from the viewpoint of heat resistance, anthraquinone-based yellow colorants, such as Pigment Yellow 147, are known.

[0004] Furthermore, as photosensitive compositions used for solder resists and the like, compositions containing various carboxylic acid-containing resins have been proposed in order to improve not only the heat resistance described above but also PCT resistance, toughness, and various other durability properties (for example, Patent Document 2, etc.).

[0005] Patent Document 1: JP 2000-7974 A Patent Document 2: Japanese Patent No. 3964326 A

[0006] However, there is still room for improvement in resolution and heat resistance in photosensitive compositions containing colorants. Therefore, an object of the present invention is to provide a photosensitive composition having excellent resolution and heat resistance. Another object of the present invention is to provide a laminate structure, a cured product, and an electronic component using the photosensitive composition.

[0007] As a result of extensive investigations, the present inventors have discovered that a photosensitive composition having excellent resolution and heat resistance can be obtained by using a quinophthalone compound having a specific amide structure as a colorant and a specific resin as a carboxylic acid-containing resin. The present invention is based on this discovery. Specifically, the gist of the present invention is as follows.

[0008] [1] A photosensitive composition comprising: (A) a carboxylic acid-containing resin; (B) a photopolymerization initiator; (C) a photosensitive monomer; and (D) a colorant, wherein the (A) carboxylic acid-containing resin comprises at least one resin selected from the group consisting of (A1) a carboxylic acid-containing photosensitive resin made from a phenol compound as a starting material, (A2) a carboxylic acid-containing photosensitive resin having a urethane skeleton, (A3) a carboxylic acid-containing copolymer photosensitive resin, and (A4) a carboxylic acid-containing photosensitive resin made from an epoxy compound as a starting material, and the (D) colorant is a compound represented by the following formula (1): (In formula (1), R １ and R ２ are each independently —OH, —OR ａ , -NR ｂ R ｃ , —C(═O)NR ｂ R ｃ , halogen atoms, —CN, —NO ２ , -COOH, -C(=O)OR ｄ , -OC(=O)R ｄ , -COOM ａ , -SO ３ H, -S(=O) ２ OR ｄ , -O-S(=O)2R ｄ , -SO ３ M ａ a hydrocarbon group having 1 to 30 carbon atoms, a group represented by formula (2) and a group represented by formula (3), wherein the hydrocarbon group having 1 to 30 carbon atoms may be substituted; R ３ are each independently —OH, —OR ａ , -NR ｂ R ｃ , —C(═O)NR ｂ R ｃ , halogen atoms, —CN, —NO ２, -COOH, -C(=O)OR ｄ , -OC(=O)R ｄ , -COOM ａ , -SO ３ H, -S(=O) ２ OR ｄ , —O—S(═O) ２ R ｄ , -SO ３ M ａ and a hydrocarbon group having 1 to 30 carbon atoms, which may be substituted; m is an integer of 0 to 5; n is an integer of 0 to 5; p is an integer of 0 to 4; R ａ is an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the aralkyl group may be substituted; R ｂ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the aralkyl group may be substituted; R ｃ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the aralkyl group may be substituted; R ｄ represents an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the aralkyl group may be substituted; M ａ is sodium or potassium, with the proviso that m+n is an integer of 1 or more, and formula (1) has at least one group selected from a group represented by the following formula (2) and a group represented by the following formula (3), In formula (2) and formula (3), X １ , X ２ , X ３ and X ４ are each independently —OH, —OX ａ , -NX ｂ X ｃ , -C(=O)NX ｂ X ｃ , halogen atoms, —CN, —NO ２, -COOH, -C(=O)OX ｄ , -OC(=O)X ｄ , -COOM ｂ , -SO ３ H, -S(=O) ２ OX ｄ , —O—S(═O) ２ X ｄ , -SO ３ M ｂ and a hydrocarbon group having 1 to 30 carbon atoms, wherein adjacent groups may be bonded to each other to form a carbocyclic or heterocyclic ring, and the hydrocarbon group having 1 to 30 carbon atoms may be substituted; L １ and L ２ are each independently a linking group selected from a single bond, —O—, —C(═O)O—, —S(═O)2O— and —NH—C(═O)—, q is an integer of 0 to 6, r is an integer of 0 to 3, s is an integer of 0 to 5, t is an integer of 0 to 4, and X ａ represents an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the aralkyl group may be substituted; X ｂ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group and the aralkyl group may be substituted; X ｃ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group and the aralkyl group may be substituted; X ｄ represents an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the aralkyl group may be substituted; M ｂis sodium or potassium.) [2] The photosensitive composition according to [1], wherein the content of the quinophthalone compound is 0.1 to 5 parts by mass, calculated as solid content, per 100 parts by mass of the carboxylic acid-containing resin (A). [3] The photosensitive composition according to [1] or [2], wherein the formula (1) has at least two groups selected from the group represented by the formula (2) and the group represented by the formula (3). [4] The photosensitive composition according to [1], wherein the formula (1) has at least two groups selected from the group represented by the formula (2) and the group represented by the formula (3). １ and R is a group selected from the group represented by the formula (2) and the group represented by the formula (3). ２ [5] A laminate structure comprising a first film and a resin layer provided on the first film, wherein the resin layer is made of the photosensitive composition according to any one of [1] to [4]. [6] A cured product of the photosensitive composition according to any one of [1] to [4] or the resin layer of the laminate structure according to [5]. [7] An electronic component having the cured product according to [6].

[0009] According to the present invention, a photosensitive composition having excellent resolution and heat resistance can be realized by using a colorant made of a quinophthalone compound having a specific amide structure in combination with a specific carboxylic acid-containing resin.

[0010] 1 is an FT-IR chart of quinophthalone compound 1 of an example. 2 is an FT-IR chart of quinophthalone compound 2 of an example. 3 is an FT-IR chart of quinophthalone compound 3 of an example. 4 is a TG / DTA chart of quinophthalone compound 1 and compound 4 of an example. 5 is a TG / DTA chart of quinophthalone compound 1 and compound 5 of an example. 6 is a chart of ultraviolet-visible absorption spectra of solutions of quinophthalone compound 1, compound 4, and compound 5 of an example.

[0011] <Photosensitive composition> The photosensitive composition according to the present invention contains, as essential components, (A) a carboxylic acid-containing photosensitive resin, (B) a photopolymerization initiator, (C) a photosensitive monomer, and (D) a colorant. Each component constituting the photosensitive resin according to the present invention will be described below.

[0012] (A) Carboxylic Acid-Containing Resin The photosensitive composition according to the present invention contains, as the carboxylic acid-containing resin (A), at least one resin selected from (A1) a carboxylic acid-containing photosensitive resin made from a phenolic compound as a starting material, (A2) a carboxylic acid-containing photosensitive resin having a urethane skeleton, (A3) a carboxylic acid-containing copolymeric photosensitive resin, and (A4) a carboxylic acid-containing photosensitive resin made from an epoxy compound as a starting material. By using these carboxylic acid-containing photosensitive resins having a specific structure in combination with a colorant comprising a quinophthalone compound having a specific amide structure, which will be described later, a photosensitive composition having excellent resolution and heat resistance can be realized.

[0013] The carboxylic acid-containing photosensitive resin (A1) made from a phenolic compound as a starting material is different from the resin (A4) made from an epoxy compound as a starting material, and refers to a resin having a photosensitive group and a carboxyl group made from a phenolic compound as a starting material. The photosensitive group is a functional group having an ethylenically unsaturated double bond, such as a (meth)acryloyl group or a vinyl group, and is preferably a (meth)acryloyl group. In this specification, the term (meth)acryloyl group collectively refers to an acryloyl group, a methacryloyl group, and mixtures thereof, and the same applies to other similar expressions. Examples of the carboxylic acid-containing photosensitive resin (A1) made from a phenolic compound as a starting material include the following (A1-1) and (A1-2). (A1-1) A carboxylic acid-containing photosensitive resin obtained by reacting a compound having multiple phenolic hydroxyl groups per molecule with an alkylene oxide such as ethylene oxide or propylene oxide, reacting the reaction product obtained with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride. (A1-2) A carboxylic acid-containing photosensitive resin obtained by reacting a compound having multiple phenolic hydroxyl groups per molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, reacting the reaction product obtained with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.

[0014] In the present invention, by using, as the carboxylic acid-containing resin, a carboxylic acid-containing photosensitive resin made from the above-mentioned phenolic compound (A1) as a starting material and a colorant consisting of a quinophthalone compound having a specific amide structure (described below), in combination, the resolution of both thick and thin portions of the coating film of the photosensitive composition can be improved. That is, with conventional photosensitive compositions containing colorants, when a coating film has thick and thin portions, reducing the exposure dose to improve the resolution of the thin portion reduces the resolution of the thick portion, resulting in undercuts, etc. On the other hand, increasing the exposure dose to improve the resolution of the thick portion results in halation, reducing the resolution of the thin portion. In the present invention, by using, as the carboxylic acid-containing resin, a carboxylic acid-containing photosensitive resin made from the above-mentioned phenolic compound as a starting material, the resolution of both thick and thin portions can be improved. This is thought to be because, while DI exposure machines commonly used for exposure irradiate light of 365 nm and 405 nm in a ratio of approximately 1:1, the quinophthalone compound with a specific structure has a low absorbance of approximately 0.2 at a light wavelength of around 365 nm, so exposure is not inhibited, and its absorbance at a light wavelength of around 430 nm is relatively low at approximately 0.95, so long wavelength light can also be used effectively, thereby improving the balance between surface curability and deep curability.

[0015] In addition, in the present invention, the photosensitive composition containing (A1) a carboxylic acid-containing photosensitive resin produced from a phenol compound as a starting material has improved resolution compared to the photosensitive composition containing (A4) a carboxylic acid-containing photosensitive resin produced from an epoxy compound as a starting material.

[0016] The (A2) carboxylic acid-containing photosensitive resin having a urethane skeleton refers to a resin having a urethane bond, a photosensitive group, and a carboxyl group in the molecule. Examples of the (A2) carboxylic acid-containing photosensitive resin having a urethane skeleton include the following (A2-1), (A2-2), and (A2-3). (A2-1) A carboxylic acid-containing photosensitive resin obtained by adding a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as a hydroxyalkyl (meth)acrylate, during the synthesis of a carboxyl group-containing urethane resin by polyaddition reaction of a diisocyanate, such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate, with a carboxyl group-containing dialcohol compound, such as dimethylolpropionic acid or dimethylolbutanoic acid, and a diol compound, such as a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group or an alcoholic hydroxyl group, to form a carboxyl group-containing urethane resin. (A2-2) A carboxylic acid-containing photosensitive resin having terminal (meth)acrylates, obtained by adding a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as a hydroxyalkyl (meth)acrylate, during the synthesis of a carboxyl-terminated urethane resin obtained by reacting an acid anhydride with the terminal of a urethane resin obtained by polyaddition reaction of a diisocyanate compound, such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate, with a diol compound, such as a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group or an alcoholic hydroxyl group.(A2-3) Carboxylic acid-containing photosensitive resins obtained by polyaddition reaction of diisocyanates with (meth)acrylates or partially acid anhydride-modified products thereof of bifunctional epoxy resins such as bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bixylenol epoxy resins, and biphenol epoxy resins, carboxyl group-containing dialcohol compounds, and diol compounds. In this specification, (meth)acrylate is a general term for acrylates, methacrylates, and mixtures thereof, and the same applies to other similar expressions.

[0017] Examples of these carboxylic acid-containing photosensitive resins having a urethane skeleton include UXE-3000 (acid value 98 KOH / mg) and UXE-3024 (acid value 60 KOH / mg) manufactured by Nippon Kayaku Co., Ltd.

