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

Abstract

To provide a photosensitive composition having excellent resolution and heat resistance.MEANS: The photosensitive composition contains (A) a carboxylic acid-containing resin, (B) a photopolymerization initiator, (C) a photosensitive monomer, and (D) a colorant. The photosensitive monomer (C) contains at least one acrylate selected from a polyfunctional (meth)acrylate having a bisphenol A skeleton, a polyfunctional (meth)acrylate having an alicyclic skeleton, and a polyfunctional (meth)acrylate having a dipentaerythritol skeleton. The colorant (D) contains a quinophthalone compound represented by the following formula (1).SELECTED DRAWING: None

Description

[Technical Field]

[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. [Background technology]

[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 usually contain a colorant, and it is common to use a mixture of blue and yellow colorants instead of conventional green colorants (see, for example, Patent Document 1). Taking into account resolution, deep curing, and the like, it is preferable to use a colorant that has low absorption in the exposure wavelength region (around 365 nm). Quinophthalone-based yellow colorants are known as such colorants. From the standpoint of heat resistance, anthraquinone-based yellow colorants, such as Pigment Yellow 147, are also known.

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

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-7974 [Patent Document 2] Patent No. 3964326 Summary of the Invention [Problem to be solved by the invention]

[0006] However, there is still room for improvement in resolution and heat resistance in photosensitive compositions containing a colorant. 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. [Means for solving the problem]

[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 polyfunctional (meth)acrylate as a photosensitive monomer. The present invention is based on this discovery. Specifically, the gist of the present invention is as follows.

[0008] [1] (A) a carboxylic acid-containing resin; (B) a photopolymerization initiator; (C) a photosensitive monomer; (D) a colorant; A photosensitive composition comprising: the (C) photosensitive monomer contains at least one (meth)acrylate selected from the group consisting of a polyfunctional (meth)acrylate having a bisphenol A skeleton, a polyfunctional (meth)acrylate having an alicyclic skeleton, and a polyfunctional (meth)acrylate having a dipentaerythritol skeleton, The colorant (D) is a compound represented by the following formula (1): [ka] (In formula (1), R1 and R2 each independently represent -OH, -OR a , -NR b R c , -C(=O)NR b R c, halogen atoms, -CN, -NO2, -COOH, -C(=O)OR d , -OC(=O)R d , -COOM a , -SO3H, -S(=O)2OR d , -OS(=O)2R d , -SO3M 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 is optionally substituted; R3 each independently represents -OH, -OR a , -NR b R c , -C(=O)NR b R c , halogen atoms, -CN, -NO2, -COOH, -C(=O)OR d , -OC(=O)R d , -COOM a , -SO3H, -S(=O)2OR d , -OS(=O)2R d , -SO3M a and a hydrocarbon group having 1 to 30 carbon atoms, which may be substituted; m is an integer from 0 to 5, n is an integer from 0 to 5, p is an integer from 0 to 4, R 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; 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 drepresents 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, however, m+n is an integer equal to or greater than 1, Formula (1) has at least one group selected from the group represented by the following formula (2) and the group represented by the following formula (3), [ka] In formula (2) and formula (3), X1, X2, X3 and X4 each independently represent -OH, -OX a , -NX b X c , -C(=O)NX b X c , halogen atoms, -CN, -NO2, -COOH, -C(=O)OX d , -OC(=O)X d , -COOM b , -SO3H, -S(=O)2OX d , -OS(=O)2X d , -SO3M 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; L1 and L2 each independently represent a linking group selected from a single bond, -O-, -C(=O)O-, -S(=O)2O-, and -NH-C(=O)-; q is an integer from 0 to 6, r is an integer from 0 to 3, s is an integer from 0 to 5, t is an integer from 0 to 4, 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 brepresents 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.) A photosensitive composition comprising a quinophthalone compound represented by the formula: [2] The photosensitive composition according to [1], wherein the content of the quinophthalone compound is 0.1 to 5 parts by mass in terms of solid content per 100 parts by mass of the (A) carboxylic acid-containing resin. [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 any one of [1] to [3], wherein the formula (1) has at least one R1 selected from the group represented by the formula (2) and the group represented by the formula (3), and has at least one R2 selected from the group represented by the formula (2) and the group represented by the formula (3). [5] A laminated structure including a first film and a resin layer provided on the first film, 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]. [Effects of the Invention]

[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 photosensitive monomer. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is an FT-IR chart of quinophthalone compound 1 of an example. [Figure 2] 1 is an FT-IR chart of quinophthalone compound 2 of an example. [Figure 3] 1 is an FT-IR chart of quinophthalone compound 3 of an example. [Figure 4] 1 is a TG / DTA chart of quinophthalone compound 1 and compound 4 of the examples. [Figure 5] 1 is a TG / DTA chart of quinophthalone compound 1 and compound 5 of the examples. [Figure 6] 1 is a chart showing ultraviolet-visible absorption spectra of solutions of quinophthalone compound 1, compound 4, and compound 5 of the examples. DETAILED DESCRIPTION OF THE INVENTION

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

[0012] (A) Carboxylic acid-containing resin The (A) carboxylic acid-containing resin may be any resin having a carboxyl group, and known and commonly used resins can be used. The carboxylic acid-containing resin can be used alone or in combination of two or more. The carboxylic acid-containing resin can be made alkali-soluble by containing a carboxyl group. From the viewpoint of curability, it is preferable that the carboxylic acid-containing resin has a photosensitive group in the molecule in addition to the carboxyl group, but it is also possible to use only a carboxylic acid-containing resin without a photosensitive group. 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.

[0013] Specific examples of carboxylic acid-containing resins include the following compounds (which may be either oligomers or polymers): In this specification, (meth)acrylate is a general term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

[0014] (1) Carboxylic acid-containing resins obtained by copolymerizing unsaturated carboxylic acids such as (meth)acrylic acid with unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth)acrylates, and isobutylene.

[0015] (2) Carboxylic acid-containing urethane resins obtained by the polyaddition reaction of diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxylic acid-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and diol compounds such as polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.

[0016] (3) Carboxylic acid-containing photosensitive urethane resins obtained by polyaddition reaction of diisocyanates with 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, and monocarboxylic acid compounds having ethylenically unsaturated double bonds such as (meth)acrylic acid, partially acid anhydride-modified products thereof, carboxylic acid-containing dialcohol compounds, and diol compounds.

[0017] (4) A carboxylic acid-containing photosensitive urethane resin in which a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as a hydroxyalkyl (meth)acrylate, is added during the synthesis of the resin (2) or (3) to form a terminal (meth)acrylate.

