Photosensitive resin composition, cured product, method for forming cured product, partition wall, and image display device

Abstract

The photosensitive resin composition is characterized by containing (a) an alkali-soluble resin, (b) a photopolymerization initiator, and (c) an ethylenically unsaturated compound, and the mass ratio of the alkali-soluble resin (a) to the ethylenically unsaturated compound (c) (alkali-soluble resin (a) / ethylenically unsaturated compound (c)) is 5 or more. The aforementioned (c) ethylenically unsaturated compound contains an ethylenically unsaturated compound (c1) having an alkylene oxide group and three or more ethylenically unsaturated groups.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a cured product obtained by curing the photosensitive resin composition, a method for forming the same, a partition wall formed from the cured product, and an image display device including the partition wall. Background Art

[0002] Image display devices including organic electroluminescent elements (also called organic electroluminescence, organic EL) have attracted much attention as the next generation of flat panel displays (FPDs) because of their excellent visual recognition and responsiveness such as contrast and viewing angle, and their ability to achieve low power consumption, thinness and lightness, and flexibility of the display body.

[0003] The organic electroluminescent element has a structure in which an organic layer including a light-emitting layer or various functional layers is sandwiched between a pair of electrodes, and at least one of the pair of electrodes has light-transmitting properties.

[0004] The image display device displays images by driving a panel in which an organic electroluminescent element is arranged for each pixel.

[0005] Such an organic electroluminescent element is currently manufactured by forming partition walls (banks) on a substrate and then laminating a light-emitting layer or various functional layers in the region surrounded by the partition walls.

[0006] As a method for easily forming a partition wall, a method of forming by photolithography using a photosensitive resin composition is known. In addition, a colored partition wall with a light-shielding function has also been developed. For example, Patent Document 1 describes a photosensitive colored resin composition composed of a specific organic pigment, a specific dispersant, and a specific resin.

[0007] When the colored partition walls are produced by photolithography, the photosensitive colored resin composition is first applied on a substrate, then dried under reduced pressure using a vacuum drying apparatus, then dried by heating using a hot plate, image-wise exposed and developed, and then cured by high temperature treatment.

[0008] In this curing step, curing may be performed in an inert atmosphere such as nitrogen gas to prevent the electrodes on the substrate from being damaged by the high-temperature treatment.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: International Publication No. 2018 / 101314 Summary of the invention

[0012] Problem that the invention aims to solve

[0013] The present inventors have conducted research and found that the photosensitive colored resin composition described in Patent Document 1 has the following problem: since curing is not hindered by oxygen in a nitrogen atmosphere, it is cured quickly before heat flow occurs, and as a result, the side surface of the partition wall becomes nearly perpendicular to the substrate surface, that is, the taper angle of the side surface of the partition wall becomes larger. If the taper angle of the side surface of the partition wall becomes larger, when various functional layers are stacked, each layer becomes discontinuous, resulting in poor display.

[0014] An object of the present invention is to provide a photosensitive resin composition that can form a cured product having an excellent taper shape even by curing in an inert atmosphere.

[0015] Another object of the present invention is to provide a cured product obtained by curing the photosensitive resin composition and a method for forming the same, a partition wall formed from the cured product, and an image display device including the partition wall.

[0016] Solutions for solving problems

[0017] The present inventors have found that the above-mentioned problems can be solved by a photosensitive resin composition prepared by combining and blending an alkali-soluble resin and a specific ethylenically unsaturated compound at a predetermined ratio, thereby completing the present invention.

[0018] That is, the gist of the present invention is as follows.

[0019] [1] A photosensitive resin composition comprising (a) an alkali-soluble resin, (b) a photopolymerization initiator, and (c) an ethylenically unsaturated compound,

[0020] The mass ratio of the above-mentioned (a) alkali-soluble resin to the above-mentioned (c) ethylenically unsaturated compound ((a) alkali-soluble resin / (c) ethylenically unsaturated compound) is 5 or more,

[0021] The (c) ethylenically unsaturated compound includes an ethylenically unsaturated compound (c1) having an alkylene oxide group and having three or more ethylenically unsaturated groups.

[0022] [2] A photosensitive resin composition comprising (a) an alkali-soluble resin, (b) a photopolymerization initiator, and (c) an ethylenically unsaturated compound,

[0023] The total double bond equivalent of the alkali-soluble resin (a) and the ethylenically unsaturated compound (c) is 270 g / mol or more, which is a weighted average of the values ​​obtained by dividing the contents (mass) of the alkali-soluble resin (a) and the ethylenically unsaturated compound (c) by the molar numbers of their respective ethylenically unsaturated bonds.

[0024] The (c) ethylenically unsaturated compound includes an ethylenically unsaturated compound (c1) having an alkylene oxide group and having three or more ethylenically unsaturated groups.

[0025] [3] The photosensitive resin composition according to [2], wherein the total double bond equivalent of the (a) alkali-soluble resin and the (c) ethylenically unsaturated compound is 380 g / mol or more.

[0026] [4] The photosensitive resin composition according to [3], wherein the total double bond equivalent of the (a) alkali-soluble resin and the (c) ethylenically unsaturated compound is 410 g / mol or more.

[0027] [5] The photosensitive resin composition according to [1], wherein the mass ratio of the (a) alkali-soluble resin to the (c) ethylenically unsaturated compound ((a) alkali-soluble resin / (c) ethylenically unsaturated compound) is 6 or more.

[0028] [6] The photosensitive resin composition according to [5], wherein the mass ratio of the (a) alkali-soluble resin to the (c) ethylenically unsaturated compound ((a) alkali-soluble resin / (c) ethylenically unsaturated compound) is 8 or more.

[0029] [7] The photosensitive resin composition according to any one of [1] to [6], wherein the content ratio of the ethylenically unsaturated compound (c1) in the (c) ethylenically unsaturated compound is 50% by mass or more.

[0030] [8] The photosensitive resin composition according to any one of [1] to [7], wherein the ethylenically unsaturated compound (c1) has an alkylene oxide group in a side chain.

[0031] [9] The photosensitive resin composition according to any one of [1] to [8], wherein the ethylenically unsaturated compound (c1) has three or more alkylene oxide-modified ethylenically unsaturated groups.

[0032]

[10] The photosensitive resin composition according to any one of [1] to [9], wherein the ethylenically unsaturated compound (c1) contains a compound (c1-1) represented by the following general formula (c1-1-1).

[0033]

[0034] (X in formula (c1-1-1) is represented by the following general formula (c1-1-2); X may be the same or different; Y is methyl or represented by the following general formula (c1-1-4).)

[0035]

[0036] (R in formula (c1-1-2) 1 represents an alkylene group having 2 to 4 carbon atoms; a represents an integer of 1 to 9; when a is 2 or more, multiple R 1 Optionally the same or different; R 2 It is represented by the following general formula (c1-1-3); * represents a connecting bond. )

[0037]

[0038] (R in formula (c1-1-3) 3 represents a hydrogen atom or a methyl group; * represents a connecting bond. )

[0039]

[0040] (In formula (c1-1-4), m is 0 or 1; * represents a connecting bond; X is represented by the above general formula (c1-1-2); X may be the same or different.)