[0018] In the present invention, by using, as the carboxylic acid-containing resin, the above-mentioned carboxylic acid-containing photosensitive resin (A2) having a urethane skeleton in combination with a colorant consisting of a quinophthalone compound having a specific amide structure (described below), not only can the resolution and heat resistance be improved, but also, in particular, the PCT resistance and flexibility of the cured product are improved. This is thought to be because, when the urethane skeleton and the amide structure coexist in the cured product, part of the urethane skeleton is decomposed in a PCT environment, but the amide structure caps the decomposition point, thereby improving the PCT resistance and flexibility of the cured product.

[0019] The (A3) carboxylic acid-containing copolymer photosensitive resin refers to a resin obtained by adding a compound having a photosensitive group to some of the carboxyl groups of a (meth)acrylic copolymer having carboxyl groups in the main chain or side chain. Examples of the (A3) carboxylic acid-containing copolymer photosensitive resin include the following (A3-1). (A3-1) A carboxylic acid-containing copolymer photosensitive resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, or isobutylene, and then adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the carboxyl group-containing resin.

[0020] Examples of these carboxylic acid-containing copolymer photosensitive resins include those obtained by reacting some of the carboxyl groups of a terpolymer of methyl methacrylate, methacrylate, and acrylate with an epoxy (meth)acrylate that does not have an alicyclic skeleton, such as glycidyl (meth)acrylate, or an epoxy (meth)acrylate that has an alicyclic skeleton, such as 3,4-epoxycyclohexyl (meth)acrylate. Examples of these carboxylic acid-containing copolymer photosensitive resins include Cyclomer Z250 (acid value 69 KOH / mg) and Cyclomer Z320 (acid value 135 KOH / mg), both manufactured by Daicel Allnex Corporation.

[0021] Furthermore, as the compound having a photosensitive group, from the viewpoint of resolution, an epoxy (meth)acrylate having an alicyclic skeleton is more preferable than an epoxy (meth)acrylate not having an alicyclic skeleton.

[0022] In the present invention, by using the above-mentioned carboxylic acid-containing copolymer photosensitive resin (A3) in combination with a colorant consisting of a quinophthalone compound having a specific amide structure (described later) as the carboxylic acid-containing resin, not only can the resolution and heat resistance be improved, but also the light transmittance is less likely to change even when the drying conditions after coating the photosensitive composition change, and the haze in particular is stable. This is thought to be because the coexistence of the copolymer skeleton and the amide structure in the cured product allows the dispersibility of the entire photosensitive composition to be maintained.

[0023] (A4) A carboxylic acid-containing photosensitive resin made from an epoxy compound as a starting material refers to a resin having a photosensitive group and a carboxyl group, which is made from an epoxy compound as a starting material. Examples of (A4) a carboxylic acid-containing photosensitive resin made from an epoxy compound as a starting material include the following (A4-1) to (A4-4). (A4-1) A carboxylic acid-containing photosensitive resin obtained by reacting an epoxy resin, such as an orthocresol novolac epoxy resin, with an unsaturated group-containing monocarboxylic acid, such as acrylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride, such as tetrahydroxyphthalic anhydride. (A4-2) A carboxylic acid-containing photosensitive resin obtained by reacting an unsaturated group-containing monocarboxylic acid with a polyfunctional epoxy resin, in which the hydroxyl groups of a bifunctional epoxy resin have been further epoxidized with epichlorohydrin, and then adding a polybasic acid anhydride to the resulting hydroxyl groups. (A4-3) A carboxylic acid-containing photosensitive resin obtained by reacting an epoxy compound having multiple epoxy groups with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and an unsaturated group-containing monocarboxylic acid, and then reacting the alcoholic hydroxyl group of the resulting reaction product with a polybasic acid anhydride. (A4-4) A carboxylic acid-containing photosensitive resin obtained by further adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule, such as glycidyl methacrylate, to any one of the resins (A4-1) to (A4-3) above.

[0024] An example of a carboxylic acid-containing photosensitive resin using an epoxy compound as a starting material is UE-9210 (acid value 53 KOH / mg) manufactured by DIC Corporation.

[0025] In the present invention, by using a carboxylic acid-containing photosensitive resin made from the above-mentioned epoxy compound (A4) as a starting material as a carboxylic acid-containing resin in combination with a colorant made from a quinophthalone compound having a specific amide structure (described below), not only can resolution and heat resistance be improved, but resistance to the Highly Accelerated Stress Test (HAST) (i.e., HAST resistance) is also improved. This is thought to be because, while chlorine is contained in the carboxylic acid-containing photosensitive resin made from an epoxy compound as a starting material, the colorant made from a quinophthalone compound having a specific amide structure (described below) adsorbs the chlorine, thereby improving HAST resistance. This is also thought to be due to the fact that the colorant inhibits the migration of chlorine in the cured product, and the improved curability makes chlorine less likely to migrate.

[0026] In the present invention, a carboxylic acid-containing resin other than the four types of carboxylic acid-containing photosensitive resins described above may be contained, and a conventionally known carboxyl group-containing resin having an ethylenically unsaturated double bond in the molecule may be contained.

[0027] The weight-average molecular weight of the carboxylic acid-containing resin varies depending on the resin skeleton, but is generally preferably 2,000 to 150,000. Within the range of 2,000 to 150,000, the tack-free performance is good, the moisture resistance of the cured coating after exposure is good, and film loss during development is unlikely to occur. Furthermore, within the above weight-average molecular weight range, the resolution is improved, the developability is good, and storage stability is improved. A more preferred range is 5,000 to 100,000.

[0028] (B) Photopolymerization Initiator The photopolymerization initiator is added to initiate polymerization of the above-mentioned (A) carboxylic acid-containing resin and / or the later-described (C) photosensitive monomer. Examples of the photopolymerization initiator include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, and bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide. )-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and other bisacylphosphine oxides; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester monoacylphosphine oxides such as ethyl (2,4,6-trimethylbenzoyl) phenyl phosphine oxide; acyl phosphinates such as ethyl (2,4,6-trimethylbenzoyl) phenyl phosphonate; hydroxyacetophenones such as 1-hydroxy-cyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoins such as benzoin, benzil, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; benzoin alkyl ethers;Benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio) (e) acetophenones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and N,N-dimethylaminoacetophenone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, and the like; Thioxanthones such as oxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; acetophenone dimethyl ketal, benzyl dimethyl ketals such as ketals; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, and p-dimethylbenzoic acid ethyl ester; oxime esters such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, and 1-(O-acetyloxime); titanocenes such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyr-1-yl)ethyl)phenyl]titanium;Examples of the disulfide include phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, and tetramethylthiuram disulfide. These may be used alone or in combination of two or more.

[0029] Among the above, at least one of monoacylphosphine oxides, acylphosphinates, and oxime esters is preferred, and at least one of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl (2,4,6-trimethylbenzoyl)phenylphosphineate, and ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) is more preferred.

[0030] The amount of the photopolymerization initiator (B) to be blended is preferably 0.1 parts by mass or more and 40 parts by mass or less, and more preferably 0.3 parts by mass or more and 15 parts by mass or less, in terms of solid content, per 100 parts by mass of the carboxylic acid-containing resin (A).

[0031] (C) Photosensitive Monomer The photosensitive composition of the present invention contains (C) a photosensitive monomer. The photosensitive monomer is a monomer having an ethylenically unsaturated double bond. Examples of such photosensitive monomers include commonly known polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, carbonate (meth)acrylates, and epoxy (meth)acrylates. Specific examples include alkyl acrylates such as 2-ethylhexyl acrylate and cyclohexyl acrylate; hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; mono- or diacrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide, and N,N-dimethylaminopropylacrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and trishydroxyethyl isocyanurate. The photosensitive monomer may be selected from at least one of the following: polyhydric acrylates such as polyhydric alcohols or their alkylene oxide adducts or ε-caprolactone adducts; phenols such as phenoxy acrylate and bisphenol A diacrylate or their alkylene oxide adducts; acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; and, without limitation, acrylates and melamine acrylates obtained by directly acridating polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, and polyester polyols or by urethane acrylates via diisocyanates, and methacrylates corresponding to the above acrylates. Such photosensitive monomers can also be used as reactive diluents.

[0032] The photosensitive monomers can be used alone or in combination of two or more. The content of the photopolymerizable monomer is preferably 0.5 to 30 parts by mass, calculated as solid content, per 100 parts by mass of the (A) carboxylic acid-containing resin. When the content is 0.5 parts by mass or more, the photocurability is good, and pattern formation is easy in alkaline development after irradiation with active energy rays. Furthermore, when the content is 30 parts by mass or less, halation is less likely to occur, and good resolution is more likely to be obtained. In particular, from the viewpoint of resolution, the content of the photopolymerizable monomer is more preferably 6 to 18 parts by mass, calculated as solid content, per 100 parts by mass of the (A) carboxylic acid-containing resin.

[0033] (D) Colorant The photosensitive composition of the present invention contains, as a colorant (D), a quinophthalone compound represented by the following formula (1), which is a compound having an amide structure to which at least one substituent having a quinophthalone structure (hereinafter also referred to as a quinophthalone substituent) has been introduced:

[0034] In formula (1), R １ and R ２ are each independently —OH, —OR ａ , -NR ｂ R ｃ , —C(═O)NR ｂ R ｃ , halogen atoms, —CN, —NO ２ , -COOH, -C(=O)OR ｄ , -OC(=O)R ｄ , -COOM ａ , -SO ３ H, -S(=O) ２ OR ｄ , -OS(=O)2R ｄ , -SO ３ M ａ a hydrocarbon group having 1 to 30 carbon atoms, a group represented by formula (2) and a group represented by formula (3), wherein the hydrocarbon group having 1 to 30 carbon atoms may be substituted; R ３ are each independently —OH, —OR ａ , -NR ｂ R ｃ , —C(═O)NR ｂR ｃ , halogen atoms, —CN, —NO ２ , -COOH, -C(=O)OR ｄ , -OC(=O)R ｄ , -COOM ａ , -SO ３ H, -S(=O) ２ OR ｄ , —O—S(═O) ２ R ｄ , -SO ３ M ａ and a hydrocarbon group having 1 to 30 carbon atoms, which may be substituted; m is an integer of 0 to 5; n is an integer of 0 to 5; p is an integer of 0 to 4; R ａ is an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the aralkyl group may be substituted; R ｂ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the aralkyl group may be substituted; R ｃ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the aralkyl group may be substituted; R ｄ represents an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the aralkyl group may be substituted; M ａ is sodium or potassium, with the proviso that m+n is an integer of 1 or more, and formula (1) has at least one group selected from a group represented by the following formula (2) and a group represented by the following formula (3):

[0035]

[0036] In formula (2) and formula (3), X １ , X ２ , X ３ and X ４ are each independently —OH, —OX ａ , -NXｂ X ｃ , -C(=O)NX ｂ X ｃ , halogen atoms, —CN, —NO ２ , -COOH, -C(=O)OX ｄ , -OC(=O)X ｄ , -COOM ｂ , -SO ３ H, -S(=O) ２ OX ｄ , —O—S(═O) ２ X ｄ , -SO ３ M ｂ and a hydrocarbon group having 1 to 30 carbon atoms, wherein adjacent groups may be bonded to each other to form a carbocyclic or heterocyclic ring, and the hydrocarbon group having 1 to 30 carbon atoms may be substituted; L １ and L ２ are each independently a linking group selected from a single bond, —O—, —C(═O)O—, —S(═O)2O— and —NH—C(═O)—, q is an integer of 0 to 6, r is an integer of 0 to 3, s is an integer of 0 to 5, t is an integer of 0 to 4, and X ａ represents an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the aralkyl group may be substituted; X ｂ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group and the aralkyl group may be substituted; X ｃ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group and the aralkyl group may be substituted; X ｄ represents an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the aralkyl group may be substituted; M ｂ is sodium or potassium.