[0018] (5) A carboxylic acid-containing photosensitive urethane resin that is (meth)acrylated at the end by adding a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, during the synthesis of the resin (2) or (3).

[0019] (6) A carboxylic acid-containing photosensitive resin obtained by reacting a bifunctional or more polyfunctional epoxy resin with (meth)acrylic acid and adding a dibasic acid anhydride to the hydroxyl groups present in the side chains.

[0020] (7) A carboxylic acid-containing photosensitive resin in which the hydroxyl groups of a bifunctional epoxy resin are further epoxidized with epichlorohydrin, and then (meth)acrylic acid is reacted with a multifunctional epoxy resin, and a dibasic acid anhydride is added to the resulting hydroxyl groups.

[0021] (8) Carboxylic acid-containing polyester resins obtained by reacting a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid with a bifunctional oxetane resin, and then adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to the resulting primary hydroxyl groups.

[0022] (9) A carboxylic acid-containing photosensitive resin obtained by reacting an epoxy compound having multiple epoxy groups in one molecule 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, such as (meth)acrylic acid, and then reacting the alcoholic hydroxyl groups of the resulting reaction product with a polybasic acid anhydride, such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic acid.

[0023] (10) A carboxylic acid-containing photosensitive resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, reacting the resulting reaction product with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.

[0024] (11) A carboxylic acid-containing photosensitive resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, reacting the resulting reaction product with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.

[0025] (12) A carboxylic acid-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins (1) to (11).

[0026] These carboxylic acid-containing resins are not limited to those listed above, and may be used alone or in combination. Among the above, carboxylic acid-containing resins synthesized using phenolic compounds as starting materials, such as carboxylic acid-containing resins (10) and (11), are preferably used because of their excellent HAST resistance and PCT resistance.

[0027] The acid value of the carboxylic acid-containing resin is preferably 40 to 150 mgKOH / g. By making the acid value of the carboxylic acid-containing resin 40 mgKOH / g or more, alkaline development becomes good. Furthermore, by making the acid value 150 mgKOH / g or less, it becomes easier to draw a good resist pattern. More preferably, it is 50 to 130 mgKOH / g.

[0028] 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. By making the weight-average molecular weight 2,000 or more, tack-free performance and resolution can be improved. Furthermore, by making the weight-average molecular weight 150,000 or less, developability and storage stability can be improved. A weight-average molecular weight of 5,000 to 15,000 is more preferred. The weight-average molecular weight can be measured by gel permeation chromatography (GPC).

[0029] The amount of the (A) carboxylic acid-containing resin in the photosensitive composition is preferably 10 to 50% by mass, calculated as solid content. By adjusting the amount to 10% by mass or more, the coating strength can be improved. By adjusting the amount to 50% by mass or less, the viscosity becomes appropriate and printability improves. A more preferred amount is 10 to 30% by mass.

[0030] (B) Photopolymerization initiator The photopolymerization initiator is added to initiate polymerization of the (A) carboxylic acid-containing resin and / or the (C) photosensitive monomer described below. 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, and bis-(2,6-dimethoxybenzoyl). )-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 methylbenzoyl, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; acylphosphinates such as ethyl (2,4,6-trimethylbenzoyl)phenylphosphonate; hydroxyacetophenones such as 1-hydroxycyclohexyl 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)phenyl]-2-morpholino-1-propanone, and 2-benzyl-2 acetophenones such as -dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl)]-1-[4-(4-morpholinyl)phenyl]-1-butanone and N,N-dimethylaminoacetophenone; thioxanthones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 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; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, and p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1-[ 4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) and other oxime esters; bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyr-1-yl)ethyl)phenyl]titanium and other titanocenes;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.

[0031] 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.

[0032] The content of the (B) photopolymerization initiator 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, relative to 100 parts by mass of the (A) carboxylic acid-containing resin.

[0033] (C) Photosensitive monomer The photosensitive composition of the present invention contains, as the (C) photosensitive monomer, at least one polyfunctional (meth)acrylate selected from the group consisting of polyfunctional (meth)acrylates having a bisphenol A skeleton, polyfunctional (meth)acrylates having an alicyclic skeleton, and polyfunctional (meth)acrylates having a dipentaerythritol skeleton. In the present invention, the use of the specific polyfunctional (meth)acrylate described above in combination with the (D) colorant described below further improves the resolution and heat resistance of the photosensitive composition. In particular, the use of a polyfunctional (meth)acrylate having a bisphenol A skeleton as the photosensitive monomer not only improves the resolution and heat resistance, but also reduces the difference in glossiness of the surface of the cured product (cured coating) before and after development, i.e., the rate of change in glossiness before and after development. The polyfunctional (meth)acrylate having a bisphenol A skeleton is preferably a bifunctional (meth)acrylate having a bisphenol A skeleton, and examples thereof include bisphenol A ethylene oxide adduct di(meth)acrylate, bisphenol A propylene oxide adduct di(meth)acrylate, bisphenol A diglycidyl ether (meth)acrylic acid adduct, and hydrogenated bisphenol A propylene oxide adduct di(meth)acrylate. Of these, bisphenol A ethylene oxide adduct di(meth)acrylate (ethoxylated bisphenol A (meth)acrylate) is preferred.

[0034] Furthermore, as the polyfunctional (meth)acrylate having an alicyclic skeleton, a bifunctional (meth)acrylate having an alicyclic skeleton is preferred. Conventionally, increasing the exposure dose to promote deep curing has been problematic in that halation occurs. However, bifunctional (meth)acrylates having an alicyclic skeleton have a relatively small molecular weight and are easily increased in molecular weight through photoreaction during exposure, thereby improving sensitivity and promoting deep curing without causing halation. Examples of bifunctional (meth)acrylates having an alicyclic skeleton include tricyclodecane dimethanol di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, and dicyclopentanyl di(meth)acrylate. Among these, tricyclodecane dimethanol di(meth)acrylate is preferred.

[0035] Furthermore, by using a polyfunctional (meth)acrylate having a dipentaerythritol skeleton, particularly a polyfunctional (meth)acrylate having a caprolactone-modified dipentaerythritol skeleton, in combination with a colorant (D) described below, traces of a negative film are less likely to remain on the coating surface when a negative film is laminated during exposure, resulting in an improved appearance of the cured product. Examples of polyfunctional (meth)acrylates having a caprolactone-modified dipentaerythritol skeleton include caprolactone-modified dipentaerythritol penta(meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate, and among these, caprolactone-modified dipentaerythritol hexa(meth)acrylate is preferred.