[0041]

[11] The photosensitive resin composition according to

[10] , wherein a in the formula (c1-1-2) represents an integer of 2 to 9.

[0042]

[12] The photosensitive resin composition according to

[10] or

[11] , wherein Y in the formula (c1-1-1) is represented by the formula (c1-1-4), and m in the formula (c1-1-4) is 1.

[0043]

[13] The photosensitive resin composition according to any one of [1] to

[12] , wherein the (a) alkali-soluble resin contains an alkali-soluble resin (a1) having a cardo skeleton.

[0044]

[14] The photosensitive resin composition according to

[13] , wherein the alkali-soluble resin (a1) has a partial structure represented by the following general formula (a1-0).

[0045]

[0046] (The benzene ring in formula (a1-0) may be further substituted by any substituent; Q represents O, S, CO or a direct bond; * represents a connecting bond.)

[0047]

[15] The photosensitive resin composition according to

[14] , wherein the alkali-soluble resin (a1) has a partial structure represented by the following general formula (a1-1).

[0048]

[0049] (The benzene ring in formula (a1-1) may be further substituted by any substituent; R9 Each independently represents a hydrogen atom or a methyl group; Q represents O, S, CO or a direct bond; n represents an integer of 0 to 4; multiple Qs may be the same or different; * represents a connecting bond.

[0050]

[16] The photosensitive resin composition according to any one of [1] to

[15] , further comprising (d) a colorant.

[0051]

[17] The photosensitive resin composition according to

[16] , wherein the colorant (d) contains an organic black pigment.

[0052]

[18] The photosensitive resin composition according to

[17] , wherein the organic black pigment comprises at least one selected from the group consisting of a compound represented by the following general formula (d1), a geometric isomer of the compound, a salt of the compound, and a salt of a geometric isomer of the compound.

[0053]

[0054] (In formula (d1), R 11 and R 16 Each independently represents a hydrogen atom, CH3, CF3, a fluorine atom or a chlorine atom;

[0055] R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 and R 20 Each independently represents a hydrogen atom, a halogen atom, R 21 、COOH、COOR 21 、COO - ,CONH2,CONHR 21 ,CONR 21 R 22 、CN、OH、OR 21 、COCR 21 、OOCNH2、OOCNHR 21 、OOCNR 21 R 22 、NO2、NH2、NHR 21 NR 21 R 22 、NHCOR 22 NR 21 COR 22 、N=CH2、N=CHR 21 、N=CR 21 R 22 , SH, SR21 , SOR 21 、SO2R 21 、SO3R 21 、SO3H、SO3 - 、SO2NH2、SO2NHR 21 or SO2NR 21 R 22 ;

[0056] Choose from R 12 With R 13 , R 13 With R 14 , R 14 With R 15 , R 17 With R 18 , R 18 With R 19 , and R 19 With R 20 At least one of the groups consisting of the above may be directly bonded to each other, or may be bonded to each other via an oxygen atom, a sulfur atom, NH or NR 21 Bridge and bond to each other;

[0057] R 21 and R 22 Each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.)

[0058]

[19] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to

[18] .

[0059]

[20] A partition wall formed from the cured product described in

[19] .

[0060]

[21] An image display device comprising the partition wall described in

[20] .

[0061]

[22] A method for forming a cured product, characterized in that at least the following steps (1) to (4) are carried out using the following photosensitive resin composition, wherein the photosensitive resin composition contains (a) an alkali-soluble resin, (b) a photopolymerization initiator and (c) an ethylenically unsaturated compound, and the above-mentioned (c) ethylenically unsaturated compound contains: an ethylenically unsaturated compound (c1') having an alkylene oxide group.

[0062] Step (1): a step of forming a coating film of the photosensitive resin composition on a substrate.

[0063] Step (2): a step of exposing at least a portion of the coating film formed in step (1) to light.

[0064] Step (3): A step of developing the coating film exposed in step (2).

[0065] Step (4): A step of baking the coating film developed in step (3) in an inert atmosphere.

[0066]

[23] The method for forming a cured product according to

[22] , wherein the step (4) is a step of baking the coating film developed in the step (3) under an inert atmosphere or under vacuum.

[0067]

[24] The method for forming a cured product according to

[22] or

[23] , wherein the ethylenically unsaturated compound (c1′) has three or more ethylenically unsaturated groups.

[0068]

[25] A method for forming a cured product according to any one of

[22] to

[24] , wherein the mass ratio of the (a) alkali-soluble resin to the (c) ethylenically unsaturated compound in the photosensitive resin composition ((a) alkali-soluble resin / (c) ethylenically unsaturated compound) is 5 or more.

[0069]

[26] The method for forming a cured product according to any one of

[22] to

[25] , wherein the ethylenically unsaturated compound (c1′) has an alkylene oxide group in a side chain.

[0070]

[27] The method for forming a cured product according to any one of

[22] to

[26] , wherein the ethylenically unsaturated compound (c1′) has three or more alkylene oxide-modified ethylenically unsaturated groups.

[0071] Effects of the Invention

[0072] According to the present invention, there are provided a photosensitive resin composition that can form a cured product having an excellent tapered shape even by curing in an inert atmosphere, a cured product, a partition formed of the cured product, and an image display device including such a partition. BRIEF DESCRIPTION OF THE DRAWINGS

[0073] Figure 1 It is a schematic cross-sectional view showing a gently tapered partition wall. DETAILED DESCRIPTION

[0074] The present invention will be described in detail below. The following description is an example of an embodiment of the present invention, and the present invention is not limited thereto unless it deviates from the gist of the invention.

[0075] In the present invention, "(meth)acrylic acid" means "either or both of acrylic acid and methacrylic acid." The same applies to "(meth)acrylate" and "(meth)acryloyl."

[0076] The term “total solid content” refers to all components other than the solvent in the photosensitive resin composition. Even if components other than the solvent are liquid at room temperature, such components are not included in the solvent but are included in the total solid content.

[0077] In the present invention, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0078] In the present invention, the so-called partition material refers to a bank material, a wall material, or a wall material, and similarly, the so-called partition wall refers to a bank, a wall, or a wall.

[0079] The so-called partition wall is, for example, a material used to divide the functional layer (organic layer) in an actively driven organic electroluminescent element, and is used to gradually form pixels including the functional layer and the partition wall by applying the material used to constitute the functional layer to the divided area (pixel area) by vapor deposition or inkjet and drying.

[0080] In the present invention, the weight average molecular weight refers to a polystyrene-equivalent weight average molecular weight (Mw) obtained by GPC (gel permeation chromatography).

[0081] In the present invention, the "amine value" means the amine value converted to effective solid content unless otherwise specified, and is a value represented by the mass of KOH equivalent to the amount of alkali per 1 g of solid content of the dispersant.