[0037] In this specification, the alkyl group may be branched or linear, and examples thereof include alkyl groups having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, etc. The alkenyl group may be branched or linear, and examples thereof include alkenyl groups having 2 to 20 carbon atoms, preferably 2 to 8 carbon atoms, and specific examples thereof include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, butadienyl, pentenyl, pentadienyl, hexadienyl, etc. The alkynyl group may be branched or linear, and examples thereof include alkynyl groups having 2 to 20 carbon atoms, preferably 2 to 8 carbon atoms, such as vinyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, butidienyl, pentynyl, pentidienyl, and 1-hexynyl. Aralkyl groups are groups in which one hydrogen atom of an alkyl group is substituted with an aryl group, and examples include aralkyl groups having 7 to 30 carbon atoms. Specific examples include benzyl, methylbenzyl, 1-phenylethyl, and naphthylmethyl. The hydrocarbon group is not particularly limited as long as it has one or more carbon atoms, and includes alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, aryl groups, and aralkyl groups. When the above groups are substituted, examples of the substituent include a hydroxyl group, an alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted amide group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a nitro group, a carboxyl group (which may be in the form of a salt), a carboxylic acid ester residue, a sulfonic acid group (which may be in the form of a salt), and a sulfonic acid ester residue. The carbocyclic ring is not particularly limited as long as all of the ring-constituting atoms are carbon atoms, and examples include 4- to 20-membered rings, and preferably 4- to 14-membered rings. The carbocyclic ring may be aromatic or non-aromatic, and may be monocyclic or polycyclic.Examples include cycloalkanes (e.g., cyclopropane, cyclopentane, cyclohexane, etc.) and arenes (e.g., benzene, naphthalene, etc.). The carbocyclic ring can contain the above-mentioned substituents and hydrocarbon groups. The heterocyclic ring is not particularly limited as long as the ring-constituting atoms are carbon atoms and heteroatoms, and examples include 4- to 20-membered rings, preferably 4- to 14-membered rings. Examples of heteroatoms include nitrogen atoms, oxygen atoms, sulfur atoms, etc. The heterocyclic ring may be aromatic or non-aromatic, and may be monocyclic or polycyclic. Examples include a pyridine ring, lactone ring, imidazole ring, thiazole ring, oxazole ring, etc. The heterocyclic ring can contain the above-mentioned substituents and hydrocarbon groups.

[0038] In formula (2), X １ may be bonded to either the pyridine ring or the benzene ring. ３ and L ２ may be bonded to either the pyridine ring or the benzene ring. ２ is preferably bonded to the benzene ring in formula (3).

[0039] L １ and L ２ When L is —C(═O)O— or —NH—C(═O)—, it is preferred that the carbon atom of these groups is directly bonded to formula (2) or formula (3). １ and L ２ is -S (=O) ２ In the case of O—, it is preferred that the sulfur atom of this group is directly bonded to formula (2) or formula (3). １ and L ２ are each independently preferably —NH—C(═O)—, —C(═O)O— or —O—, more preferably —C(═O)O— or —O—.

[0040] q is preferably 0 or 1. r is preferably 0 or 1. s is preferably 0 or 1. t is preferably 0 or 1.

[0041] X １ , X２ , X ３ or X ４ When present, these are preferably each independently -OH, an alkyl group having 1 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms which is partially or fully substituted with fluorine, or a halogen atom.

[0042] The quinophthalone substituent of formula (2) includes groups represented by the following formulae (2-1) to (2-4).

[0043]

[0044] In formulas (2-1) to (2-4), L 10 represents a single bond, -O-, -C(=O)O-, -S(=O) ２ is a linking group selected from —O— and —NH—C(═O)—; １ ~Y ６ and Y ７ ~Y １０ are each independently a hydrogen atom, —OH, or —OX ａ , -NX ｂ X ｃ , -C(=O)NX ｂ X ｃ , halogen atoms, —CN, —NO ２ , -COOH, -C(=O)OX ｄ , -OC(=O)X ｄ , -COOM ｂ , -SO ３ H, -S(=O)2OX ｄ , —O—S(═O) ２ X ｄ , -SO ３ M ｂ and a hydrocarbon group having 1 to 30 carbon atoms, wherein adjacent groups may be linked to each other to form a carbocyclic ring or a heterocyclic ring, and the hydrocarbon group having 1 to 30 carbon atoms may be substituted.

[0045] L 10 is preferably —C(═O)O—, —NH—C(═O)—, or —O—, and more preferably —C(═O)O— or —O—. １ and Y ２ is preferably a hydrogen atom, —OH, or an alkyl group having 1 to 30 carbon atoms.３ ~Y ６ is preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 30 carbon atoms. ７ ~Y １０ is preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 30 carbon atoms.

[0046] The quinophthalone substituent of formula (3) includes the following formulae (3-1) to (3-5).

[0047] In formulas (3-1) to (3-5), L 20 represents a single bond, -O-, -C(=O)O-, -S(=O) ２ is a linking group selected from —O— and —NH—C(═O)—; １ ~Y 10 are each independently a hydrogen atom, —OH, or —OX ａ , -NX ｂ X ｃ , -C(=O)NX ｂ X ｃ , halogen atoms, —CN, —NO ２ , -COOH, -C(=O)OXd, -OC(=O)X ｄ , -COOM ｂ , -SO ３ H, -S(=O) ２ OX ｄ , —O—S(═O) ２ X ｄ , -SO ３ M ｂ and a hydrocarbon group having 1 to 30 carbon atoms, wherein adjacent groups may be linked to each other to form a carbocyclic ring or a heterocyclic ring, and the hydrocarbon group having 1 to 30 carbon atoms may be substituted.

[0048] L 20 is preferably —C(═O)O—, —NH—C(═O)—, or —O—, and more preferably —C(═O)O— or —O—. １ and Y ２ , a hydrogen atom, —OH, or an alkyl group having 1 to 30 carbon atoms is preferred. ３ ~Y ６ is preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 30 carbon atoms.７ ~Y 10 is preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 30 carbon atoms.

[0049] The quinophthalone substituent is preferably a group represented by formula (2).

[0050] The quinophthalone compound is represented by the formula (1), １ and R ２ has at least one quinophthalone substituent represented by formula (2) or formula (3).

[0051] The above formula (1) preferably has at least two quinophthalone substituents represented by formula (2) or (3), and the quinophthalone substituents R １ and R is a quinophthalone substituent. ２ It is more preferred that the quinophthalone substituent R １ and one quinophthalone substituent, R ２ It is particularly preferred that the compound has one of the following:

[0052] R １ and R ２ Although the quinophthalone group may have only the quinophthalone substituent, other substituents may also be present. When a substituent other than the quinophthalone substituent is present, it is preferably a halogen atom, more preferably a chlorine atom or a bromine atom.

[0053] The quinophthalone compound includes a compound of formula (1-1).

[0054] In formula (1-1), R 11 ~R 20 Among them, R 13 and R 18 are groups selected from the group represented by formula (2) and the group represented by formula (3), and the others are each independently a hydrogen atom, —OH, —OR ａ , -NR ｂ R ｃ , —C(═O)NR ｂ R ｃ , halogen atoms, —CN, —NO ２, -COOH, -C(=O)OR ｄ , -OC(=O)R ｄ , -COOM ａ , -SO ３ H, -S(=O) ２ OR ｄ , —O—S(═O) ２ R ｄ , -SO ３ M ａ a hydrocarbon group having 1 to 30 carbon atoms, a group represented by formula (2) and a group represented by formula (3), wherein the hydrocarbon group having 1 to 30 carbon atoms may be substituted; R 21 ~R 24 are each independently a hydrogen atom, —OH, —OR ａ , -NR ｂ R ｃ , —C(═O)NR ｂ R ｃ , halogen atoms, —CN, —NO ２ , -COOH, -C(=O)OR ｄ , -OC(=O)R ｄ , -COOM ａ , -SO ３ H, -S(=O) ２ OR ｄ , —O—S(═O) ２ R ｄ , -SO ３ M ａ and hydrocarbon groups having 1 to 30 carbon atoms, which may be substituted.

[0055] In formula (1-1), R 13 and R 18 and R are quinophthalone substituents represented by formula (2) or (3), 13 and R 18 and R are quinophthalone substituents represented by formula (2). 11 ~R 12、 R 14 ~R 17、 R 19 ~R 20 is preferably a hydrogen atom or a halogen atom (chlorine atom, bromine atom), more preferably a hydrogen atom.21 ~R 24 is preferably a hydrogen atom.

[0056] The quinophthalone compound is represented by the formula (1-1), 13 and R 18 and R is a quinophthalone substituent represented by formula (2) or (3). 13 and R 18 The other is —OH or —NH ２ and the monosubstituted compound is preferably L 10 or L 20 When L has -NHC(=O)-, the other is preferably -OH. 10 or L 20 When the other has -NH ２ It is preferable that:

[0057] In formula (1-1), R 13 and R 18 and R are quinophthalone substituents represented by formula (2) or (3) (disubstituted compounds), including compounds represented by formulas (i) to (vii) below. 13 and R 18 The compound of formula (i) is a quinophthalone substituent represented by formula (2-1), the compound of formula (ii) is a quinophthalone substituent represented by formula (2-2), the compound of formula (iii) is a quinophthalone substituent represented by formula (3-1), the compound of formula (iv) is a quinophthalone substituent represented by formula (3-2), the compound of formula (v) is a quinophthalone substituent represented by formula (3-3), the compound of formula (vi) is a quinophthalone substituent represented by formula (3-4), and the compound of formula (vii) is a quinophthalone substituent represented by formula (3-5).

[0058]

[0059] In formulas (i) to (vii), R11, R12, R14 to R17, R19, R20, R21 to R24, Y1 to Y10, L 10 and L 20The above definitions and preferred examples apply to L. When a plurality of the above groups are present, they may be the same or different. １ and L ２ When L is -C(=O)O- or -NH-C(=O)-, it is preferred that the carbon atom of these groups is directly bonded to the quinophthalone substituent, and that the -O- of these groups is directly bonded to formula (1-1). １ and L ２ is -S (=O) ２ In the case of O-, it is preferred that the sulfur atom of this group is directly bonded to the quinophthalone substituent, and that -O- or -NH- of these groups is directly bonded to formula (1-1).

[0060] L 10 Examples of compounds of formula (i) in which is —C(═O)O— include the following compounds: In the following chemical formulas, Me represents a methyl group, and Bn represents a benzyl group (the same applies hereinafter in this specification).

[0061]

[0062] L 10 Examples of the compound of formula (ii) in which is —C(═O)O— include the following compounds:

[0063] L 20 Examples of the compound of formula (iii) in which is —C(═O)O— include the following compounds:

[0064] L 20 Examples of the compound of formula (iv) in which is —C(═O)O— include the following compounds:

[0065] L 20Examples of the compound of formula (v) in which is —C(═O)O— include the following compounds:

[0066] L 20 Examples of the compound of formula (vi) in which is —C(═O)O— include the following compounds:

[0067] L 20 Examples of the compound of formula (vii) in which is —C(═O)O— include the following compounds:

[0068] In formula (1-1), R 13 and R 18 and the other is —OH (monosubstituted compounds), 10 or L 20 Examples of compounds in which is —C(═O)O— include the following:

[0069] Examples of compounds in which the quinophthalone substituent is represented by formula (2-1) include the following compounds.

[0070]

[0071] Examples of compounds in which the quinophthalone substituent is represented by formula (2-2) include the following compounds:

[0072] Examples of compounds in which the quinophthalone substituent is represented by formula (3-1) include the following compounds.

[0073] Examples of compounds in which the quinophthalone substituent is represented by formula (3-2) include the following compounds:

[0074] Examples of compounds in which the quinophthalone substituent is represented by formula (3-3) include the following compounds:

[0075] Examples of compounds in which the quinophthalone substituent is represented by formula (3-4) include the following compounds:

[0076] Examples of compounds in which the quinophthalone substituent is represented by formula (3-5) include the following compounds.