[0036] Further, examples of polyfunctional (meth)acrylates having a dipentaerythritol skeleton other than those mentioned above include dipentaerythritol di(meth)acrylate, EO-modified dipentaerythritol di(meth)acrylate, PO-modified dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, EO-modified dipentaerythritol tri(meth)acrylate, PO-modified dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, EO Examples of such dipentaerythritol tetra(meth)acrylates include modified dipentaerythritol tetra(meth)acrylate, PO-modified dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, EO-modified dipentaerythritol penta(meth)acrylate, PO-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, EO-modified dipentaerythritol hexa(meth)acrylate, and PO-modified dipentaerythritol hexa(meth)acrylate. In particular, the use of dipentaerythritol hexa(meth)acrylate improves the surface hardness of the cured product, but at the same time increases brittleness and reduces crack resistance. However, in the present invention, the use of dipentaerythritol hexa(meth)acrylate in combination with a colorant (D) described below can improve crack resistance.

[0037] In addition to the above, conventionally known (meth)acrylates may be used in combination as the photosensitive monomer. Examples include polyester (meth)acrylate, polyether (meth)acrylate, urethane (meth)acrylate, carbonate (meth)acrylate, and epoxy (meth)acrylate. 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, and trishydroxyethylisocyanuric acid. Examples of suitable photosensitive monomers include polyhydric alcohols such as acrylates or their alkylene oxide adducts or ε-caprolactone adducts; phenols such as phenoxy acrylate 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 or via diisocyanate urethane acrylate of polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, and polyester polyols, as well as methacrylates corresponding to the above acrylates. Such photosensitive monomers can also be used as reactive diluents.

[0038] The amount 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 amount 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. When the amount is 30 parts by mass or less, halation is unlikely to occur and good resolution can be obtained.

[0039] (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: [ka]

[0040] In formula (1), R1 and R2 each independently represent -OH, -OR a , -NR b R c , -C(=O)NR b R c , halogen atoms, -CN, -NO2, -COOH, -C(=O)OR d , -OC(=O)R d , -COOM a , -SO3H, -S(=O)2OR d , -OS(=O)2R d , -SO3M 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 is optionally substituted; R3 each independently represents -OH, -OR a , -NR b R c , -C(=O)NR b R c , halogen atoms, -CN, -NO2, -COOH, -C(=O)OR d , -OC(=O)R d , -COOMa , -SO3H, -S(=O)2OR d , -OS(=O)2R d , -SO3M a and a hydrocarbon group having 1 to 30 carbon atoms, which may be substituted; m is an integer from 0 to 5, n is an integer from 0 to 5, p is an integer from 0 to 4, R 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; 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, however, m+n is an integer equal to or greater than 1, Formula (1) has at least one group selected from the group represented by the following formula (2) and the group represented by the following formula (3).

[0041] [ka]

[0042] In formula (2) and formula (3), X1, X2, X3 and X4 each independently represent -OH, -OX a , -NX b X c, -C(=O)NX b X c , halogen atoms, -CN, -NO2, -COOH, -C(=O)OX d , -OC(=O)X d , -COOM b , -SO3H, -S(=O)2OX d , -OS(=O)2X d , -SO3M 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; L1 and L2 each independently represent a linking group selected from a single bond, -O-, -C(=O)O-, -S(=O)2O-, and -NH-C(=O)-; q is an integer from 0 to 6, r is an integer from 0 to 3, s is an integer from 0 to 5, t is an integer from 0 to 4, 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.

[0043] 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, and 2-ethylhexyl. 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. Specific examples thereof include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, butadienyl, pentenyl, pentadienyl, and hexadienyl. 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. Specific examples thereof include vinyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, butidienyl, pentynyl, pentidienyl, and 1-hexynyl. The aralkyl group is a group in which one hydrogen atom of an alkyl group is substituted with an aryl group, and examples thereof 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 is a group having one or more carbon atoms, and includes alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, aryl groups, aralkyl groups, and the like. 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 its ring-constituting atoms are carbon atoms, and examples thereof include 4- to 20-membered rings, preferably 4- to 14-membered rings. The carbocyclic ring may be aromatic or non-aromatic, and may be monocyclic or polycyclic. Examples thereof include cycloalkanes (e.g., cyclopropane, cyclopentane, cyclohexane, etc.) and arenes (e.g., benzene, naphthalene, etc.). The carbocyclic ring may contain the above-mentioned substituents and hydrocarbon groups. The heterocycle is not particularly limited as long as the ring-constituting atoms are carbon atoms and hetero atoms, and examples thereof include 4- to 20-membered rings, preferably 4- to 14-membered rings. Examples of heteroatoms include nitrogen atoms, oxygen atoms, and sulfur atoms. The heterocycle may be aromatic or non-aromatic, and may be monocyclic or polycyclic. Examples thereof include a pyridine ring, lactone ring, imidazole ring, thiazole ring, and oxazole ring. The heterocycle may contain the above-mentioned substituents and hydrocarbon groups.

[0044] In formula (2), X1 may be bonded to either the pyridine ring or the benzene ring. In formula (3), X3 and L2 may be bonded to either the pyridine ring or the benzene ring. L2 is preferably bonded to the benzene ring in formula (3).

[0045] When L1 and L2 are -C(=O)O- or -NH-C(=O)-, it is preferred that the carbon atoms of these groups are directly bonded to formula (2) or formula (3). When L1 and L2 are -S(=O)2O-, it is preferable that the sulfur atom of this group is directly bonded to formula (2) or formula (3). L1 and L2 are each independently preferably -NH-C(=O)-, -C(=O)O-, or -O-, more preferably -C(=O)O- or -O-.

[0046] q is preferably 0 or 1. Preferably, r is 0 or 1. s is preferably 0 or 1. t is preferably 0 or 1.

[0047] When X1, X2, X3 or X4 is present, each of them independently represents preferably -OH, an alkyl group having 1 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms partially or fully substituted with fluorine, or a halogen atom.

[0048] Examples of the quinophthalone substituent of formula (2) include groups represented by the following formulae (2-1) to (2-4).

[0049] [ka]

[0050] In formulas (2-1) to (2-4), L 10 is a linking group selected from a single bond, —O—, —C(═O)O—, —S(═O)O—, and —NH—C(═O)—, Y1 to Y6 and Y7 to 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, -NO2, -COOH, -C(=O)OX d , -OC(=O)X d , -COOM b , -SO3H, -S(=O)2OX d , -OS(=O)2X d , -SO3M b and hydrocarbon groups 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 groups having 1 to 30 carbon atoms may be substituted.