[0082] The method for determining the amine value will be described below.

[0083] The "acid value" means the acid value converted into effective solid content unless otherwise specified, and is calculated by neutralization titration.

[0084] In this specification, the percentage or part expressed by "mass" has the same meaning as the percentage or part expressed by "weight".

[0085] [1] Photosensitive resin composition

[0086] The photosensitive resin composition of the present invention contains (a) an alkali-soluble resin, (b) a photopolymerization initiator, and (c) an ethylenically unsaturated compound as essential components, and further contains (d) a colorant, a dispersant, a pigment derivative, a surfactant, a liquid repellent, an ultraviolet absorber, a polymerization inhibitor, a thermal polymerization initiator, an amino compound, a silane coupling agent, an inorganic filler, an adhesion enhancer, and other compounding components as needed. Usually, each compounding component is used in a state of being dissolved or dispersed in a solvent.

[0087] [1-1] Components and composition of photosensitive resin composition

[0088] The components and compositions constituting the photosensitive resin composition of the present invention will be described in order.

[0089] [1-1-1] (a) Alkali-soluble resin

[0090] The photosensitive resin composition of the present invention contains (a) an alkali-soluble resin. By containing (a) an alkali-soluble resin, development with an alkali developer can be performed, and a pattern of partition walls or the like can be produced.

[0091] The (a) alkali-soluble resin in the photosensitive resin composition of the present invention may contain an alkali-soluble resin (a1) having a cardo skeleton.

[0092] By containing the alkali-soluble resin (a1), the taper angle tends to become smaller.

[0093] [Alkali-soluble resin (a1)]

[0094] The alkali-soluble resin (a1) is not particularly limited as long as it contains a cardo skeleton, but preferably has a partial structure represented by the following general formula (a1-0) from the viewpoint of the taper angle.

[0095]

[0096] (The benzene ring in formula (a1-0) may be further substituted by any substituent; Q represents O, S, CO or a direct bond; * represents a connecting bond.)

[0097] The partial structure represented by the above formula (a1-0) contained in the alkali-soluble resin (a1) may be one type or two or more types.

[0098] In the above general formula (a1-0), from the viewpoint of the taper angle, Q is preferably a direct bond.

[0099] The benzene ring in formula (a1-0) is unsubstituted or may be further substituted with an arbitrary substituent. Examples of the arbitrary substituent include a methyl group and a methoxy group. From the viewpoint of ease of synthesis, the benzene ring is preferably unsubstituted.

[0100] Moreover, about the partial structure represented by said formula (a1-0), it is preferable that it has the partial structure represented by the following general formula (a1-1) from a viewpoint of developability.

[0101]

[0102] (The benzene ring in formula (a1-1) may be further substituted by any substituent; R 9 Each independently represents a hydrogen atom or a methyl group; Q represents O, S, CO or a direct bond; n represents an integer of 0 to 4; multiple Qs may be the same or different; * represents a connecting bond.

[0103] In the above formula (a1-1), from the viewpoint of the taper angle, preferably n≤3, more preferably n≤2, and further preferably n=0. 9 Preferred is a hydrogen atom.

[0104] In the above formula (a1-1), from the viewpoint of the taper angle, Q is preferably a direct bond.

[0105] The benzene ring in formula (a1-1) is unsubstituted or may be further substituted with an arbitrary substituent. Examples of the arbitrary substituent include a methyl group and a methoxy group. From the viewpoint of ease of synthesis, the benzene ring is preferably unsubstituted.

[0106] Moreover, about the partial structure represented by said formula (a1-1), the partial structure represented by the following formula (a1-2) is preferable from a viewpoint of developability.

[0107]

[0108] (The benzene ring in formula (a1-2) may be further substituted by any substituent; R 9 , Q and n have the same meanings as in formula (a1-1); R X1 , R X2 , R X3 Each independently represents a hydrogen atom or a polyacid residue; * represents a connecting bond. )

[0109] The polyacid residue refers to a monovalent or divalent group obtained by removing one or two OH groups from a polyacid.

[0110] Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0111] Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred from the viewpoint of patterning properties; tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred; and tetrahydrophthalic acid is further preferred.

[0112] The acid value of the alkali-soluble resin (a1) is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 60 mgKOH / g or more, still more preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. In addition, it is preferably 150 mgKOH / g or less, more preferably 140 mgKOH / g or less, further preferably 130 mgKOH / g or less, and still more preferably 120 mgKOH / g or less.

[0113] When the acid value of the alkali-soluble resin (a1) is equal to or greater than the above lower limit, developability tends to be improved. When the acid value of the alkali-soluble resin (a1) is equal to or less than the above upper limit, resolution tends to be improved.

[0114] The weight average molecular weight (Mw) of the alkali-soluble resin (a1) is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, further preferably 4000 or more, and particularly preferably 4500 or more. In addition, it is usually 20000 or less, preferably 15000 or less, more preferably 10000 or less, further preferably 8000 or less, and particularly preferably 6000 or less.

[0115] When the Mw of the alkali-soluble resin (a1) is equal to or greater than the above lower limit, the developing adhesion tends to be improved. When the Mw of the alkali-soluble resin (a1) is equal to or less than the above upper limit, the developing property tends to be good.

[0116] The content of the alkali-soluble resin (a1) relative to the total amount of the alkali-soluble resin (a) is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 40% by mass or more, particularly preferably 60% by mass or more.

[0117] When the content of the alkali-soluble resin (a1) is equal to or greater than the above lower limit, the taper angle tends to be improved. When the content of the alkali-soluble resin (a1) is equal to or less than the above upper limit, the developed morphology tends to be improved.

[0118] The (a) alkali-soluble resin in the photosensitive resin composition of the present invention may contain an alkali-soluble resin other than the alkali-soluble resin (a1), that is, an alkali-soluble resin not having a cardo skeleton (hereinafter, sometimes referred to as "other alkali-soluble resin").

[0119] The other alkali-soluble resin contained in the (a) alkali-soluble resin may be one kind or two or more kinds.

[0120] As other alkali-soluble resin, it is preferable that an alkali-soluble resin (a2) having a partial structure represented by the following general formula (a2-1) is contained from the viewpoint of developability.

[0121]

[0122] (R in formula (a2-1) 10 represents a hydrogen atom or a methyl group; * represents a connecting bond. )

[0123] In the above general formula (a2-1), from the viewpoint of reducing the residue, R 10 Preferred is methyl.

[0124] The partial structure represented by the above formula (a2-1) contained in the alkali-soluble resin (a2) may be one kind or two or more kinds.

[0125] Moreover, about the partial structure represented by said formula (a2-1), the partial structure represented by the following formula (a2-2) is preferable from a viewpoint of developability.

[0126]

[0127] (R in formula (a2-2) 10 Same as in formula (a2-1); * represents a connecting bond; R Y represents a hydrogen atom or a polyacid residue. )

[0128] The polyacid residue has the same meaning as in the above formula (a1-2).