[0077] L in the compounds of formulae (i) to (vii) 10 or L 20 Also preferred are compounds in which is —NH—C(═O)— (amide-altered disubstituted compounds). For example, the following compounds can be mentioned:

[0078]

[0079] In formula (1-1), R 13 and R 18 is a quinophthalone substituent represented by formula (2) or formula (3), and the other is -NH ２ Among the compounds (monosubstituted compounds) in which L 10 Examples of compounds in which is —NHC(═O)— include the following compounds:

[0080] The above-mentioned quinophthalone compound can be obtained by reacting a compound having an amide structure with a compound having a quinophthalone substituent.

[0081] As the compound having an amide structure, a compound represented by formula (4) or a derivative thereof (hereinafter, these may be collectively referred to as compounds of formula (4) or the like), a compound represented by formula (4') or a derivative thereof (hereinafter, these may be collectively referred to as compounds of formula (4') or the like), etc. can be used. 11 ~R 20 and R 21 ~R 24 Examples include derivatives having a substituent at a position corresponding to the position of the quinophthalone. The substituent may be introduced after the quinophthalone substituent is introduced.

[0082]

[0083] It is known that the compound of formula (4) can be synthesized by the following reaction.

[0084] In the above reaction, instead of aminophenol, a substituted aminophenol in which hydrogen atoms on the aromatic ring of aminophenol are substituted with a substituent may be used. By using such a substituted aminophenol, a substituent can be introduced into the compound represented by formula (4). Examples of the substituted aminophenol include aminophenols substituted with alkyl groups such as 4-amino-3-methylphenol and 4-amino-2,3-xylenol; aminophenols substituted with halogen atoms such as 4-amino-3-fluorophenol and 4-amino-3-chlorophenol; and aminophenols substituted with alkoxy groups such as 4-amino-2-methoxyphenol.

[0085] Furthermore, in the above reaction, by using an excess amount of phenylenediamine instead of aminophenol, a compound of formula (4') can be synthesized. Furthermore, instead of phenylenediamine, a substituted phenylenediamine in which hydrogen atoms on the aromatic ring of phenylenediamine are substituted with a substituent may be used. By using such a substituted phenylenediamine, a substituent can be introduced into the compound of formula (4'). Examples of substituted phenylenediamines include phenylenediamines substituted with alkyl groups such as 2,5-diaminotoluene and 2,5-dimethyl-1,4-phenylenediamine; phenylenediamines substituted with halogen atoms such as 2-chloro-1,4-phenylenediamine and 2,3,5,6-tetrafluoro-1,4-phenylenediamine; phenylenediamines substituted with fluoroalkyl groups such as 2-(trifluoromethyl)-1,4-phenylenediamine; and phenylenediamines substituted with sulfo groups such as 1,4-phenylenediamine-2-sulfonic acid.

[0086] The compound of formula (4) can also be synthesized by hydrolyzing polyethylene terephthalate (PET), for example, by the method described in Polymer Chemistry (2013), 4(5), 1610-1616.

[0087] As the compound having a quinophthalone substituent, compounds in which the linking moiety (L1 in formula (2) and L2 in formula (3)) in formula (2) is replaced with a corresponding monovalent group can be used. The monovalent group corresponding to the linking moiety of this compound can be reacted with a hydroxyl group of a compound of formula (4) or a derivative thereof, or an amino group of a compound of formula (4') or a derivative thereof, to obtain a compound of formula (1).

[0088] In the following, in formula (1-1), R 13 and R 18 Both are represented by formula (2-1), and L 10 The synthesis of compounds in which the quinophthalone substituent is —C(═O)O— (ester bond) will be mainly described.

[0089] For the introduction of a quinophthalone substituent, a compound represented by formula (5) or a derivative thereof (hereinafter, sometimes referred to as a compound of formula (5) or the like) can be used. １ ~Y ８ and Y 10 The corresponding substituent may be introduced after the reaction.

[0090]

[0091] The compound of formula (5) can be obtained by reacting 2-methylquinoline with trimellitic anhydride by a known method.

[0092] The amounts of the compound of formula (4) etc. and the compound of formula (5) etc. used can be such that the compound of formula (5) etc. is in excess, and preferably the amount of the compound of formula (5) etc. is more than 2 moles per mole of the compound of formula (4) etc. Note that, for example, when the compound of formula (5) etc. is used in an amount of less than 2 moles per mole of the compound of formula (4) etc., a quinophthalone compound having one quinophthalone substituent can also be obtained.

[0093] The reaction temperature for the reaction of the compound of formula (4) or the like with the compound of formula (5) or the like can be 0 to 120°C, preferably 80 to 100°C. The reaction time can be 1 to 24 hours, more preferably 12 to 20 hours. The reaction can be carried out under atmospheric pressure.

[0094] The reaction between the compound of formula (4) or the like and the compound of formula (5) or the like can be carried out using a dehydration condensation agent. The dehydration condensation agent is not particularly limited, and examples thereof include carbodiimides such as dicyclohexylcarbodiimide, diisopropylcarbodiimide, and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride; and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide that is not a hydrochloride salt. Furthermore, additives such as 1-hydroxybenzotriazole and N,N-dimethylaminopyridine can also be used.

[0095] The reaction is preferably carried out in a solvent. Examples of the solvent include amide solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and dimethylformamide; hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; ketone solvents such as methyl isobutyl ketone; ether solvents such as tetrahydrofuran and 1,4-dioxane; and nitrile solvents such as acetonitrile, among which amide solvents are preferred.

[0096] After the reaction, the resulting product may be subjected to post-treatment and purification, as necessary, to isolate the target compound, for example, by filtration, washing, extraction, concentration under reduced pressure, recrystallization, distillation, column chromatography, etc.

[0097] When the linking moiety is other than -C(=O)O- (ester bond), and when the quinophthalone substituent is represented by formula (3), the compound can be synthesized in the same manner as above. For example, when a compound in which the -OH group in the compound of formula (4) is replaced with an -NH group is used instead of the compound of formula (4), a quinophthalone compound in which the linking moiety is -NH-C(=O)- (amide bond) can be obtained. Furthermore, when a compound in which the position of the carboxyl group is different, for example, L of each of formulas (3-1) to (3-5) is used instead of the compound of formula (5), ２０ By using a compound having a carboxyl group at the position corresponding to the formula (1), a quinophthalone compound in which the quinophthalone substituent is represented by formula (3) can be obtained.

[0098] Specific examples of the synthesis method for the quinophthalone compound of the present invention include the synthesis scheme shown below. Scheme 1 (Synthesis of Compound No. 2)

[0099] Scheme 2 (Synthesis of Compound No. 4)

[0100] Scheme 3 (Synthesis of Compound No. 35)

[0101] Scheme 4 (Synthesis of Compound No. 65)

[0102] Scheme 5 (Synthesis of Compound No. 101)

[0103] Scheme 6 (Synthesis of Compound No. 135)

[0104] Scheme 7 (Synthesis of Compound No. 329)

[0105] Scheme 8

[0106] Scheme 9

[0107] The photosensitive composition of the present invention contains, as the colorant (D), the above-mentioned quinophthalone compounds alone or in combination of two or more kinds in any ratio.

[0108] The content of the quinophthalone compound is preferably 0.1 to 5 parts by mass, calculated as solid content, per 100 parts by mass of the carboxylic acid-containing resin (A), and more preferably 0.3 to 3.0 parts by mass from the viewpoint of resolution.

[0109] The photosensitive composition of the present invention may contain a colorant other than the above-mentioned quinophthalone compound as the colorant (D). For example, red pigments such as C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; blue pigments such as C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60; purple pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38; green pigments such as C.I. Pigment Green 7, 36, 58, etc. Examples of suitable dyes include compounds classified as compounds having a hue other than pigments, and known dyes described in Dyeing Notes (manufactured by Irosen Co., Ltd.), and, based on their chemical structure, examples include azo dyes, anthraquinone dyes, cyanine dyes, phthalocyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes.

[0110] The photosensitive composition of the present invention can be made into a photosensitive composition of various colors, such as a green photosensitive composition or a black photosensitive composition, by combining the above-mentioned quinophthalone compound with a colorant other than the above-mentioned quinophthalone compound as the colorant (D). When a colorant other than the above-mentioned quinophthalone compound is used in combination, it is preferable to include an anthraquinone-based blue colorant. Anthraquinone-based blue colorants have higher transmittance than common phthalocyanine-based blue colorants and therefore can exhibit excellent resolution. From the viewpoint of resolution, the content of the anthraquinone-based blue colorant is preferably 0.01 to 4.0 parts by mass, and more preferably 0.20 to 2.0 parts by mass, calculated as solids, per 100 parts by mass of the carboxylic acid-containing resin (A). Furthermore, in the present invention, the above-mentioned quinophthalone compound may be combined with a violet colorant or the like to form a black photosensitive composition. A typical black photosensitive composition has low deep section curability, making it difficult to obtain high resolution. However, by including the above-described quinophthalone compound, the black photosensitive composition has excellent resolution.

[0111] (E) Thermosetting Resin The photosensitive composition of the present invention may contain (E) a thermosetting resin in addition to the above-mentioned components. Examples of the thermosetting resin include known and commonly used thermosetting resins such as isocyanate compounds, blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, epoxy compounds, oxetane compounds, and episulfide resins. Among these, the preferred thermosetting resin is an epoxy resin.

[0112] Examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, and triphenylmethane type epoxy resins. These may be used alone or in combination of two or more.

[0113] Examples of commercially available epoxy resins include jER (registered trademark) 828, 806, 807, YX8000, YX8034, and 834 manufactured by Mitsubishi Chemical Corporation; YD-128, YDF-170, ZX-1059, and ST-3000 manufactured by Nippon Steel Chemical & Material Co., Ltd.; EPICLON (registered trademark) 830, 835, 840, 850, N-730A, and N-695 manufactured by DIC Corporation; and RE-306 manufactured by Nippon Kayaku Co., Ltd.

[0114] The epoxy group equivalent of the epoxy resin in the photosensitive composition is preferably 0.5 to 2.5 in terms of solid content per equivalent of carboxyl group of the carboxylic acid-containing resin. By setting the amount to 0.5 equivalents or more, it is possible to prevent carboxyl groups from remaining in the cured product and obtain good heat resistance, etc. Furthermore, by setting the blending amount to 2.5 equivalents or less, it is possible to prevent low-molecular-weight cyclic (thio)ether groups from remaining in the dried coating film and ensure good strength, etc. of the cured product.

[0115] When the photosensitive composition of the present invention contains a thermosetting resin, it may contain a thermosetting catalyst for accelerating the curing of the thermosetting resin. Examples of the thermosetting catalyst include imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Commercially available compounds include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all of which are trade names of imidazole-based compounds) manufactured by Shikoku Chemicals Corporation, and U-CAT 3513N (a trade name of a dimethylamine-based compound), DBU, DBN, and U-CAT SA 102 (all of which are bicyclic amidine compounds and salts thereof) manufactured by San-Apro Co., Ltd.

[0116] The compounds are not limited to those listed above, and any heat curing catalyst for epoxy resins or oxetane compounds, or any compound that promotes the reaction between at least one of an epoxy group and an oxetanyl group and a carboxyl group, may be used alone or in combination of two or more. Also usable are S-triazine derivatives such as 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-isocyanuric acid adduct, and 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct. These compounds that also function as adhesion promoters are preferably used in combination with the heat curing catalyst.

[0117] The thermosetting catalyst may be used alone or in combination of two or more. From the viewpoint of the storage stability of the photosensitive composition and the heat resistance of the cured coating, the content of the thermosetting catalyst is preferably 0.01 to 30 parts by mass, and more preferably 0.1 to 20 parts by mass, calculated as solid content, per 100 parts by mass of the carboxylic acid-containing resin (A).