[0051] L 10 is preferably —C(═O)O—, —NH—C(═O)—, or —O—, and more preferably —C(═O)O— or —O—. Y1 and Y2 are preferably a hydrogen atom, —OH, or an alkyl group having 1 to 30 carbon atoms. Y3 to Y6 are preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 30 carbon atoms. Y7~Y 10 is preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 30 carbon atoms.

[0052] Examples of the quinophthalone substituent of formula (3) include the following formulae (3-1) to (3-5). [ka]

[0053] In formulas (3-1) to (3-5), L 20 is a linking group selected from a single bond, —O—, —C(═O)O—, —S(═O)O—, and —NH—C(═O)—, Y1~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, -NO2, -COOH, -C(=O)OX d , -OC(=O)X d , -COOM b , -SO3H, -S(=O)2OX d , -OS(=O)2X d , -SO3M b and hydrocarbon groups 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 groups having 1 to 30 carbon atoms may be substituted.

[0054] L 20 is preferably —C(═O)O—, —NH—C(═O)—, or —O—, and more preferably —C(═O)O— or —O—. Y1 and Y2 are preferably a hydrogen atom, -OH, or an alkyl group having 1 to 30 carbon atoms. Y3 to Y6 are preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 30 carbon atoms. Y7~Y 10 is preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 30 carbon atoms.

[0055] The quinophthalone substituent is preferably a group represented by formula (2).

[0056] The above-mentioned quinophthalone compound is represented by formula (1) and has at least one quinophthalone substituent represented by formula (2) or formula (3) as R1 and R2.

[0057] The above formula (1) preferably has at least two quinophthalone substituents represented by formula (2) or formula (3), more preferably has at least one quinophthalone substituent R1 and at least one quinophthalone substituent R2, and particularly preferably has one quinophthalone substituent R1 and one quinophthalone substituent R2.

[0058] R1 and R2 may have only the quinophthalone substituent, or other substituents may 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.

[0059] The quinophthalone compound includes a compound of formula (1-1). [ka]

[0060] In formula (1-1), R 11 ~R 20 Among them, R 13 and R 18 or both of the above 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, -NO2, -COOH, -C(=O)OR d , -OC(=O)R d , -COOM a , -SO3H, -S(=O)2OR d , -OS(=O)2R d , -SO3M 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 is optionally substituted; R 21 ~R 24 are each independently a hydrogen atom, -OH, or -OR a , -NR b R c , -C(=O)NR b R c , halogen atoms, -CN, -NO2, -COOH, -C(=O)OR d , -OC(=O)R d , -COOM a , -SO3H, -S(=O)2OR d , -OS(=O)2R d , -SO3M a and hydrocarbon groups having 1 to 30 carbon atoms, and the hydrocarbon groups having 1 to 30 carbon atoms may be substituted.

[0061] In formula (1-1), R 13 and R 18 are quinophthalone substituents represented by formula (2) or (3), and 13 and R 18 and (2) are quinophthalone substituents represented by formula (2). R 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. R 21 ~R 24 is preferably a hydrogen atom.

[0062] The quinophthalone compound is a compound 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 preferably -OH or -NH2, and the monosubstituted compound is L which is -C(=O)O-. 10 or L 20 When L has -NHC(=O)-, the other is preferably -OH. 10 or L 20 When the other is —NH2, it is preferred that the other is —NH2.

[0063] 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 (vi) 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).

[0064] [ka] [ka] [ka]

[0065] In formulas (i) to (vii), R11 , R 12 , R 14 ~R 17 , R 19 , R 20 , R 21 ~R 24 , Y1~Y 10 , L 10 and L 20 The above definitions and preferred examples apply to L1 and L2. When a plurality of the above groups are present, they may be the same or different. When L1 and L2 are -C(=O)O- or -NH-C(=O)-, it is preferred that the carbon atoms of these groups are directly bonded to the quinophthalone substituent, and that the -O- of these groups is directly bonded to formula (1-1). When L1 and L2 are -S(=O)2O-, 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).

[0066] 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).

[0067] [ka] [ka] [ka] [ka] [ka]

[0068] L 10 Examples of the compound of formula (ii) in which is -C(=O)O- include the following compounds: [ka] [ka] [ka] [ka]

[0069] L 20 Examples of the compound of formula (iii) in which is -C(=O)O- include the following compounds: [ka] [ka] [ka]

[0070] L 20 Examples of the compound of formula (iv) in which is -C(=O)O- include the following compounds: [ka] [ka] [ka]

[0071] L 20 Examples of the compound of formula (v) in which is —C(═O)O— include the following compounds: [ka] [ka] [ka]

[0072] L 20 Examples of the compound of formula (vi) in which is —C(═O)O— include the following compounds: [ka] [ka]

[0073] L 20 Examples of the compound of formula (vii) in which is -C(=O)O- include the following compounds: [ka] [ka] [ka]

[0074] In formula (1-1), R 13 and R 18 Among compounds (monosubstituted compounds) in which one of the substituents is a quinophthalone substituent represented by formula (2) or (3) and the other is -OH, L 10 or L 20 Examples of compounds in which is -C(=O)O- include the following:

[0075] Examples of compounds in which the quinophthalone substituent is represented by formula (2-1) include the following compounds.

[0076] [ka] [ka] [ka] [ka]

[0077] Examples of compounds in which the quinophthalone substituent is represented by formula (2-2) include the following compounds. [ka] [ka] [ka] [ka]

[0078] Examples of compounds in which the quinophthalone substituent is represented by formula (3-1) include the following compounds. [ka] [ka] [ka]

[0079] Examples of compounds in which the quinophthalone substituent is represented by formula (3-2) include the following compounds. [ka] [ka] [ka]

[0080] Examples of compounds in which the quinophthalone substituent is represented by formula (3-3) include the following compounds. [ka] [ka] [ka] [ka]

[0081] Examples of compounds in which the quinophthalone substituent is represented by formula (3-4) include the following compounds. [ka] [ka] [ka]

[0082] Examples of compounds in which the quinophthalone substituent is represented by formula (3-5) include the following compounds. [ka] [ka] [ka] [ka]

[0083] L in the compounds of formulas (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 are mentioned:

[0084] [ka] [ka] [ka] [ka]

[0085] In formula (1-1), R 13 and R 18 Among compounds (monosubstituted compounds) in which one of the above is a quinophthalone substituent represented by formula (2) or (3) and the other is -NH, L 10 Examples of compounds in which is -NHC(=O)- include the following compounds. [ka] [ka] [ka] [ka]

[0086] The above-mentioned quinophthalone compound can be obtained by reacting a compound having an amide structure with a compound having a quinophthalone substituent.