[0129] Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0130] Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred from the viewpoint of patterning properties; tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred; and tetrahydrophthalic acid is further preferred.

[0131] The acid value of the alkali-soluble resin (a2) is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 60 mgKOH / g or more, still more preferably 80 mgKOH / g or more, and particularly preferably 90 mgKOH / g or more. In addition, it is preferably 150 mgKOH / g or less, more preferably 140 mgKOH / g or less, further preferably 130 mgKOH / g or less, and further more preferably 120 mgKOH / g or less.

[0132] When the acid value of the alkali-soluble resin (a2) is equal to or greater than the above lower limit, developability tends to be improved. When the acid value of the alkali-soluble resin (a2) is equal to or less than the above upper limit, resolution tends to be improved.

[0133] The weight average molecular weight (Mw) of the alkali-soluble resin (a2) is not particularly limited, but is usually 1000 or more, preferably 1500 or more, more preferably 2000 or more, further preferably 2500 or more, and particularly preferably 3000 or more. In addition, it is usually 20000 or less, preferably 15000 or less, more preferably 10000 or less, further preferably 6000 or less, and particularly preferably 4000 or less.

[0134] When the Mw of the alkali-soluble resin (a2) is equal to or greater than the above lower limit, the developing adhesiveness tends to be improved. When the Mw of the alkali-soluble resin (a2) is equal to or less than the above upper limit, the developing property tends to be good.

[0135] The content ratio of the alkali-soluble resin (a2) relative to the total amount of the alkali-soluble resin (a) is preferably 1% by mass or more, more preferably 5% by mass or more, particularly preferably 10% by mass or more, and is preferably 90% by mass or less, more preferably 70% by mass or less, further preferably 50% by mass or less, and particularly preferably 30% by mass or less.

[0136] When the content of the alkali-soluble resin (a2) is equal to or greater than the above lower limit, the developed morphology tends to be improved. When the content of the alkali-soluble resin (a2) is equal to or less than the above upper limit, the taper angle tends to be improved.

[0137] Furthermore, as other alkali-soluble resins, an acrylic copolymer resin (A11) having an ethylenically unsaturated group in a side chain (hereinafter, sometimes simply referred to as "acrylic copolymer resin (A11)") may be contained. Furthermore, an epoxy (meth)acrylate resin (A12) may be contained.

[0138] The acrylic copolymer resin (A11) will be described in detail below.

[0139] [Acrylic copolymer resin (A11)]

[0140] The acrylic copolymer resin (A11) may have an ethylenically unsaturated group in a side chain.

[0141] (Partial structure represented by general formula (I))

[0142] The partial structure containing a side chain having an ethylenically unsaturated group in the acrylic copolymer resin (A11) is not particularly limited, but preferably has a partial structure represented by the following general formula (I) from the viewpoint of ease of radical emission accompanying film flexibility.

[0143]

[0144] (In formula (I), R 111 and R 112 Each independently represents a hydrogen atom or a methyl group; * represents a connecting bond. )

[0145] The partial structure represented by the above formula (I) contained in the acrylic copolymer resin (A11) may be one type or two or more types.

[0146] Moreover, among the partial structures represented by the above-mentioned formula (I), the partial structures represented by the following general formula (I′) are also preferred from the viewpoints of sensitivity and alkali developability.

[0147]

[0148] (In formula (I'), R 111 and R 112 Each independently represents a hydrogen atom or a methyl group; R x represents a hydrogen atom or a polyacid residue; * represents a connecting bond. )

[0149] (R x )

[0150] In the above formula (I'), R x represents a hydrogen atom or a polyacid residue.

[0151] The polyacid residue refers to a monovalent or divalent group obtained by removing one or two OH groups from a polyacid.

[0152] Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0153] Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred from the viewpoint of patterning properties, and tetrahydrophthalic acid and succinic acid are more preferred.

[0154] When the acrylic copolymer resin (A11) contains the partial structure represented by the above formula (I), the content ratio thereof is not particularly limited, and is, for example, 10 mol% to 90 mol% based on the total number of moles of the structural units of the acrylic copolymer resin (A11).

[0155] When the acrylic copolymer resin (A11) contains the partial structure represented by the above formula (I'), the content ratio thereof is not particularly limited, and is, for example, 10 mol% to 80 mol% based on the total number of moles of the structural units of the acrylic copolymer resin (A11).

[0156] (Partial structure represented by general formula (II))

[0157] When the acrylic copolymer resin (A11) includes the partial structure represented by the above formula (I), other partial structures contained are not particularly limited, and from the viewpoint of development adhesion, for example, the partial structure represented by the following general formula (II) may be included.

[0158]

[0159] (In the above formula (II), R 113 Represents a hydrogen atom or a methyl group; R 114 represents an alkyl group optionally having a substituent, an aromatic ring group optionally having a substituent, or an alkenyl group optionally having a substituent; * represents a connecting bond. )

[0160] The partial structure represented by the above formula (II) contained in the acrylic copolymer resin (A11) may be one kind or two or more kinds.

[0161] (R 114 )

[0162] In the above formula (II), R 114 It represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent.

[0163] As R 114 The alkyl group in the alkyl group may be a linear, branched or cyclic alkyl group, and the number of carbon atoms thereof is, for example, 1 to 20.

[0164] As R 114 Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentyl group, and a dodecyl group.

[0165] Examples of the substituent which the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group.

[0166] As R 114 The aromatic ring group in the formula (a) may be a monovalent aromatic hydrocarbon ring group or a monovalent aromatic heterocyclic group. The carbon number thereof is, for example, 6 or more and 24 or less.

[0167] The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring.

[0168] The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and examples thereof include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furanopyrrole ring, a furanofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a phenanthridine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.

[0169] Examples of the substituent which the aromatic ring group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group.

[0170] As R 114 The alkenyl group in the alkylene group may be a linear, branched or cyclic alkenyl group. The number of carbon atoms is, for example, 2 or more and 22 or less.

[0171] Examples of the substituent which the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group.

[0172] R 114 It represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent.

[0173] When the acrylic copolymer resin (A11) contains the partial structure represented by the above formula (II), the content ratio thereof is not particularly limited, and is, for example, 1 mol % to 70 mol % based on the total molar number of the structural units of the acrylic copolymer resin (A11).

[0174] (Partial structure represented by general formula (III))

[0175] When the acrylic copolymer resin (A11) contains the partial structure represented by the above formula (I), it may contain a partial structure represented by the following general formula (III) as another partial structure contained from the viewpoint of heat resistance and film strength.

[0176]

[0177] (In the above formula (III), R 115 Represents a hydrogen atom or a methyl group; R 116 represents an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an alkynyl group optionally having a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group optionally having a substituent, a thiol group, or an alkyl sulfide group optionally having a substituent; t represents an integer of 0 to 5; when t is 2 or more, a plurality of R 116 Optional same or different; * indicates a connecting bond. )

[0178] The partial structure represented by the above formula (III) contained in the acrylic copolymer resin (A11) may be one type or two or more types.