[0118] (F) Filler The photosensitive composition of the present invention may contain a filler as needed, from the viewpoint of improving the physical strength of the cured film of the photosensitive composition or adjusting the thermal expansion coefficient. As the filler, known inorganic or organic fillers can be used, but it is particularly preferable to use an inorganic filler. Examples of inorganic fillers include silica, talc, mica, aluminum oxide, calcium oxide, magnesium oxide, zinc oxide, calcium carbonate, magnesium carbonate, fly ash, dewatered sludge, kaolin, clay, calcium hydroxide, aluminum hydroxide, magnesium hydroxide, hydrotalcite, aluminum silicate, magnesium silicate, calcium silicate, wollastonite, potassium titanate, magnesium sulfate, calcium sulfate, magnesium phosphate, sepiolite, zonolite, boron nitride, aluminum borate, silica balloons, glass flakes, glass balloons, steelmaking slag, copper, iron, iron oxide, sendust, alnico magnets, various magnetic powders such as ferrites, cement, glass powder, Neuburg silica, diatomaceous earth, antimony trioxide, magnesium oxysulfate, aluminum hydrate, hydrated gypsum, alum, and barium sulfate. These fillers may be used alone or in combination of two or more. Among the above, silica can be preferably used from the viewpoint of reducing the thermal expansion coefficient of the cured product of the photosensitive composition.

[0119] The shape of the filler is not particularly limited, and examples thereof include spherical, needle-like, plate-like, scaly, hollow, irregular, hexagonal, cubic, and flaky shapes. From the viewpoint of uniform dispersion of the filler in the photosensitive composition, a spherical shape is preferred.

[0120] When an inorganic filler is used as the filler, it may be surface-treated to enhance dispersibility in the photosensitive composition. By using a surface-treated filler, aggregation can be suppressed. The surface treatment method is not particularly limited, and a known, commonly used method may be used. However, it is preferable to treat the surface of the inorganic filler with a surface treatment agent having a curable reactive group, for example, a coupling agent having a curable reactive group as an organic group.

[0121] Examples of coupling agents that can be used include silane-based, titanate-based, aluminate-based, and zircoaluminate-based coupling agents. Among these, silane-based coupling agents are preferred. Examples of such silane-based coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminomethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. These can be used alone or in combination. It is preferable that these silane-based coupling agents are immobilized on the surface of the inorganic filler in advance by adsorption or reaction. Here, the amount of the coupling agent to be treated is preferably 0.5 to 10 parts by mass per 100 parts by mass of the inorganic filler.

[0122] The surface-treated inorganic filler may be contained in the photosensitive composition in a surface-treated state. The inorganic filler and the surface treatment agent may be separately blended into the photosensitive composition to surface-treat the inorganic filler in the photosensitive composition, but it is preferable to blend a pre-surface-treated inorganic filler. Blending a pre-surface-treated inorganic filler can prevent a decrease in crack resistance, etc., due to the surface treatment agent that may remain unconsumed during the surface treatment if blended separately. When performing pre-surface treatment, it is preferable to blend a pre-dispersion in which the inorganic filler is pre-dispersed in a solvent or curable resin. It is preferable to pre-disperse the surface-treated inorganic filler in a solvent and blend the pre-dispersion into the composition, or it is more preferable to thoroughly surface-treat an inorganic filler when pre-dispersing it in a solvent, and then blend the pre-dispersion into the composition.

[0123] From the viewpoint of dispersibility, the average particle size of the inorganic filler is suitably in the range of 0.1 μm to 25 μm, preferably 0.1 μm to 15 μm, and more preferably 1 μm to 10 μm. The average particle size means the average primary particle size, and the average particle size (D50) can be measured by a laser diffraction / scattering method.

[0124] The content of the filler is not particularly limited, but from the viewpoints of the viscosity, coatability, moldability, etc. of the photosensitive composition, it is preferably 300 parts by mass or less, more preferably 50 to 200 parts by mass, based on 100 parts by mass of the carboxylic acid-containing resin (A) in terms of solid content.

[0125] In addition to the above-mentioned components, the photosensitive composition of the present invention may contain, if necessary, components such as elastomers, mercapto compounds, urethanization catalysts, thixotropic agents, adhesion promoters, block copolymers, chain transfer agents, polymerization inhibitors, copper inhibitors, antioxidants, rust inhibitors, thickeners such as organic bentonite and montmorillonite, at least one of silicone-based, fluorine-based, and polymer-based antifoaming agents and leveling agents, and flame retardants such as phosphinates, phosphate ester derivatives, and phosphorus compounds such as phosphazene compounds. These may be compounds known in the field of electronic materials.

[0126] The photosensitive composition of the present invention may contain an organic solvent from the viewpoint of ease of preparation and coating properties. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, and tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, petroleum naphtha, and solvent naphtha. These organic solvents can be used alone or in combination of two or more.

[0127] The content of the organic solvent in the photosensitive composition can be appropriately changed depending on the materials constituting the photosensitive composition.

[0128] The photosensitive composition of the present invention may be used in the form of a dry film or in the form of a liquid. When used in the form of a liquid, it may be a one-component type or a two-component or more-component type.

[0129] <Laminate Structure> The laminate structure of the present invention comprises a first film and a resin layer provided on the first film, the resin layer comprising the photosensitive composition described above. To produce the laminate structure, the photosensitive composition of the present invention is applied to a uniform thickness on the first film using a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater, or the like, and then dried at a temperature of 60 to 180°C for 1 to 30 minutes to obtain a resin layer. There are no particular restrictions on the thickness of the applied film, but the thickness of the resin layer after drying is generally selected appropriately from the range of 1 to 200 μm, preferably 10 to 150 μm.

[0130] Examples of the first film include metal foils (e.g., copper foils), carrier films, etc. The carrier film is not particularly limited, and examples thereof include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyimide films, polyamideimide films, polyethylene films, polytetrafluoroethylene films, polypropylene films, and polystyrene films. From the viewpoint of improving mechanical strength, the above-mentioned films are preferably uniaxially or biaxially stretched films.

[0131] The laminate structure may have a second film releasably provided on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer, etc. Examples of the second film include a polyester film, a polyethylene film, a polypropylene film, etc. Note that "releasable" means that when the second film is peeled from the resin layer, the adhesive strength between the resin layer and the second film is smaller than the adhesive strength between the resin layer and the first film, and for example, the surface of the second film may be release-treated.

[0132] <Cured Product and Electronic Component> The cured product of the present invention can be obtained by curing the resin layer of the photosensitive composition or laminate structure described above. For example, the photosensitive composition can be applied by a method such as dip coating, flow coating, roll coating, bar coating, screen printing, or curtain coating, and then the organic solvent contained in the composition is evaporated and dried (pre-dried) at a temperature of 60 to 180°C to form a tack-free resin layer. The cured product can then be obtained by thermal curing at a temperature of 150 to 250°C for 30 to 90 minutes.

[0133] Examples of substrates onto which the resin layer of the laminated structure is laminated include printed wiring boards and flexible printed wiring boards on which circuits have been formed in advance using copper or the like, as well as copper-clad laminates for high-frequency circuits made from materials such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluororesin / polyethylene / polyphenylene ether, polyphenylene oxide / cyanate, and the like, including copper-clad laminates of all grades (FR-4, etc.), as well as metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates, etc.

[0134] To laminate the resin layer surface of the laminated structure onto the substrate, it is preferable to use a vacuum laminator or the like, and to carry out the process under pressure and heat. By using such a vacuum laminator, even if the circuit board surface is uneven, the resin layer adheres to the circuit board, preventing the inclusion of air bubbles and improving the filling of recesses on the substrate surface. After laminating the resin layer surface of the laminated structure onto the substrate, it can be thermally cured at a temperature of 80 to 250°C for 30 to 90 minutes to obtain a cured product.

[0135] A cured product obtained using the photosensitive composition or laminate structure of the present invention can be used for producing electronic components such as printed wiring boards, and is preferably used to form a passivation film for a semiconductor, a protective film for a semiconductor element, an interlayer insulating film for a semiconductor, or an interlayer insulating film for multilayer wiring for high-density packaging.

[0136] Examples of electronic components include permanent protective films for printed wiring boards, particularly solder resist layers, interlayer insulating layers, and coverlays for flexible printed wiring boards. Electronic components also include applications other than printed wiring boards, such as passive components such as inductors. In addition to the above applications, the material can also be suitably used for permanent hole filling in printed wiring boards, such as filling through holes and via holes. It can also be used as an encapsulant for semiconductor chips, and as a material for copper-clad laminates (CCLs) and prepregs.

[0137] The cured product of the photosensitive composition of the present invention has excellent dielectric properties, and its use can result in good transmission quality even in high-frequency applications. Specific examples of high-frequency applications include substrates for millimeter-wave radar and millimeter-wave sensors for autonomous driving, motherboards for mobile devices compatible with high-speed communication, SLP (Substrate-Like PCB) circuits formed by the modified semi-additive process (MSAP), application processors (AP) for mobile devices and personal computers, highly multilayer substrates for base station servers and routers, substrates for antennas, and semiconductor encapsulation materials. Furthermore, a wiring board may be formed by bonding wiring using the laminate structure of the present invention.

[0138] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following, "parts" and "%" are all by mass unless otherwise specified.

[0139] <Preparation of Colorant> (Synthesis of Quinophthalone Compound 1) Quinophthalone compound 1 was synthesized according to the following scheme.

[0140] 3.6 mmol of 2,3-dihydro-1,3-dioxy-2-(2-quinolinyl)-1H-indene-5-carboxylic acid (compound 2), 4.3 mmol of N,N'-dicyclohexylcarbodiimide, 4.3 mmol of 1-hydroxybenzotriazole, and 57 mL of N-methylpyrrolidone were mixed and heated in a nitrogen atmosphere. After stirring at 60°C for 30 minutes, １ , N ４1.4 mmol of N,N'-bis(4-hydroxyphenyl)-1,4-benzenedicarboxamide and 3.6 mmol of N,N'-dimethylformamide were added and reacted. After stirring at 90°C for 15 hours, the mixture was cooled to room temperature. The reaction solution was filtered to obtain a solid, which was washed with 15 mL of N-methylpyrrolidone. After further washing with 15 mL of ethanol, the solid was dried at 100°C under reduced pressure for 15 hours to obtain 1.4 mmol of quinophthalone compound 1.

[0141] FT-IR: Wave number (cm -1 ) = 3340 (amide NH), 3100-3000 (aromatic CH), 1720 (ester C=O), 1640 (amide C=O), 1625 (quinophthalone C=O). The IR chart is shown in Figure 1.

[0142] Quinophthalone Compound 1 was identified from the peak obtained in positive mode by laser desorption ionization using a time-of-flight mass spectrometer (rapifleX (registered trademark) (TOF-MS, manufactured by Bruker Daltonics)). MS (m / z) = 947.4 ([M+H] + )

[0143] (Synthesis of Quinophthalone Compound 2) Quinophthalone compound 2 was synthesized according to the following scheme.

[0144] 2-(8-nitroquinolin-2(1H)-ylidene)-1,3-dioxo-2,3-dihydro-1H-indene-5-carboxylic acid 2.76 mmol, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride 6.87 mmol, 1-hydroxybenzotriazole 3.29 mmol, N-methylpyrrolidone 20 mL, N １ , N ４1.31 mmol of 1,4-bis(4-hydroxyphenyl)-1,4-benzenedicarboxamide and 2.7 mmol of N,N-dimethylformamide were mixed and heated under a nitrogen atmosphere. The mixture was stirred at 100°C for 27 hours and then cooled to room temperature. The solid obtained by filtering the reaction solution was washed with 60 mL of N-methylpyrrolidone. After further washing with 60 mL of methanol, the solid was dried at 100°C under reduced pressure for 15 hours to obtain 0.97 mmol of quinophthalone compound 2.