[0087] 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)), a compound represented by formula (4') or a derivative thereof (hereinafter, these may be collectively referred to as compounds of formula (4')), etc. can be used. As the derivative, R 11 ~R 20and 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.

[0088] [ka]

[0089] It is known that the compound of formula (4) can be synthesized by the following reaction. [ka]

[0090] 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.

[0091] In addition, by using an excess amount of phenylenediamine instead of aminophenol in the above reaction, a compound of formula (4') can be synthesized. Alternatively, instead of phenylenediamine, a substituted phenylenediamine in which hydrogen atoms on the aromatic ring of phenylenediamine are substituted with a substituent can be used. By using such a substituted phenylenediamine, a substituent can be introduced into the compound of formula (4'). Examples of substituted phenylenediamines include alkyl-substituted phenylenediamines such as 2,5-diaminotoluene and 2,5-dimethyl-1,4-phenylenediamine; halogen-substituted phenylenediamines such as 2-chloro-1,4-phenylenediamine and 2,3,5,6-tetrafluoro-1,4-phenylenediamine; fluoroalkyl-substituted phenylenediamines such as 2-(trifluoromethyl)-1,4-phenylenediamine; and sulfo-substituted phenylenediamines such as 1,4-phenylenediamine-2-sulfonic acid.

[0092] 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.

[0093] Compounds having a quinophthalone substituent can be compounds of formula (2) and formula (3) in which the linking moiety (L1 in formula (2) and L2 in formula (3)) is replaced with a corresponding monovalent group. 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).

[0094] In the following, in formula (1-1), R 13 and R 18 Both are shown in equation (2-1), and L 10 This article focuses on the synthesis of compounds in which the quinophthalone substituent is -C(=O)O- (ester bond).

[0095] 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. As the derivative, Y1 to Y8 and Y in formula (2-1) can be used. 10 The corresponding substituent may be introduced after the reaction.

[0096] [ka]

[0097] The compound of formula (5) can be obtained by reacting 2-methylquinoline with trimellitic anhydride by a known method.

[0098] 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 less than 2 moles per mole of the compound of formula (4) etc., a quinophthalone compound having one quinophthalone substituent can also be obtained.

[0099] The reaction temperature in 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.

[0100] 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 be used.

[0101] The reaction is preferably carried out in a solvent, such as amide solvents like N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and dimethylformamide; hydrocarbon solvents like toluene and xylene; halogenated hydrocarbon solvents like chlorobenzene, dichlorobenzene, and chloroform; ketone solvents like methyl isobutyl ketone; ether solvents like tetrahydrofuran and 1,4-dioxane; and nitrile solvents like acetonitrile, among which amide solvents are preferred.

[0102] 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.

[0103] When the linking moiety is other than -C(=O)O- (ester bond), and when the quinophthalone substituent is represented by formula (3), it 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 -NH2 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), it is possible to obtain a quinophthalone compound in which the linking moiety is -NH-C(=O)- (amide bond). 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.

[0104] A specific example of a method for synthesizing the quinophthalone compound of the present invention is the synthesis scheme shown below. Scheme 1 (Synthesis of Compound No. 2) [ka]

[0105] Scheme 2 (Synthesis of Compound No. 4 above) [ka]

[0106] Scheme 3 (Synthesis of Compound No. 35) [ka]

[0107] Scheme 4 (Synthesis of Compound No. 65) [ka]

[0108] Scheme 5 (Synthesis of Compound No. 101) [ka]

[0109] Scheme 6 (Synthesis of Compound No. 135) [ka]

[0110] Scheme 7 (Synthesis of Compound No. 329) [ka]

[0111] Scheme 8 [ka]

[0112] Scheme 9 [ka]

[0113] 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.

[0114] The content of the quinophthalone compound is preferably 0.1 to 5 parts by mass in terms of solid content relative to 100 parts by mass of the (A) carboxylic acid-containing resin.

[0115] The photosensitive composition of the present invention may contain a colorant (D) other than the quinophthalone compounds described above. Examples of the colorant include red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, and 265; blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, and 60; purple pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38; and green pigments such as CI Pigment Green 7, 36, and 58. Examples of the colorant include compounds classified as having hues other than CI pigments and known dyes described in Dyeing Notes (Shikisensha). Further, based on the chemical structure, examples of the dyes 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, nitro dyes, etc. Coloring materials other than quinophthalone compounds can be used in an amount that does not impair the effects of the present invention.

[0116] 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 coloring material other than the above-mentioned quinophthalone compound as the coloring agent (D). When a coloring material other than the above-mentioned quinophthalone compound is used in combination, a phthalocyanine blue coloring agent may be contained. In this case, The content of the phthalocyanine blue colorant is preferably 0.01 to 5.0 parts by mass, calculated as solid content, relative to 100 parts by mass of (A) carboxylic acid-containing photosensitive resin, and from the viewpoint of resolution, more preferably 0.01 to 1.5 parts by mass, calculated as solid content.

[0117] When the photosensitive composition contains a polyfunctional (meth)acrylate having a bisphenol A skeleton as a photosensitive monomer, the content of the (D) colorant containing a quinophthalone compound is preferably 0.01 to 5.0 parts by mass in terms of solid content per 100 parts by mass of the (A) carboxylic acid-containing resin, from the viewpoint of reducing the gloss difference.

[0118] Furthermore, when the photosensitive composition contains a polyfunctional (meth)acrylate having an alicyclic skeleton as a photosensitive monomer, the content of the (D) colorant containing a quinophthalone compound is preferably 0.01 to 5.0 parts by mass in terms of solid content relative to 100 parts by mass of the (A) carboxylic acid-containing resin, from the viewpoint of improving resolution.

[0119] Furthermore, when the photosensitive composition contains a polyfunctional (meth)acrylate having a dipentaerythritol skeleton as a photosensitive monomer, the content of the (D) colorant containing a quinophthalone compound is preferably 0.01 to 5.0 parts by mass in terms of solid content per 100 parts by mass of the (A) carboxylic acid-containing resin, from the viewpoint of improving the appearance and crack resistance of the cured product.

[0120] (E) Thermosetting resin The photosensitive composition of the present invention may contain, in addition to the above-mentioned components, a thermosetting resin (E). Examples of thermosetting resins include known and commonly used ones 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.

[0121] 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.