[0179] (R 116 )

[0180] In the above formula (III), R 116 It represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkylthioether group which may have a substituent.

[0181] As R 116 The alkyl group in the alkyl group may be a linear, branched or cyclic alkyl group, and the number of carbon atoms thereof is, for example, 1 to 20.

[0182] As R 116 Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentyl group, and a dodecyl group.

[0183] Examples of the substituent which the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group.

[0184] As R 116 The alkenyl group in the alkylene group may be a linear, branched or cyclic alkenyl group. The number of carbon atoms is, for example, 2 or more and 22 or less.

[0185] Examples of the substituent which the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group.

[0186] As R 116 The alkynyl group in alkynyl may be a linear, branched or cyclic alkynyl group. The carbon number thereof is, for example, 2 or more and 20 or less.

[0187] Examples of the substituent which the alkynyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group.

[0188] As R 116 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0189] As R 116 The alkoxy group in the alkoxy group may be a linear, branched or cyclic alkoxy group. The carbon number thereof is, for example, 1 to 20.

[0190] Examples of the substituent which the alkoxy group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group.

[0191] As R 116 The alkyl sulfide group in the alkyl sulfide group may be a linear, branched or cyclic alkyl sulfide group. The carbon number thereof is, for example, 1 to 20.

[0192] Examples of the substituent which the alkyl group in the alkyl thioether group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group.

[0193] R 116 It represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkylthioether group which may have a substituent.

[0194] In the above formula (III), t represents an integer of 0-5.

[0195] When the acrylic copolymer resin (A11) contains the partial structure represented by the above formula (III), the content ratio thereof is not particularly limited, and is, for example, 0.5 mol% to 50 mol% based on the total molar number of the structural units of the acrylic copolymer resin (A11).

[0196] (Partial structure represented by general formula (IV))

[0197] When the acrylic copolymer resin (A11) has the partial structure represented by the above formula (I), it may have a partial structure represented by the following general formula (IV) as another partial structure contained therein.

[0198]

[0199] (In formula (IV), R 117 represents a hydrogen atom or a methyl group; * represents a connecting bond. )

[0200] The partial structure represented by the above formula (IV) contained in the acrylic copolymer resin (A11) may be one type or two or more types.

[0201] When the acrylic copolymer resin (A11) contains the partial structure represented by the above formula (IV), the content ratio thereof is not particularly limited, and is, for example, 5 mol% to 80 mol% based on the total molar number of the structural units of the acrylic copolymer resin (A11).

[0202] The acid value of the acrylic copolymer resin (A11) is not particularly limited, and is, for example, 30 mgKOH / g or more and 150 mgKOH / g or less.

[0203] The weight average molecular weight (Mw) of the acrylic copolymer resin (A11) is not particularly limited, and is, for example, 1,000 or more and 30,000 or less.

[0204] The content ratio of the acrylic copolymer resin (A11) with respect to the total amount of the (a) alkali-soluble resin is not particularly limited, and is, for example, 3% by mass or more and 70% by mass or less.

[0205] Specific examples of the acrylic copolymer resin (A11) include resins described in Japanese Patent Application Laid-Open No. 8-297366 or Japanese Patent Application Laid-Open No. 2001-89533.

[0206] Hereinafter, the epoxy (meth)acrylate resin (A12) will be described in detail.

[0207] [Epoxy (meth)acrylate resin (A12)]

[0208] Epoxy (meth) acrylate resin (A12) is a resin obtained by adding an ethylenically unsaturated monocarboxylic acid and / or its ester compound to an epoxy resin, optionally reacting an isocyanate group-containing compound, and then reacting a polybasic acid and / or its anhydride. Among them, epoxy (meth) acrylate resins having an aromatic ring in the main chain can be preferably used.

[0209] For example, a resin obtained by ring-opening addition of a carboxyl group of an unsaturated monocarboxylic acid to an epoxy group of an epoxy resin, adding an ethylenically unsaturated bond to the epoxy compound via an ester bond (-COO-), and adding a carboxyl group of a polyacid anhydride to the hydroxyl group generated at this time. In addition, a resin obtained by simultaneously adding a polyol to the addition of a polyacid and / or its anhydride can also be mentioned.

[0210] The epoxy (meth)acrylate resin (A12) also includes a resin obtained by further reacting the carboxyl group of the resin obtained by the above reaction with a compound having a reactive functional group.

[0211] As described above, epoxy (meth)acrylate resin does not substantially have an epoxy group in chemical structure and is not limited to "(meth)acrylate", but is named as such by convention because epoxy compounds (epoxy resins) are raw materials and "(meth)acrylate" is a representative example.

[0212] Here, so-called epoxy resin, also comprises the raw material compound before forming resin by heat curing.As this epoxy resin, can be suitably selected and used from among known epoxy resin.In addition, epoxy resin can use the compound that makes phenolic compound and epihalohydrin react and obtain.As phenolic compound, preferably have the compound of divalent or more divalent phenolic hydroxyl group, can be monomer, also can be polymer.

[0213] Examples of the epoxy resin used as a raw material include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, dihydroxyfluorene type epoxy resin, dihydroxyalkyleneoxyfluorene type epoxy resin, and diglycidyl ether of 1,1-bis(4′-hydroxyphenyl)adamantane. Resins having an aromatic ring in the main chain can be preferably used.

[0214] Among them, from the viewpoint of high cured film strength, bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, etc. are preferred.

[0215] As the epoxy resin, for example, bisphenol A type epoxy resin (for example, "jER (registered trademark, hereinafter the same) 828", "jER1001", "jER1002", "jER1004" manufactured by Mitsubishi Chemical Corporation, "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323, softening point 76°C) etc.); bisphenol F type resin (for example, "jER807", "jER4004P", "jER4005P", "jER4007P" manufactured by Mitsubishi Chemical Corporation, "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66°C) etc.), bisphenol S type epoxy resin; biphenyl glycidyl ether (for example, "jERYX-4000" manufactured by Mitsubishi Chemical Corporation); phenol novolac type epoxy resin (for example, "EP PN (registered trademark, the same below)-201", "jER152", "jER154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Company); (o-, m-, p-) cresol novolac type epoxy resins (for example, "EOCN (registered trademark, the same below)-102S", "EOCN-1020", "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.); triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd.); trisphenol methane type epoxy resins (for example, "EPPN-501", "EPPN-502", "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.); alicyclic epoxy resins (for example, "Celloxide (registered trademark, the same below) 2021P", "Celloxide EHPE" manufactured by Daicel Corporation); epoxy resins represented by the following general formulas (i-12) and (i-13).

[0216] Specifically, examples of the epoxy resin represented by the following general formula (i-12) include "NC-3000" manufactured by Nippon Kayaku Co., Ltd.

[0217]

[0218] (In formula (i-12), b is the average value, which represents a number from 0 to 10; R 121 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group; a plurality of R groups present in one molecule 121 They can be the same or different.)