[0145] FT-IR: Wave number (cm -1 ) = 3310 (amide NH), 3100-3000 (aromatic CH), 1730 (ester C=O), 1640 (amide C=O), 1625 (quinophthalone C=O). The IR chart is shown in Figure 2.

[0146] Quinophthalone Compound 2 was identified from the peak obtained in positive mode by laser desorption ionization using a time-of-flight mass spectrometer (rapifleX (registered trademark) (TOF-MS, manufactured by Bruker Daltonics)). MS (m / z) = 1037.3 ([M+H] + )

[0147] (Synthesis of Quinophthalone Compound 3) Quinophthalone compound 3 was synthesized according to the following scheme.

[0148] 2-(8-nitroquinolin-2(1H)-ylidene)-1,3-dioxo-2,3-dihydro-1H-indene-5-carboxylic acid 2.76 mmol, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride 6.87 mmol, 1-hydroxybenzotriazole 3.29 mmol, N-methylpyrrolidone 20 mL, N １ , N ４1.31 mmol of 1,4-bis(4-hydroxyphenyl)-1,4-benzenedicarboxamide and 2.7 mmol of N,N-dimethylformamide were mixed and heated under a nitrogen atmosphere. The mixture was stirred at 100°C for 27 hours and then cooled to room temperature. The solid obtained by filtering the reaction solution was washed with 60 mL of N-methylpyrrolidone. The solid was further washed with 60 mL of methanol and then dried at 100°C under reduced pressure for 15 hours to obtain 0.97 mmol of quinophthalone compound 3.

[0149] FT-IR: Wave number (cm -1 ) = 3310 (amide NH), 3100-3000 (aromatic CH), 1730 (ester C=O), 1640 (amide C=O), 1625 (quinophthalone C=O). The IR chart is shown in Figure 3.

[0150] Quinophthalone compound 3 was identified from the peak obtained in positive mode by laser desorption ionization using a time-of-flight mass spectrometer (rapifleX (registered trademark) (TOF-MS, manufactured by Bruker Daltonics)). MS (m / z) = 947.3 ([M+H] + )

[0151] The heat resistance, color fixation, and light absorption in the ultraviolet region of the quinophthalone compound 1 obtained as described above were evaluated by thermogravimetry. For comparison, the following compounds 4 and 5 were also similarly evaluated.

[0152] Compound 4: 2,3-dihydro-1,3-dioxy-2-(2-quinolinyl)-1H-indene-5-carboxylic acid

[0153] Compound 5: Pigment Yellow 147 (AGR)

[0154] (Heat Resistance) Quinophthalone Compound 1 was subjected to thermogravimetric measurement using a thermogravimetric analyzer (manufactured by Waters, device name: TGA5500) to evaluate its heat resistance. The amount of sample used per measurement was 1 to 2 mg. The measurement was performed in a nitrogen atmosphere, with the temperature rising from 50°C to 600°C at a rate of 10°C per minute. The results are shown in Figures 4 and 5. The Td5 (5% weight loss temperature) was 440°C for quinophthalone compound 1, 380°C for compound 4, and 450°C for compound 5.

[0155] (Color Fixation) Quinophthalone Compound 1 and Compound 4 were dispersed in 2 g of N-methylpyrrolidone, and 0.986 g of resin (Cyclomer P (ACA) Z320, manufactured by Daicel Chemical Industries, Ltd.) and 0.014 g of a 4 wt % solution of leveling agent (BYK-333, manufactured by BYK-Chemie Co., Ltd.) in propylene glycol monomethyl ether acetate (PMA) were added to prepare a solution. The resulting solution was applied to a glass plate to a thickness of 2 μm and prebaked on a hot plate at 100° C. for 3 minutes. The film was then kept in a thermostatic bath at 230° C. for 2 hours, and the film after the keeping was visually observed to confirm the color fixation. Quinophthalone Compound 1: No change in color before and after keeping Compound 4: Significant color fading after keeping

[0156] (Light absorption in the ultraviolet region) A solution was prepared by dissolving quinophthalone compound 1 in NMP as a solvent so that the concentration in NMP was 1.0 mmol / L. Similarly, solutions were prepared by dissolving compounds 4 and 5. The absorption spectra of these solutions were measured using a spectrophotometer (manufactured by JASCO Corporation, instrument name: V-770). The results are shown in FIG. 6.

[0157] As shown in the thermogravimetric results in Figures 4 and 5, quinophthalone compound 1 had improved heat resistance compared to its raw material, compound 4, and also exhibited heat resistance comparable to that of compound 5, a conventional yellow pigment (Pigment Yellow 147). On the other hand, as shown in Figure 6, the light absorption at 365 nm of quinophthalone compound 1 was significantly suppressed compared to compound 5. Furthermore, as is clear from the evaluation of color fixation, when compound 4, a raw material for quinophthalone compound 1, was used, significant color fading was observed due to heat. In contrast, the quinophthalone compounds showed no color change due to heat, indicating their heat resistance.

[0158] <Preparation of Carboxylic Acid-Containing Resin> Synthesis Example 1 (Synthesis of Carboxylic Acid-Containing Photosensitive Resin (A1) Using a Phenol Compound as a Starting Material) 119.4 parts of a novolak cresol resin (trade name "Shounol CRG-951", manufactured by Showa Polymer Co., Ltd., OH equivalent: 119.4), 1.19 parts of potassium hydroxide, and 119.4 parts of toluene were introduced into an autoclave equipped with a thermometer, a nitrogen introducing device / alkylene oxide introducing device, and a stirrer, and the system was purged with nitrogen while stirring, and heated to a temperature of 125 to 132°C and 0 to 4.8 kg / cm. Next, 63.8 parts of propylene oxide were slowly added dropwise, and the temperature was raised to 125 to 132°C and 0 to 4.8 kg / cm. ２The mixture was reacted at 100°C for 16 hours. The mixture was then cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to the reaction solution to neutralize the potassium hydroxide, yielding a propylene oxide reaction solution of novolac cresol resin with a solids content of 62.1% and a hydroxyl value of 182.2 mgKOH / g (307.9 g / eq.). This solution contained an average of 1.08 moles of propylene oxide added per equivalent of phenolic hydroxyl group. 293.0 parts of the resulting propylene oxide reaction solution of novolac cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone, and 252.9 parts of toluene. A reactor equipped with a stirrer, thermometer, and air inlet tube was charged with air at a rate of 10 ml / min and the mixture was reacted at 110°C for 12 hours with stirring. The water produced by the reaction was distilled as an azeotrope with toluene, and 12.6 parts of water were distilled off. The mixture was then cooled to room temperature, neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. The toluene was then removed by distillation using an evaporator, while being replaced with 118.1 parts of diethylene glycol monoethyl ether acetate, to obtain a novolac acrylate resin solution. Next, 332.5 parts of the resulting novolac acrylate resin solution and 1.22 parts of triphenylphosphine were introduced into a reactor equipped with a stirrer, thermometer, and air inlet tube. Air was blown in at a rate of 10 ml / min. While stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added. The mixture was allowed to react at 95 to 101°C for 6 hours, cooled, and then discharged. The solids content of the resin solution thus obtained was 65%, and the acid value of the solids was 87.7 mgKOH / g.

[0159] Synthesis Example 2 (Synthesis of Carboxylic Acid-Containing Photosensitive Resin (A4-1) Using Epoxy Compound as Starting Material) 1,070 g (number of glycidyl groups (total number of aromatic rings): 5.0 mol) of orthocresol novolac epoxy resin [EPICLON (registered trademark) N-695 manufactured by DIC Corporation, softening point 95°C, epoxy equivalent 214, average functionality 7.6], 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged into 600 g of diethylene glycol monoethyl ether acetate, and the mixture was heated to 100°C with stirring to obtain a homogeneous solution. Next, 4.3 g of triphenylphosphine was charged, heated to 110°C, and reacted for 2 hours, and then heated to 120°C and reacted for an additional 12 hours. To the resulting reaction solution, 415 g of an aromatic hydrocarbon (Solvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added, and the mixture was reacted at 110°C for 4 hours. The mixture was then cooled to obtain a carboxylic acid-containing photosensitive resin solution using an epoxy compound as a starting material. The solids content of the resin solution thus obtained was 65%, and the acid value of the solids content was 89 mgKOH / g.

[0160] Synthesis Example 3 (Synthesis of Carboxylic Acid-Containing Photosensitive Resin (A2-1) Having a Urethane Skeleton) Into a flask equipped with a stirrer and a reflux condenser were charged 300.0 g of NC-3000 (epoxy equivalent: 255 g / eq.) manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin having a plurality of epoxy groups in one molecule, 84.7 g of acrylic acid as a monocarboxylic acid having an ethylenically unsaturated group in the molecule, 1.8 g of 2,6-ditertiarybutyl-4-methylphenol as a thermal polymerization inhibitor, 1.8 g of triphenylphosphine as a reaction catalyst, and 207.2 g of propylene glycol monomethyl ether acetate (PGMEA) as a reaction solvent, and the mixture was reacted at a reaction temperature of 98°C until the acid value of the reaction liquid reached 1 mgKOH / g or less, thereby obtaining a hydroxyl group-containing epoxy carboxylate compound. Next, 335.5 g of the resulting reaction liquid containing a hydroxyl group-containing epoxy carboxylate compound, 60.7 g of dimethylol butanoic acid as a carboxyl group-containing diol compound, 104.1 g of 2,4,4-trimethylhexamethylene diisocyanate as an aliphatic diisocyanate compound, and 88.7 g of PGMEA as a reaction solvent were charged and reacted at a reaction temperature of 80°C. The reaction was terminated when the NCO content reached 0.1% or less, yielding a carboxylic acid-containing photosensitive resin (A2-1) (solids content 65%) having a urethane skeleton. The acid value of the solids of the carboxylic acid-containing photosensitive resin (A2-1) having a urethane skeleton was 60 mgKOH / g.

[0161] Synthesis Example 4 (Synthesis of Carboxylic Acid-Containing Photosensitive Resin (A2-2) Having a Urethane Skeleton) Into a 5-liter separable flask equipped with a thermometer, a stirrer, and a reflux condenser, 1,245 g of polycaprolactone diol (PLACCEL 208, molecular weight 830, manufactured by Daicel Chemical Industries, Ltd.) as a polymer polyol, 201 g of dimethylolpropionic acid as a dihydroxyl compound having a carboxyl group, 777 g of isophorone diisocyanate as a polyisocyanate, 119 g of 2-hydroxyethyl acrylate as a (meth)acrylate having a hydroxyl group, and 0.5 g each of p-methoxyphenol and di-t-butyl-hydroxytoluene were added. The mixture was heated to 60°C with stirring, and the mixture was stopped, and 0.8 g of dibutyltin dilaurate was added. When the temperature inside the reaction vessel began to decrease, the mixture was heated again, and stirring was continued at 80°C. The absorption spectrum of the isocyanate group (at 2280 cm) was measured by infrared absorption spectroscopy. －１ The reaction was terminated upon confirmation that the carboxylic acid-containing photosensitive resin (A2-2) had disappeared, yielding a viscous liquid urethane skeleton-containing carboxylic acid-containing photosensitive resin (A2-2). The resulting urethane skeleton-containing carboxylic acid-containing photosensitive resin (A2-2) was adjusted to a solids content of 50 mass% using carbitol acetate. The acid value of the solid content of the urethane skeleton-containing carboxylic acid-containing photosensitive resin (A2-2) was 47 mgKOH / g.