[0122] Examples of commercially available epoxy resins include jER 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 830, 835, 840, 850, N-730A, and N-695 manufactured by DIC Corporation; and RE-306 manufactured by Nippon Kayaku Co., Ltd.

[0123] 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.

[0124] 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. Other commercially available compounds include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd., and U-CAT 3513N (trade name of dimethylamine-based compounds), DBU, DBN, and U-CAT SA 102 (all bicyclic amidine compounds and salts thereof) manufactured by San-Apro Co., Ltd.

[0125] 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 of at least one of an epoxy group and an oxetanyl group with a carboxyl group, may be used alone or in combination. 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, which also function as adhesion promoters, are preferably used in combination with the heat-curing catalyst.

[0126] 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 (A) carboxylic acid-containing resin.

[0127] (F) Filler The photosensitive composition of the present invention may contain a filler as needed in order to improve the physical strength of the cured film of the photosensitive composition or to adjust 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.

[0128] 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, spherical shapes are preferred.

[0129] 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.

[0130] 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 preferred 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 with respect to 100 parts by mass of the inorganic filler.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] The photosensitive composition of the present invention may contain an organic solvent from the viewpoint of ease of preparation and coating properties. Examples of organic solvents that can be used 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.

[0136] The content of the organic solvent in the photosensitive composition can be appropriately changed depending on the materials constituting the photosensitive composition.

[0137] The photosensitive composition of the present invention may be used in the form of a dry film or in a liquid form. When used in a liquid form, it may be a one-component type or a two-component or more-component type.

[0138] <Laminated structure> The laminate structure of the present invention comprises a first film and a resin layer provided on the first film, the resin layer being composed of 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 the resin layer. There are no particular limitations 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.

[0139] 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.

[0140] The laminated 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. Examples of the second film include a polyester film, a polyethylene film, and a polypropylene film. The term "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 weaker than the adhesive strength between the resin layer and the first film. For example, the surface of the second film may be subjected to a release treatment.

[0141] <Cured products and electronic components> 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.

[0142] The substrates onto which the resin layer of the laminated structure is laminated include printed wiring boards and flexible printed wiring boards with circuits already formed 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, etc., 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.

[0143] 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 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 board 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.

[0144] 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.

[0145] 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 passive components other than printed wiring boards, 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 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.

[0146] The cured product of the photosensitive composition of the present invention has excellent dielectric properties, and its use is expected to provide 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 communications, SLPs (Substrate-Like PCBs) in which circuits are formed using the modified semi-additive process (MSAP), application processors (APs) 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. [Example]

[0147] The present invention will now be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following, "parts" and "%" are all by mass unless otherwise specified.

[0148] <Preparation of Colorant> (Synthesis of quinophthalone compound 1) Quinophthalone compound 1 was synthesized according to the following scheme. [ka]

[0149] 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 under a nitrogen atmosphere. After stirring at 60°C for 30 minutes, the mixture was heated under a nitrogen atmosphere. 1 ,N 4 1.4 mmol of 1,4-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 solid obtained by filtering the reaction solution 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.

[0150] 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.

[0151] Quinophthalone compound 1 was identified by the peak obtained in positive mode using laser desorption ionization (LDI) with a time-of-flight mass spectrometer (rapifleX (TOF-MS, Bruker Daltonics)). MS (m / z) = 947.4 ([M+H] + )

[0152] (Synthesis of quinophthalone compound 2) Quinophthalone compound 2 was synthesized according to the following scheme. [ka]

[0153] 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 4 1.31 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. After stirring at 100°C for 27 hours, the mixture was 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.

[0154] 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.

[0155] Quinophthalone compound 2 was identified by the peak obtained in positive mode by laser desorption ionization using a time-of-flight mass spectrometer (rapifleX (TOF-MS, Bruker Daltonics)). MS (m / z) = 1037.3 ([M+H] + )

[0156] (Synthesis of quinophthalone compound 3) Quinophthalone compound 3 was synthesized according to the following scheme. [ka]

[0157] 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 4 1.31 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. After stirring at 100°C for 27 hours, the mixture was 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 3.

[0158] 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.

[0159] Quinophthalone compound 3 was identified by the peak obtained in positive mode by laser desorption ionization using a time-of-flight mass spectrometer (rapifleX (TOF-MS, Bruker Daltonics)). MS (m / z) = 947.3 ([M+H] + )

[0160] The heat resistance, color fixation, and light absorption in the ultraviolet region were evaluated by thermogravimetry for the quinophthalone compounds 1 to 3 obtained as described above. For comparison, the following compounds 4 and 5 were also evaluated in the same manner.

[0161] Compound 4: 2,3-Dihydro-1,3-dioxy-2-(2-quinolinyl)-1H-indene-5-carboxylic acid [ka]

[0162] Compound 5: Pigment Yellow 147 (AGR) [ka]

[0163] (heat resistance) Quinophthalone Compound 1 was subjected to thermogravimetric measurement using a thermogravimetric analyzer (Waters, model name: TGA5500) to evaluate its heat resistance. The amount of sample used per measurement was 1 to 2 mg. The temperature was raised from 50°C to 600°C at a rate of 10°C per minute in a nitrogen atmosphere. 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.

[0164] (Color fixation) Quinophthalone Compound 1 and Compound 4 were dispersed in 2 g of N-methylpyrrolidone, and 0.986 g of resin (Daicel Chemical's Cyclomer P (ACA) Z320) and 0.014 g of a 4 wt% solution of leveling agent (BYK-333, BYK-Chemie) 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. Next, the film was kept in a thermostatic chamber at 230° C. for 2 hours, and after the holding, the film was visually observed to check the color fixation. Quinophthalone compound 1: No change in color before and after storage Compound 4: Significant fading after storage

[0165] (light absorption in the ultraviolet region) A solution was prepared by dissolving quinophthalone compound 1 in NMP as a solvent to a concentration of 1.0 mmol / L in NMP. 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 Figure 6.

[0166] As shown in the thermogravimetric measurement results in Figures 4 and 5, quinophthalone compound 1 has improved heat resistance compared to the raw material compound 4, and also exhibits heat resistance comparable to that of compound 5, a conventional yellow pigment (Pigment Yellow 147). On the other hand, as shown in FIG. 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, the 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, demonstrating their heat resistance.