[0219]

[0220] (In formula (i-13), Z represents a linking group represented by the following general formula (i-13-1) or (i-13-2); wherein the molecular structure contains one or more adamantane structures; and c represents 2 or 3.)

[0221]

[0222] (In formula (i-13-1) and (i-13-2), R 131 ~R 134 and R 135 ~R 137 Each independently represents an adamantyl group optionally having a substituent, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms optionally having a substituent, or a phenyl group optionally having a substituent; * represents a connecting bond. )

[0223] Among these, the epoxy resin represented by any one of formula (i-12) and (i-13) is preferably used.

[0224] Examples of the ethylenically unsaturated monocarboxylic acid include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and pentaerythritol tri(meth)acrylate succinic anhydride adduct, pentaerythritol tri(meth)acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta(meth)acrylate succinic anhydride adduct, dipentaerythritol penta(meth)acrylate phthalic anhydride adduct, dipentaerythritol penta(meth)acrylate tetrahydrophthalic anhydride adduct, and a reaction product of (meth)acrylic acid and ε-caprolactone. Among them, (meth)acrylic acid is preferred from the viewpoint of sensitivity.

[0225] Examples of the polyacid and / or its anhydride include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and anhydrides thereof. Among these, from the viewpoint of outgassing, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are preferred, and succinic anhydride and tetrahydrophthalic anhydride are more preferred.

[0226] By using a polyol as a raw material for the epoxy (meth) acrylate resin (A12), the molecular weight of the epoxy (meth) acrylate resin (A12) can be increased and branches can be introduced into the molecule, thereby showing a tendency to achieve a balance between the molecular weight and the viscosity. In addition, the introduction rate of the acid group into the molecule can be increased, showing a tendency to easily achieve a balance between sensitivity and adhesion.

[0227] As the polyol, for example, one or more polyols selected from the group consisting of trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol are preferred.

[0228] As epoxy (meth)acrylate resin (A12), in addition to the above, for example, resins described in Korean Patent Publication No. 10-2013-0022955 can be mentioned.

[0229] The acid value of the epoxy (meth)acrylate resin (A12) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 30 mgKOH / g or more, still more preferably 40 mgKOH / g or more, particularly preferably 50 mgKOH / g or more, and is preferably 200 mgKOH / g or less, more preferably 180 mgKOH / g or less, further preferably 150 mgKOH / g or less, further more preferably 120 mgKOH / g or less, and particularly preferably 110 mgKOH / g or less.

[0230] When the acid value of the epoxy (meth)acrylate resin (A12) is equal to or greater than the above lower limit, developability tends to be improved. When the acid value of the epoxy (meth)acrylate resin (A12) is equal to or less than the above upper limit, film strength tends to be improved.

[0231] For example, the acid value of the epoxy (meth)acrylate resin (A12) is preferably 10 to 200 mgKOH / g, more preferably 20 to 180 mgKOH / g, further preferably 30 to 150 mgKOH / g, still more preferably 40 to 120 mgKOH / g, particularly preferably 50 to 110 mgKOH / g.

[0232] The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (A12) is not particularly limited, but is usually 1,000 or more, preferably 2,000 or more, more preferably 3,000 or more, and further preferably 3,500 or more, and is usually 30,000 or less, preferably 15,000 or less, more preferably 10,000 or less, further preferably 8,000 or less, and particularly preferably 6,000 or less.

[0233] When the Mw of the epoxy (meth)acrylate resin (A12) is greater than or equal to the above lower limit, the film strength tends to be improved, while when the Mw of the epoxy (meth)acrylate resin (A12) is less than or equal to the above upper limit, the residue tends to be reduced.

[0234] For example, the weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (A12) is preferably 1,000 to 30,000, more preferably 2,000 to 15,000, further preferably 3,000 to 10,000, still more preferably 3,500 to 8,000, particularly preferably 3,500 to 6,000.

[0235] When the (a) alkali-soluble resin contains the epoxy (meth)acrylate resin (A12), the content ratio of the epoxy (meth)acrylate resin (A12) relative to the total amount of the (a) alkali-soluble resin is not particularly limited, and is, for example, preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more.

[0236] When the content ratio is equal to or greater than the above lower limit, the amount of residue tends to decrease.

[0237] Epoxy (meth) acrylate resin (A12) can be synthesized by a known method. Specifically, the following method can be used: dissolve the above-mentioned epoxy resin in an organic solvent, add the above-mentioned acid and / or its ester compound having an ethylenically unsaturated bond in the presence of a catalyst and a thermal inhibitor to carry out an addition reaction, and then add a polyacid and / or its anhydride to continue the reaction. For example, the method described in Japanese Patent No. 3938375 Gazette and Japanese Patent No. 5169422 Gazette can be used.

[0238] Here, examples of the organic solvent used in the reaction include one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate.

[0239] Examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine; quaternary ammonium salts such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, and trimethylbenzylammonium chloride; phosphorus compounds such as triphenylphosphine; and antimonides such as triphenylstibine.

[0240] Examples of the thermal polymerization inhibitor include one or more of hydroquinone, hydroquinone monomethyl ether, and methyl hydroquinone.

[0241] The amount of the ethylenically unsaturated monocarboxylic acid and / or its ester compound used is usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, relative to 1 chemical equivalent of the epoxy group of the epoxy resin.

[0242] The amount of the polybasic acid and / or its anhydride used is usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1 chemical equivalents, relative to 1 chemical equivalent of the hydroxyl group generated by the above-mentioned addition reaction.

[0243] The temperature during the addition reaction can be generally 60 to 150°C, preferably 80 to 120°C.

[0244] Among the epoxy (meth)acrylate resins (A12), from the viewpoint of film strength and linearity, epoxy (meth)acrylate resins having at least one of the partial structures represented by the following general formula (i), the following general formula (ii-1), the following general formula (ii-2), and the following general formula (iii) are preferred.

[0245]

[0246] (In formula (i), R a Represents a hydrogen atom or a methyl group; R b represents a linear or branched divalent aliphatic group optionally having a substituent, a divalent aromatic ring group optionally having a substituent, or a group formed by connecting one or more divalent aliphatic groups optionally having a substituent and one or more divalent aromatic ring groups; the benzene ring in formula (i) is optionally further substituted by any substituent; * represents a connecting bond. )

[0247]

[0248] (In formula (ii-1), R c Each independently represents a hydrogen atom or a methyl group; R α represents a monovalent cyclic hydrocarbon group optionally having a substituent; q is an integer greater than 1; the benzene ring in formula (ii-1) may be further substituted by any substituent.

[0249]

[0250] (In formula (ii-2), R c Each independently represents a hydrogen atom or a methyl group; R β represents a divalent cyclic hydrocarbon group which may optionally have a substituent; the benzene ring in formula (ii-2) may further be substituted by any substituent. )

[0251]

[0252] (In formula (iii), R e represents a hydrogen atom or a methyl group; δ represents a single bond, -CO-, an alkylene group optionally having a substituent, or a divalent cyclic hydrocarbon group optionally having a substituent; the benzene ring in formula (iii) may be further substituted by any substituent; * represents a connecting bond. )

[0253] The epoxy (meth)acrylate resin having a partial structure represented by the following general formula (i) (hereinafter, sometimes referred to as “epoxy (meth)acrylate resin (A12-1)”) will be described in detail.