[0162] Synthesis Example 5 (Synthesis of Carboxylic Acid-Containing Copolymeric Photosensitive Resin (A3)) In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, 325.0 parts of dipropylene glycol monomethyl ether as a solvent was heated to 110°C, and a mixture of 174.0 parts of methacrylic acid, 174.0 parts of ε-caprolactone-modified methacrylic acid (average molecular weight 314), 77.0 parts of methyl methacrylate, 222.0 parts of dipropylene glycol monomethyl ether, and 12.0 parts of t-butylperoxy 2-ethylhexanoate (Perbutyl (registered trademark) O manufactured by NOF Corporation) as a polymerization catalyst was added dropwise over 3 hours, and the mixture was further stirred at 110°C for 3 hours to inactivate the polymerization catalyst, thereby obtaining a resin solution. After cooling this resin solution, 289.0 parts of 3,4-epoxycyclohexyl methacrylate (Cyclomer A200 manufactured by Daicel Corporation), 3.0 parts of triphenylphosphine, and 1.3 parts of hydroquinone monomethyl ether were added, and the mixture was heated to 100°C and stirred to carry out a ring-opening addition reaction of the epoxy groups, yielding a solution of carboxylic acid-containing copolymer resin (A3). The resin (A3) solution thus obtained had a weight-average molecular weight (Mw) of 15,000, a solids content of 57%, and an acid value of 79.8 mg KOH / g of the solids. The weight-average molecular weight was measured by high-performance liquid chromatography using a pump LC-6AD manufactured by Shimadzu Corporation and three columns, Shodex (registered trademark) KF-804, KF-803, and KF-802 manufactured by Showa Denko K.K., connected together.

[0163] Synthesis Example 6 (Synthesis of carboxylic acid-containing photosensitive resin (A4-2) using an epoxy compound as a starting material) 700 g of diethylene glycol monoethyl ether acetate was added to 1070 g of orthocresol novolac epoxy resin (EPICLON (registered trademark) N-695 manufactured by DIC Corporation, softening point 95 ° C., epoxy equivalent 214, average number of reactive groups 7.6) (number of glycidyl groups (total number of aromatic rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were added, heated to 100 ° C. and stirred, and dissolved uniformly. Next, 4.3 g of triphenylphosphine was added, heated to 110 ° C. and reacted for 2 hours, and then 1.6 g of triphenylphosphine was added, and the temperature was raised to 120 ° C. and the reaction was continued for another 12 hours. To the resulting reaction solution, 562 g of an aromatic hydrocarbon (Solvesso 150) and 684 g (4.5 mol) of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110°C for 4 hours. Furthermore, 142.0 g (1.0 mol) of glycidyl methacrylate was added to the resulting reaction solution, and the reaction was carried out at 115°C for 4 hours, yielding a solution of a carboxylic acid-containing photosensitive resin (A4-2) using an epoxy compound as a starting material. The solids content of the resin (A4-2) solution thus obtained was 65%, and the acid value of the solids content was 87 mgKOH / g.

[0164] <(A1) Preparation of photosensitive compositions using carboxylic acid-containing photosensitive resins prepared from phenolic compounds as starting materials> The components shown in Tables 1 to 5 below were blended and mixed to obtain the photosensitive compositions shown in the tables. Note that each value in the tables indicates parts by mass or % by mass converted to solid content.

[0165] The carboxylic acid-containing resin in Table 1 below is the carboxylic acid-containing photosensitive resin of Synthesis Example 1 or 2. The components other than the carboxylic acid-containing resin in Table 1 below are as follows. Melamine: manufactured by Nissan Chemical Industries, Ltd. DICY: dicyandiamide, manufactured by Mitsubishi Chemical Corporation Quinophthalone Compound 1,2,3 (yellow): the above quinophthalone compound 1,2,3 Pigment Yellow 147, manufactured by BASF Paliogen Blue L 6480, manufactured by BASF, an anthraquinone-based blue colorant, transmittance at a light wavelength of 365 nm: 30% (15% by mass in terms of solid content in SP-3900 resin manufactured by Resonac Corporation, film thickness 18 μm) Pigment Blue 15:3, a phthalocyanine-based blue colorant, manufactured by DIC Corporation FARSTOGEN BLUE FA5380, transmittance at a light wavelength of 365 nm: 5% (15% by mass in terms of solid content in SP-3900 resin manufactured by Resonac Corporation, film thickness 18 μm) m) Pigment Violet 37, BASF CROMOPHTAL VIOLET B, purple colorant Solvent Green 5, Arimoto Chemical Industry Co., Ltd. PLAST YELLOW 8025, green colorant KS-66: silicone defoamer manufactured by Shin-Etsu Chemical Co., Ltd. Omnirad TPO-L: ethyl (2,4,6-trimethylbenzoyl)phenyl phosphinate manufactured by IGM Resins B.V. jER (registered trademark) 828: bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation DPHA: dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd. Silica: SO-C2 manufactured by Admatec Co., Ltd.

[0166] <Preparation of Evaluation Substrate> Each photosensitive composition was applied to a single-sided printed wiring board with a copper thickness of 15 μm, which had been pretreated with CZ8100 manufactured by MEC Co., Ltd., so that the thickness would be 20 μm after drying, and the resulting coating was dried at 80 ° C. for 30 minutes in a hot air circulation drying oven to obtain a dried coating film. The resulting dried coating film was irradiated with a step tablet (Stuffer 41 stage) using a DXP-3580 manufactured by Oak Manufacturing Co., Ltd., at an exposure dose of * 1 (7 stages) or * 2 (8 stages). Next, development was performed for 60 seconds using a 1% by mass sodium carbonate solution at 30 ° C. under a spray pressure of 0.2 MPa, and then cured for 60 minutes at 150 ° C. in a hot air circulation drying oven to obtain an evaluation substrate having a cured film.

[0167] <Evaluation of Color Tone> The color tone of the surface of the cured film on each evaluation substrate was visually confirmed. The evaluation results are shown in Tables 2 to 4.

[0168] <Evaluation of Appearance> The surface of the cured film on each evaluation substrate was observed under an optical microscope at approximately 25x magnification. The evaluation criteria were as follows. The evaluation results are shown in Tables 2 to 4. ○: Uniform coloring ×: Uneven coloring pattern observed

[0169] <Evaluation of heat resistance (discoloration after reflow)> Each photosensitive composition was applied to a single-sided printed wiring board with a copper thickness of 15 μm, which had been pretreated with CZ8100 manufactured by MEC Co., Ltd., so that the thickness would be 20 μm after drying, and the board was dried in a hot air circulation drying oven at 80 ° C. for 30 minutes to obtain a dried coating film. The resulting dried coating film was then irradiated entirely onto the board using a DXP-3580 manufactured by Oak Manufacturing Co., Ltd., with an exposure amount of *1 (7 steps) or *2 (8 steps) on a step tablet (Stuffer 41 steps). Next, development was performed for 60 seconds using a 1% by mass sodium carbonate solution at 30 ° C. under a spray pressure of 0.2 MPa, and then cured for 60 minutes at 150 ° C. in a hot air circulation drying oven to obtain an evaluation substrate having a cured film. The cured film on the obtained evaluation substrate was measured using a spectrophotometer SPECTROPHOTOMETER CM-2600d manufactured by Konica Minolta, Inc., and L*a*b* value analysis was performed using color management software CM-S100W SpectraMagic NX ver. 2.6 manufactured by Konica Minolta, Inc. The result was designated as (1). Furthermore, the evaluation substrate was passed through a reflow furnace at a temperature of 260°C, and the L*a*b* value analysis of the cured film was similarly performed, and the result was designated as (2). The heat resistance of the photosensitive composition was then evaluated based on the numerical difference between the L*a*b* values ​​(1) and (2) (discoloration after reflow). The evaluation criteria were as follows. The evaluation results are shown in Tables 2 to 4. Good: The difference in L*a*b* values ​​is less than 4.0, and the heat resistance is excellent. Poor: The difference in L*a*b* values ​​is 4.0 or more, and the heat resistance is somewhat poor.

[0170] <Evaluation of Resolution> Cured films for evaluation substrates were prepared according to the above <Preparation of Evaluation Substrates>, and the 150 μm openings of each evaluation substrate were observed with a scanning electron microscope to measure the opening diameter (actual size) relative to the design opening diameter (150 μm). The opening dimensions were evaluated for each of the top and bottom of the opening according to the following criteria. The evaluation results are shown in Tables 2 to 4. ⊚: The difference in actual size from the design opening diameter of 150 μm is less than 10 μm. ○: The difference in actual size from the design opening diameter of 150 μm is 10 μm or more but less than 20 μm. ×: The difference in actual size from the design opening diameter of 150 μm is 20 μm or more.

[0171] <Evaluation of Dispersion Stability> Each photosensitive composition obtained as described above was sealed and stored in an atmosphere at 15°C for one month, and then separation of the colorant upon opening was confirmed. The evaluation criteria were as follows. The evaluation results were as shown in Tables 2 to 4. ○: No change in state was observed ×: Separation of the colorant was observed

[0172] <Sensitivity Evaluation> Each photosensitive composition was applied to the entire surface of a single-sided printed wiring board with a copper thickness of 15 μm, which had been pretreated using CZ8100 manufactured by MEC Co., Ltd., so that the thickness would be 20 μm after drying, and the composition was dried in a hot air circulation drying oven at 80° C. for 30 minutes to obtain a dried coating film. Next, the dried coating film was subjected to 150 mJ / cm 2 irradiation through a step tablet (Stuffer 41 stage) using DXP-3580 manufactured by Oak Manufacturing Co., Ltd. ２ The film was exposed to light at 1000 K and then developed for 60 seconds with a 1% by weight sodium carbonate solution at 30°C under a spray pressure of 0.2 MPa, and the remaining step tablet pattern was read. The greater the number of remaining steps, the better the sensitivity, which is preferable. The evaluation results are shown in Table 5.

[0173]

[0174]

[0175]

[0176]

[0177]

[0178] <(A2) Preparation of Photosensitive Composition Using Carboxylic Acid-Containing Photosensitive Resin Having a Urethane Skeleton> The components shown in Table 6 below were blended and mixed to obtain the photosensitive compositions shown in the table. Note that each value in the table indicates parts by mass or % by mass converted to solid content. The carboxylic acid-containing resin in Table 6 below is the carboxylic acid-containing photosensitive resin of Synthesis Example 3 or 4 above, or UXE-3000 (carboxylic acid-containing photosensitive resin having a urethane skeleton, acid value: 98 mgKOH / g) manufactured by Nippon Kayaku Co., Ltd. Furthermore, each component other than the carboxylic acid-containing resin in Table 6 below is the same as that shown in Table 1.

[0179] The color tone, heat resistance, and resolution were evaluated in the same manner as above, and the evaluation results are shown in Table 6.