[0167] <Preparation of Carboxylic Acid-Containing Resin> Synthesis Example 1 (Synthesis of Carboxylic Acid-Containing Photosensitive Resin 1 Using a Phenol Compound as a Starting Material) Into an autoclave equipped with a thermometer, a nitrogen / alkylene oxide inlet, and a stirrer, 119.4 parts of a novolac cresol resin (trade name "Shonor CRG951", manufactured by Showa Highpolymer Co., Ltd., OH equivalent: 119.4), 1.19 parts of potassium hydroxide, and 119.4 parts of toluene were introduced, 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 gradually added dropwise, and the temperature was raised to 125 to 132°C and 0 to 4.8 kg / cm. 2 The mixture was reacted at 400 K for 16 hours. After cooling to room temperature, 1.56 parts of 89% phosphoric acid was added to the reaction solution and mixed to neutralize the potassium hydroxide, yielding a propylene oxide reaction solution of novolac cresol resin with a nonvolatile content of 62.1% and a hydroxyl value of 182.2 mg KOH / g (307.9 g / eq.). This resulted in an average of 1.08 moles of propylene oxide being added per equivalent of phenolic hydroxyl groups. 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 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, and the mixture was stirred at 110°C for 12 hours. The water produced by the reaction was distilled off as an azeotrope with toluene, resulting in 12.6 parts of water being distilled off. The mixture was then cooled to room temperature, neutralized with 35.35 parts of 15% aqueous sodium hydroxide, and then washed with water. The toluene was then distilled off while being replaced with 118.1 parts of diethylene glycol monoethyl ether acetate using an evaporator, yielding a novolac acrylate resin solution. Next, 332.5 parts of the obtained novolac acrylate resin solution and 1.22 parts of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer, and an air inlet tube, and 60.8 parts of tetrahydrophthalic anhydride were gradually added while blowing air at a rate of 10 ml / min and stirring, and the mixture was reacted at 95 to 101 ° C for 6 hours, cooled, and then removed. The solid content of the resin solution thus obtained was 65%, and the acid value of the solid was 87.7 mg KOH / g.

[0168] Preparation Example 1: Preparation of a photosensitive composition using a polyfunctional (meth)acrylate having a bisphenol A skeleton as a photosensitive monomer Each photosensitive composition shown in Table 1 below was obtained by blending and mixing the components shown in the same table. Each value in the table indicates parts by mass or % by mass calculated as nonvolatile content.

[0169] The components in the table below are as follows: Melamine: Nissan Chemical Co., Ltd. DICY: Dicinamide, manufactured by Mitsubishi Chemical Corporation Quinophthalone Compounds 1, 2, 3 (Yellow): The above Quinophthalone Compounds 1, 2, 3 Pigment Yellow 147 (yellow): Anthraquinone yellow colorant manufactured by BASF Japan Pigment Blue 15:3 (blue): phthalocyanine blue colorant manufactured by DIC Corporation (FASTOGEN® BLUE FA5380) KS-66: Oil compound type defoamer manufactured by Shin-Etsu Chemical Co., Ltd. Omnirad TPO-L: Acylphosphine oxide photoinitiator manufactured by IGM Resins jER828: Bisphenol A epoxy resin manufactured by Mitsubishi Chemical Corporation BPE-900: Difunctional ethoxylated bisphenol A methacrylate (molecular weight 1112) manufactured by Shin-Nakamura Chemical Co., Ltd. Silica: SO-C2 manufactured by Admatec Co., Ltd.

[0170] [Table 1]

[0171] <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 using a CZ8100 manufactured by MEC Co., Ltd., so that the thickness after drying would be 20 μm. The board was then 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 with a DXP-3580 manufactured by Oak Manufacturing Co., Ltd. at an exposure dose of 7 steps using 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 with 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 evaluated based on the difference in the L*a*b* values ​​(discoloration after reflow) between (1) and (2). The evaluation criteria were as follows: ○: The difference in L*a*b* values ​​is less than 4.0, and the material has excellent heat resistance. ×: The difference in L*a*b* values ​​is 4.0 or more, and the heat resistance is slightly poor. The evaluation results are shown in Table 1.

[0172] <Evaluation of resolution> Each photosensitive composition was applied to a single-sided printed wiring board with a copper thickness of 15 μm, pretreated using a CZ8100 manufactured by MEC Co., Ltd., to a total surface area 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 film. The resulting dried coating film was irradiated with a step tablet (Stuffer 41 step) using a DXP-3580 manufactured by Oak Manufacturing Co., Ltd. at an exposure dose of 7 steps to form an opening with a design opening diameter of 150 μm. The film was then developed with a 1% by mass 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 difference in actual size from the designed 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 between the actual opening diameter design value of 150 μm and the actual opening diameter is 20 μm or more The evaluation results are shown in Table 1.

[0173] <Color Tone Evaluation> The color tone of the surface of the cured film on each evaluation substrate was visually confirmed, and the evaluation results are shown in Table 1.

[0174] <Evaluation of gloss difference> A curable resin composition was applied by screen printing to the entire surface of a circuit pattern substrate with a copper thickness of 15 μm, which had been pretreated with a CZ8100 manufactured by MEC Co., Ltd., so that the film thickness after drying would be 20 μm, and the composition was dried in a hot air circulation drying oven at 80°C for 30 minutes to obtain a dried coating film. On the obtained dried coating film, an exposure dose of 150 mJ / cm was applied using a DXP-3580 manufactured by Oak Manufacturing Co., Ltd. 2 The evaluation substrate at this stage was designated as the "evaluation substrate before development." 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 thermal curing was performed for 60 minutes at 150°C in a hot air circulation drying oven to obtain an evaluation substrate with a cured film. The evaluation substrate at this stage was designated as the "developed evaluation substrate." The glossiness of each of the evaluation substrates before and after development was measured using Micro Trigloss (manufactured by Byck-Gardner), and the difference in optical intensity due to the rate of change in glossiness before development and after thermal curing was evaluated according to the following criteria. ◎: Change rate is less than 10% ○: Change rate is 10% or more but less than 20% ×: Change rate is 20% or more The evaluation results are shown in Table 1.

[0175] Preparation Example 2: Preparation of a photosensitive composition using a polyfunctional (meth)acrylate having an alicyclic skeleton as a photosensitive monomer Each photosensitive composition shown in Table 2 below was obtained by blending and mixing the components shown in the same table. Each value in Table 2 indicates parts by mass or % by mass calculated as nonvolatile content.

[0176] The components in Table 2 below are as follows: However, for components not listed below, the same ones as those described in Preparation Example 1 above were used. A-DCP: Tricyclodecane dimethanol diacrylate (molecular weight 304) manufactured by Shin-Nakamura Chemical Co., Ltd.