[0254]

[0255] (In formula (i), R a Represents a hydrogen atom or a methyl group; R b represents a linear or branched divalent aliphatic group optionally having a substituent, a divalent aromatic ring group optionally having a substituent, or a group formed by connecting one or more divalent aliphatic groups optionally having a substituent and one or more divalent aromatic ring groups; the benzene ring in formula (i) is optionally further substituted by any substituent; * represents a connecting bond. )

[0256] The partial structure represented by the above formula (i) contained in the epoxy (meth)acrylate resin (A12-1) may be one type or two or more types.

[0257] (R b )

[0258] In the above formula (i), R b It represents a linear or branched divalent aliphatic group which may have a substituent, a divalent aromatic ring group which may have a substituent, or a group in which one or more divalent aliphatic groups which may have a substituent are linked to one or more divalent aromatic ring groups.

[0259] The divalent aliphatic group includes linear and branched aliphatic groups, and the number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less.

[0260] When the carbon number is equal to or greater than the above lower limit, the film strength tends to be improved, while when the carbon number is equal to or less than the above upper limit, the resolution tends to be improved.

[0261] For example, the divalent aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 10 carbon atoms.

[0262] Specific examples of the divalent straight-chain aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group. Among these, a methylene group is preferred from the viewpoint of resolution and production cost.

[0263] Specific examples of the divalent branched aliphatic group include structures in which the above-mentioned divalent straight-chain aliphatic group has a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group as a side chain.

[0264] Examples of the substituent that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

[0265] Examples of the divalent aromatic ring group include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic groups, which usually have 4 or more carbon atoms, preferably 5 or more carbon atoms, more preferably 6 or more carbon atoms, and preferably 20 or less carbon atoms, more preferably 15 or less carbon atoms, and further preferably 10 or less carbon atoms.

[0266] When the carbon number is equal to or greater than the above lower limit, the film strength tends to be improved, while when the carbon number is equal to or less than the above upper limit, the developability tends to be improved.

[0267] For example, the divalent aromatic ring group has preferably 4 to 20 carbon atoms, more preferably 5 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms.

[0268] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring.

[0269] The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. As the divalent aromatic heterocyclic group, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furanopyrrole ring, a furanofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a phenanthridine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring may be cited.

[0270] Among these, from the viewpoint of production cost, a benzene ring and a naphthalene ring having two free atomic valences are preferred, and a benzene ring having two free atomic valences is more preferred.

[0271] Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, unsubstituted groups are preferred from the viewpoint of curability.

[0272] Examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked together include groups in which one or more of the above-mentioned divalent aliphatic groups and one or more of the above-mentioned divalent aromatic ring groups are linked together.

[0273] The number of the divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, and more preferably 3 or less.

[0274] When the number of divalent aliphatic groups is equal to or greater than the above lower limit, developability tends to be improved, while when the number of divalent aliphatic groups is equal to or less than the above upper limit, film strength tends to be improved.

[0275] For example, the number of the divalent aliphatic groups is preferably 1-10, more preferably 1-5, and even more preferably 1-3.

[0276] The number of the divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, and more preferably 3 or less.

[0277] When the number of the divalent aromatic ring groups is equal to or greater than the above lower limit, the film strength tends to be improved, while when the number of the divalent aromatic ring groups is equal to or less than the above upper limit, the developability tends to be improved.

[0278] For example, the number of the divalent aromatic ring groups is preferably 1-10, more preferably 1-5, and even more preferably 1-3.

[0279] Specific examples of the group formed by connecting one or more divalent aliphatic groups to one or more divalent aromatic ring groups include groups represented by the following formulae (iA) to (iF). Among these, the group represented by the following formula (iA) is preferred from the viewpoint of the rigidity of the skeleton and the hydrophobization of the membrane.

[0280] Hereinafter, * represents a connecting bond.

[0281]

[0282] As described above, the benzene ring in formula (i) may be further substituted by any substituent. Examples of such substituents include hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. The number of substituents is also not particularly limited and may be 1 or more than 2.

[0283] Among these, unsubstituted is preferred from the viewpoint of curability.

[0284] The partial structure represented by the above formula (i) is preferably a partial structure represented by the following formula (i-1) from the viewpoint of development solubility.

[0285]

[0286] (In formula (i-1), R a and R b has the same meaning as in the above formula (i); R y represents a hydrogen atom or a polyacid residue; * represents a connecting bond; the benzene ring in formula (i-1) may be further substituted by any substituent.

[0287] (R y )

[0288] R y represents a hydrogen atom or a polyacid residue.

[0289] The polyacid residue refers to a monovalent or divalent group obtained by removing one or two OH groups from a polyacid.

[0290] Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0291] Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred from the viewpoint of patterning properties, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

[0292] The partial structure represented by the above formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (A12-1) may be one type or two or more types.

[0293] The number of partial structures represented by the formula (i) contained in one molecule of the epoxy (meth)acrylate resin (A12-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, and is preferably 10 or less, even more preferably 8 or less.

[0294] When the number of the partial structures is equal to or greater than the lower limit, developability tends to be improved, while when the number of the partial structures is equal to or less than the upper limit, film strength tends to be improved.

[0295] For example, the number of the partial structures represented by the formula (i) contained in one molecule of the epoxy (meth)acrylate resin (A12-1) is preferably 1 to 10, more preferably 2 to 8, and even more preferably 3 to 8.

[0296] The number of partial structures represented by the above formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (A12-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and is preferably 10 or less, further preferably 8 or less.

[0297] When the number of the partial structures is equal to or greater than the lower limit, developability tends to be improved, while when the number of the partial structures is equal to or less than the upper limit, film strength tends to be improved.

[0298] For example, the number of the partial structures represented by the formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (A12-1) is preferably 1 to 10, more preferably 2 to 8, and even more preferably 3 to 8.

[0299] Specific examples of the epoxy (meth)acrylate resin (A12-1) are given below.

[0300]

[0301] Next, the epoxy (meth) acrylate resin having a partial structure represented by the following general formula (ii-1) and the epoxy (meth) acrylate resin having a partial structure represented by the general formula (ii-2) are described in detail. (Hereinafter, the two may be collectively referred to as "epoxy (meth) acrylate resin (A12-2)")

[0302]

[0303] (In formula (ii-1), R c Represents a hydrogen atom or a methyl group; R α represents a monovalent cyclic hydrocarbon group optionally having a substituent; q is an integer greater than 1; the benzene ring in formula (ii-1) may be further substituted by any substituent.

[0304] By having the partial structure represented by formula (ii-1), the light shielding property tends to be improved.