[0180] <Evaluation of PCT Resistance> Each photosensitive composition was applied by screen printing to a single-sided printed wiring board with a copper thickness of 15 μm that had been pretreated with CZ8100 manufactured by MEC Co., Ltd., and dried in a drying oven at 80° C. for 30 minutes to form a tack-free resin layer. Next, an exposure device equipped with a high-pressure mercury short arc lamp was used to apply a 100 mJ / cm ２ After the pattern was exposed to an exposure dose of 1000 mJ / cm, development was performed for 60 seconds using a 1% by mass aqueous solution of sodium carbonate at 30°C under a spray pressure of 0.2 MPa to obtain a resin layer pattern. This pattern was then exposed to an exposure dose of 1000 mJ / cm in a UV conveyor furnace. ２ After irradiating with ultraviolet light under the conditions of , the film was cured by heating at 160°C for 60 minutes. The properties of the cured film on the resulting printed wiring board (evaluation board) were evaluated as follows. The resulting printed wiring board (evaluation board) was placed in a high-pressure, high-temperature, high-humidity chamber at 121°C, 2 atmospheres, and 100% humidity for 300 hours, and the change in the state of the cured film was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 6. ⊚: No significant swelling or discoloration ◯: No significant peeling, but partial peeling or discoloration

[0181] <Evaluation of Flexibility> A flexible printed circuit board on which a circuit with a copper thickness of 12 μm was formed was prepared, and pre-treated using a CZ8100 manufactured by MEC Co., Ltd. Thereafter, each resin composition constituting the resin layer was applied to the pre-treated flexible printed circuit board so that the film thickness after drying would be the film thickness described in the Examples, and the substrate was dried at 90°C for 10 minutes in a hot air circulation drying oven to form a resin layer. First, an exposure apparatus (EXP-2960) equipped with a mercury short arc lamp was used to expose the substrate to 200 mJ / cm through a negative mask. ２The exposed evaluation specimen was then subjected to pattern exposure to form openings with a diameter of 300 μm. The exposed evaluation specimen was then heat-treated at 80° C. for 40 minutes, followed by development at 30° C. for 1 minute using a 1% by mass aqueous sodium carbonate solution. The developed evaluation specimen was further thermally cured at 150° C. for 60 minutes to produce a flexible printed wiring board having a cured laminate structure, which was used as an evaluation specimen. The evaluation specimen was bent 180° with the laminate structure facing outward, sandwiched between two flat plates, and a load G (a standard weight of 500 g) was applied for 10 seconds to break the laminate structure. The laminate structure at the bent portion was then inspected using an optical microscope for cracks. This cycle was recorded as the number of times before cracks occurred. The evaluation criteria were as follows. The evaluation results were as shown in Table 6. ○: 3 or more bends ×: Less than 3 bends

[0182]

[0183] <(A3) Preparation of Photosensitive Composition Using Carboxylic Acid-Containing Copolymeric Photosensitive Resin> The components listed in Table 7 below were blended and mixed to obtain the photosensitive compositions listed in the same table. The values ​​in the table represent parts by mass or % by mass calculated as solid content. The carboxylic acid-containing resin in Table 7 below is the carboxylic acid-containing copolymeric photosensitive resin of Synthesis Example 5 above, or a separately prepared carboxylic acid-containing copolymeric photosensitive resin (carboxylic acid-containing copolymeric photosensitive resin (*) (acid value 122 KOH / mg) obtained by adding glycidyl methacrylate to a copolymer of methyl methacrylate, methacrylic acid, and acrylic acid). The components other than the carboxylic acid-containing resin in Table 7 below are the same as those listed in Table 1.

[0184] The color tone, heat resistance, and resolution were evaluated in the same manner as above, and the evaluation results are shown in Table 7.

[0185] <Evaluation of Haze Stability> Each photosensitive composition obtained as described above was applied to a 25 μm thick PET film (E-5041 manufactured by Toyobo Co., Ltd.) using an applicator, and dried for 30 minutes in a hot air circulation drying oven at 80 ° C. to prepare a dry film with a film thickness of 10 μm. The standard drying conditions after application were 70 ° C. for 30 minutes. Compared to the standard conditions, drying was performed at a drying temperature of +3 ° C. and a drying time of +5 minutes, and the haze was measured after exposure, development, and thermal curing under the following conditions, and the haze difference from the standard conditions was calculated (condition 1). In addition, compared to the standard conditions, drying was performed at a drying temperature of +3 ° C. and a drying time of +10 minutes, and the haze was measured after exposure, development, and thermal curing under the following conditions, and the haze difference from the standard conditions was calculated (condition 2). Exposure conditions: Using a DXP-3580 manufactured by Oak Manufacturing Co., Ltd., the entire surface was irradiated with an exposure amount equivalent to 7 steps using a step tablet (Stuffer 41 steps). Developing conditions: Developed for 60 seconds with a 1% by mass sodium carbonate solution at 30° C. and a spray pressure of 0.2 MPa. Heat curing conditions: Heated in a hot air circulation drying oven at 150° C. for 60 minutes.

[0186] The haze value of each coating film portion of the cured product for evaluation was measured using 1 mm soda lime glass as a standard. The haze value was measured using a haze meter (Haze Meter NDH 7000II manufactured by Nippon Denshoku Industries Co., Ltd.). The haze value was measured in accordance with JIS K7361:2000. The evaluation criteria were as follows. The evaluation results are shown in Table 7. ⊚: Haze difference due to drying conditions is less than 3%. ○: Haze difference due to drying conditions is 3% or more but less than 10%. ×: Haze difference due to drying conditions is 10% or more.

[0187]

[0188] <(A4) Preparation of photosensitive composition using carboxylic acid-containing photosensitive resin using epoxy compound as starting material> Each of the components shown in Table 8 below was blended and mixed to obtain each of the photosensitive compositions shown in the same table. Note that each value in the table indicates parts by mass or mass% converted to solid content. The carboxylic acid-containing resin in Table 8 below is the carboxylic acid-containing photosensitive resin of Synthesis Example 2 or 6 above. Furthermore, each of the components other than the carboxylic acid-containing resin in Table 8 below is the same as those shown in Table 1.

[0189] The color tone, heat resistance, and resolution were evaluated in the same manner as above, and the evaluation results are shown in Table 8.

[0190] <Resolution Evaluation> Each photosensitive composition was applied to a single-sided printed wiring board with a copper thickness of 15 μm, pretreated with a CZ8100 manufactured by MEC Co., Ltd., to an entire surface to a thickness of 20 μm after drying. The composition was then dried in a hot air circulation drying oven at 80 °C for 30 minutes to obtain a dried coating. The resulting dried coating was irradiated with a step tablet (41-stage Stuffer) using a DXP-3580 manufactured by Oak Manufacturing Co., Ltd., at an exposure dose equivalent to 7 steps. The composition was then developed with a 1% by weight sodium carbonate solution at 30 °C under a spray pressure of 0.2 MPa for 60 seconds to form a 150 μm opening, which was then cured in a hot air circulation drying oven at 150 °C for 60 minutes to obtain an evaluation substrate with a cured film. The 150 μm opening of each evaluation substrate was observed using a scanning electron microscope, and the opening diameter (actual size) relative to the design opening diameter (150 μm) was measured. The opening dimensions were evaluated for the top and bottom of the opening according to the following criteria. The evaluation results are shown in Table 8. ⊚: The difference in actual size from the designed opening diameter of 150 μm is less than 10 μm. ○: The difference in actual size from the designed opening diameter of 150 μm is 10 μm or more and less than 20 μm. ×: The difference in actual size from the designed opening diameter of 150 μm is 20 μm or more.

[0191] <Evaluation of HAST resistance> Etching rate 1.0 μm / m with CZ-8101B ２Each photosensitive composition was applied to a substrate having a comb-shaped pattern with L / S = 20 / 20 μm processed under the above conditions to a film thickness of approximately 20 μm, and the entire surface was exposed to light. 10 minutes after exposure, the substrate was developed with a 1% by mass aqueous solution of sodium carbonate at 30°C for a development time twice the breakpoint (shortest development time). Subsequently, the substrate was exposed to a UV conveyor (metal halide lamp manufactured by Oak Manufacturing Co., Ltd.) with an accumulated exposure dose of 2000 mJ / cm. ２ The substrate was exposed to light at 1000 W at 170° C. for 60 minutes in a thermal circulation box furnace, and cured to obtain a substrate having a cured film. After that, electrodes were connected and a HAST test was carried out under conditions of 130° C., 85%, and 5 V. The resistance value was 1.0×10 ７ The time required for the resistance value to become less than Ω was measured. The evaluation criteria were as follows. The evaluation results are shown in Table 8. ⊚: The resistance value of the cured film after 400 hours was 1.0 × 10 ７ Ω or more ○: The resistance value of the cured film after 350 hours is 1.0 × 10 ７ Ω or more △: The resistance value of the cured film after 300 hours is 1.0 × 10 ７ Ω or more ×: Resistance value of the cured film after 300 hours is 1.0 × 10 ７ Less than Ω

[0192]

Claims

1. A photosensitive composition comprising: (A) a carboxylic acid-containing resin; (B) a photopolymerization initiator; (C) a photosensitive monomer; and (D) a colorant, wherein the (A) carboxylic acid-containing resin comprises at least one resin selected from the group consisting of (A1) a carboxylic acid-containing photosensitive resin made from a phenol compound as a starting material, (A2) a carboxylic acid-containing photosensitive resin having a urethane skeleton, (A3) a carboxylic acid-containing copolymer photosensitive resin, and (A4) a carboxylic acid-containing photosensitive resin made from an epoxy compound as a starting material, and the (D) colorant is a compound represented by the following formula (1): (In formula (1), R １ and R ２ are each independently —OH, —OR ａ , -NR ｂ R ｃ , —C(═O)NR ｂ R ｃ , halogen atoms, —CN, —NO ２ , -COOH, -C(=O)OR ｄ , -OC(=O)R ｄ , -COOM ａ , -SO ３ H, -S(=O) ２ OR ｄ , -O-S(=O)2R ｄ , -SO ３ M ａ a hydrocarbon group having 1 to 30 carbon atoms, a group represented by formula (2) and a group represented by formula (3), wherein the hydrocarbon group having 1 to 30 carbon atoms may be substituted; R ３ are each independently —OH, —OR ａ , -NR ｂ R ｃ , —C(═O)NR ｂ R ｃ , halogen atoms, —CN, —NO ２ , -COOH, -C(=O)OR ｄ , -OC(=O)R ｄ , -COOM ａ , -SO ３ H, -S(=O) ２ OR ｄ , —O—S(═O) ２ R ｄ , -SO ３ M ａ and a hydrocarbon group having 1 to 30 carbon atoms, which may be substituted; m is an integer of 0 to 5; n is an integer of 0 to 5; p is an integer of 0 to 4; R ａ is an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the aralkyl group may be substituted; R ｂ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the aralkyl group may be substituted; R ｃ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the aralkyl group may be substituted; R ｄ represents an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the aralkyl group may be substituted; M ａ is sodium or potassium, with the proviso that m+n is an integer of 1 or more, and formula (1) has at least one group selected from a group represented by the following formula (2) and a group represented by the following formula (3), In formula (2) and formula (3), X １ , X ２ , X ３ and X ４ are each independently —OH, —OX ａ , -NX ｂ X ｃ , -C(=O)NX ｂ X ｃ , halogen atoms, —CN, —NO ２ , -COOH, -C(=O)OX ｄ , -OC(=O)X ｄ , -COOM ｂ , -SO ３ H, -S(=O) ２ OX ｄ , —O—S(═O) ２ X ｄ , -SO ３ M ｂ and a hydrocarbon group having 1 to 30 carbon atoms, wherein adjacent groups may be bonded to each other to form a carbocyclic or heterocyclic ring, and the hydrocarbon group having 1 to 30 carbon atoms may be substituted; L １ and L ２ are each independently a linking group selected from a single bond, —O—, —C(═O)O—, —S(═O)2O— and —NH—C(═O)—, q is an integer of 0 to 6, r is an integer of 0 to 3, s is an integer of 0 to 5, t is an integer of 0 to 4, and X ａ represents an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the aralkyl group may be substituted; X ｂ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group and the aralkyl group may be substituted; X ｃ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group and the aralkyl group may be substituted; X ｄ represents an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group, and the alkyl group, the alkenyl group, the alkynyl group, and the aralkyl group may be substituted; M ｂ is sodium or potassium.

2. The photosensitive composition according to claim 1, wherein the content of the quinophthalone compound is 0.1 to 5 parts by mass, calculated as solid content, per 100 parts by mass of the carboxylic acid-containing resin (A).

3. The photosensitive composition according to claim 1, wherein the formula (1) has at least two groups selected from the group represented by the formula (2) and the group represented by the formula (3).

4. The formula (1) is a group selected from the group represented by the formula (2) and the group represented by the formula (3), R １ and R is a group selected from the group represented by the formula (2) and the group represented by the formula (3). ２ The photosensitive composition of claim 1 , comprising at least one of 5. A laminated structure comprising a first film and a resin layer provided on the first film, wherein the resin layer is made of the photosensitive composition according to claim 1.

6. A cured product of the photosensitive composition according to claim 1 or the resin layer of the laminate structure according to claim 5.

7. An electronic part comprising the cured product according to claim 6.

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