[0177] [Table 2]

[0178] The heat resistance and color tone of each photosensitive composition were evaluated by the same evaluation methods as described above, and the evaluation results are shown in Table 2.

[0179] <Evaluation of resolution> A 15 μm thick copper circuit pattern substrate pretreated with a CZ8100 manufactured by MEC Co., Ltd. was coated with a curable resin composition by screen printing to a dry film thickness of 20 μm. The substrate was placed in a hot air circulation drying oven at 80°C and dried for 30 minutes. After drying, various line patterns were exposed to light using a Stouffer 41-step step tablet with a DXP-3580 manufactured by Oak Manufacturing Co., Ltd., to achieve 10 and 12 curing steps. The coating was then developed with a 1% by weight sodium carbonate solution at 30°C for 60 seconds at a spray pressure of 0.2 MPa, followed by thermal curing at 150°C for 60 minutes to obtain an evaluation substrate with a cured film. The line thickness of the evaluation board obtained as described above, which had a design value of 150 μm, was measured, and the difference in line thickness due to the difference in the curing step conditions between 10 and 12 steps using a Stouffer 41-step step tablet was calculated, and evaluation was performed using the following evaluation criteria. ◎: The difference in line thickness between 10 and 12 steps is less than 10 μm ○: The difference in line thickness between 10 and 12 steps is 10 μm or more and less than 20 μm ×: The difference in line thickness between 10 and 12 steps is 20 μm or more The evaluation results are shown in Table 2.

[0180] Preparation Example 3: Preparation of photosensitive composition using caprolactone-modified dipentaerythritol hexa(meth)acrylate as photosensitive monomer Each photosensitive composition shown in Table 3 below was obtained by blending and mixing the components shown in the same table. Each value in Table 3 indicates parts by mass or % by mass calculated as nonvolatile content.

[0181] The components in Table 3 below are as follows: However, for components not listed below, the same ones as those described in Preparation Example 1 above were used. DPCA-60: Dipentaerythritol caprolactone (n=1) acrylate (molecular weight 1262) manufactured by Nippon Kayaku Co., Ltd.

[0182] [Table 3]

[0183] The heat resistance, resolution and color tone of each photosensitive composition were evaluated by the same methods as described above, and the evaluation results are shown in Table 3.

[0184] <Visual evaluation of film marks> Each photosensitive composition was applied by screen printing to the entire surface of a circuit pattern substrate with a copper thickness of 15 μm, which had been pretreated using a CZ8100 manufactured by MEC Co., Ltd., so that the film thickness after drying would be 20 μm, and the composition was dried in a hot air circulation drying oven at 80°C for 30 minutes to obtain a dried coating film. A negative pattern film (negative film) was placed on the obtained dried coating film, and the film was exposed using a contact exposure machine EXP-2960 manufactured by Oak Manufacturing Co., Ltd. At this time, the cumulative exposure dose for the dried coating film under the negative film was 150 mJ / cm. 2 The resist was then exposed to light so that the resist film was cured. The resist was then developed 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 in a hot air circulation drying oven at 150°C for 60 minutes to obtain an evaluation substrate having a cured film. Subsequently, the presence or absence of negative film traces on the surface of the cured film of the evaluation substrate was visually confirmed, and the evaluation was performed according to the following evaluation criteria. ◎: Negative film traces are almost invisible ○: Negative film marks are not noticeable ×: Negative film marks are noticeable The evaluation results are shown in Table 3.

[0185] Preparation Example 4: Preparation of photosensitive composition using biphenyl-type epoxy resin Each photosensitive composition shown in Table 4 below was obtained by blending and mixing the components shown in the same table. Each value in the table indicates parts by mass or % by mass calculated as nonvolatile content.

[0186] The components in Table 4 below are as follows: However, for components not listed below, the same ones as those described in Preparation Example 1 above were used. DPHA: Dipentaerythritol hexaacrylate (molecular weight 648) manufactured by Nippon Kayaku Co., Ltd.

[0187] [Table 4]

[0188] The heat resistance, resolution and color tone of each photosensitive composition were evaluated by the same methods as described above, and the evaluation results are shown in Table 4.

[0189] <Crack resistance evaluation> Each photosensitive composition was applied by screen printing to the entire surface of a substrate (thickness 0.2 mm, length: 500 mm, width: 500 mm) from which the copper foil had been removed, so that the film thickness after drying would be 20 μm, and the composition was dried in a hot air circulation drying oven at 80°C for 30 minutes to obtain a dried coating film. The obtained dried coating film was exposed to light at an exposure dose of 150 mJ / cm using a DXP-3580 manufactured by Oak Sakusho Co., Ltd. 2The substrate was exposed to light in a 50 mm square pattern spaced 50 mm apart so that the pattern resembled a 50 mm square. The substrate was then developed 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 oven. The cured substrate was placed on a stand (a kamaboko-shaped stand) with a curved top surface (R=100 mm) and left at room temperature for 1 minute. The cured film was visually inspected for cracks and evaluated according to the following criteria. This crack resistance evaluation test was designed to replicate cracks that occur during substrate transportation, and cracks tend to occur easily from the corners. ◎: No cracks were observed ○: Crack length is less than 500 μm ×: Crack length is 500 μm or more The evaluation results are shown in Table 4.

Claims

1. (A) a carboxylic acid-containing resin; (B) a photopolymerization initiator; (C) a photosensitive monomer; (D) a colorant; A photosensitive composition comprising: the (C) photosensitive monomer contains at least one polyfunctional (meth)acrylate selected from the group consisting of a polyfunctional (meth)acrylate having a bisphenol A skeleton, a polyfunctional (meth)acrylate having an alicyclic skeleton, and a polyfunctional (meth)acrylate having a dipentaerythritol skeleton, The colorant (D) is a compound represented by the following formula (1): 【Chemistry 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) 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 is optionally 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 from 0 to 5; n is an integer from 0 to 5, p is an integer from 0 to 4, R 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; 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, however, m+n is an integer equal to or greater than 1, 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): 【Chemistry 2】 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 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; L １ and L ２ are each independently a single bond, —O—, —C(═O)O—, or —S(═O) ２ is a linking group selected from —O— and —NH—C(═O)—; q is an integer from 0 to 6; r is an integer from 0 to 3; s is an integer from 0 to 5; t is an integer from 0 to 4, 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.) A photosensitive composition comprising a quinophthalone compound represented by the formula:

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

3. 2. 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), 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 including a first film and a resin layer provided on the first film, A laminated structure, wherein the resin layer comprises 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 component comprising the cured product according to claim 6.

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