[0305] (R α )

[0306] In the above formula (ii-1), R α It represents a monovalent cyclic hydrocarbon group which may have a substituent.

[0307] As Rα Examples of the monovalent cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

[0308] The number of rings of the aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 6 or less, preferably 4 or less, and more preferably 3 or less.

[0309] When the number of rings possessed by the aliphatic cyclic group is equal to or greater than the above lower limit, the film strength tends to be improved, while when the number of rings possessed by the aliphatic cyclic group is equal to or less than the above upper limit, the developability tends to be improved.

[0310] For example, the number of rings possessed by the aliphatic cyclic group is preferably 1 to 6, more preferably 1 to 4, further preferably 1 to 3, particularly preferably 2 to 3.

[0311] The aliphatic cyclic group generally has 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, particularly preferably 15 or less.

[0312] When the carbon number is equal to or greater than the above lower limit, the film strength tends to be improved, while when the carbon number is equal to or less than the above upper limit, the developability tends to be improved.

[0313] For example, the aliphatic ring group has preferably 4 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, further preferably 6 to 20 carbon atoms, and particularly preferably 8 to 15 carbon atoms.

[0314] Specific examples of the aliphatic ring in the aliphatic cyclic group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring. Among these, adamantane ring is preferred from the viewpoint of achieving both film strength and developability.

[0315] The number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less.

[0316] When the number of rings contained in the aromatic ring group is equal to or greater than the above lower limit, the film strength tends to be improved, while when the number of rings contained in the aromatic ring group is equal to or less than the above upper limit, the developability tends to be improved.

[0317] For example, the number of rings contained in the aromatic ring group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 5.

[0318] Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.

[0319] The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and is preferably 30 or less, more preferably 20 or less, and further preferably 15 or less.

[0320] When the number of carbon atoms is equal to or greater than the above lower limit, the film strength tends to be improved, while when the number of carbon atoms is equal to or less than the above upper limit, the developability tends to be improved.

[0321] For example, the number of carbon atoms in the aromatic ring group is preferably 4-30, more preferably 5-20, and even more preferably 6-15.

[0322] Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, a fluorene ring is preferred from the viewpoint of achieving both film strength and developability.

[0323] As R α The substituents that the cyclic hydrocarbon group may have include, for example, alkyl groups having 1 to 5 carbon atoms, such as hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, isopentyl, etc.; alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy; nitro; cyano; and carboxyl. Among these, unsubstituted is preferred from the viewpoint of ease of synthesis.

[0324] Among these, R α It is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group.

[0325] q represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less.

[0326] When q is equal to or greater than the above lower limit, developability tends to be improved, while when q is equal to or less than the above upper limit, film strength tends to be improved.

[0327] For example, q is preferably an integer of 1 to 3, and more preferably an integer of 2 to 3.

[0328] As described above, the benzene ring in formula (ii-1) is optionally further substituted by any substituent. As the substituent, for example, hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy can be listed. The number of substituents is also not particularly limited, and can be 1 or more than 2. Among these, from the perspective of curability, it is preferably unsubstituted.

[0329] Specific examples of the partial structure represented by the above formula (ii-1) are listed below. Hereinafter, * represents a connecting bond.

[0330]

[0331] Next, the epoxy (meth)acrylate resin having a partial structure represented by the following general formula (ii-2) will be described in detail.

[0332]

[0333] (In formula (ii-2), R c Represents a hydrogen atom or a methyl group; R β represents a divalent cyclic hydrocarbon group which may optionally have a substituent; the benzene ring in formula (ii-2) may further be substituted by any substituent. )

[0334] By having the partial structure represented by formula (ii-2), the light shielding property tends to be improved.

[0335] (R β )

[0336] In the above formula (ii-2), R β It represents a divalent cyclic hydrocarbon group which may have a substituent.

[0337] As R β Examples of the divalent cyclic hydrocarbon group include a divalent aliphatic ring group and a divalent aromatic ring group.

[0338] The number of rings of the divalent aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less.

[0339] When the number of rings in the divalent aliphatic ring group is equal to or greater than the above lower limit, the film strength tends to be improved, while when the number of rings in the divalent aliphatic ring group is equal to or less than the above upper limit, the developability tends to be improved.

[0340] For example, the number of rings possessed by the divalent aliphatic ring group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 5.

[0341] The carbon number of the divalent aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and is preferably 40 or less, more preferably 35 or less, and further preferably 30 or less.

[0342] When the carbon number is equal to or greater than the above lower limit, the film strength tends to be improved, while when the carbon number is equal to or less than the above upper limit, the developability tends to be improved.

[0343] For example, the divalent aliphatic ring group preferably has 4 to 40 carbon atoms, more preferably 6 to 35 carbon atoms, and even more preferably 8 to 30 carbon atoms.

[0344] Specific examples of the aliphatic ring in the divalent aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring. Among these, adamantane ring is preferred from the viewpoint of achieving both film strength and developability.

[0345] The number of rings in the divalent aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less.

[0346] When the number of rings in the divalent aromatic ring group is equal to or greater than the lower limit, the film strength tends to be improved, while when the number of rings in the divalent aromatic ring group is equal to or less than the upper limit, the developability tends to be improved.

[0347] For example, the number of rings possessed by the divalent aromatic ring group is preferably 1 to 10, more preferably 1 to 5, further preferably 2 to 5, and particularly preferably 3 to 5.

[0348] Examples of the divalent aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.

[0349] The carbon number of the divalent aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and is preferably 40 or less, more preferably 30 or less, further preferably 20 or less, particularly preferably 15 or less.

[0350] When the carbon number is equal to or greater than the above lower limit, the film strength tends to be improved, while when the carbon number is equal to or less than the above upper limit, the developability tends to be improved.

[0351] For example, the carbon number of the divalent aromatic ring group is preferably 4-40, more preferably 6-30, further preferably 8-20, and particularly preferably 10-15.

[0352] Specific examples of the aromatic ring in the divalent aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Among these, a benzene ring is preferred from the viewpoint of film strength and developability.

[0353] Examples of the substituents that the divalent cyclic hydrocarbon group may have include alkyl groups having 1 to 5 carbon atoms, such as hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and isopentyl; alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy; nitro; cyano; and carboxyl. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

[0354] Among these, R βIt is preferably a divalent aliphatic ring group, and more preferably a divalent adamantane ring group.

[0355] As described above, the benzene ring in formula (ii-2) is optionally further substituted by any substituent. As the substituent, for example, hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy can be listed. The number of substituents is also not particularly limited, and can be 1 or more than 2. Among these, from the perspective of curability, it is preferably unsubstituted.

[0356] Specific examples of the partial structure represented by the above formula (ii-2) are listed below. Hereinafter, * represents a connecting bond.

[0357]

[0358] The partial structure represented by the above formula (ii-1) is preferably a partial structure represented by the following formula (ii-3) from the viewpoint of developability.

[0359]

[0360] (In formula (ii-3), R c , R α and q has the same meaning as in the above formula (ii-1); R z1 , R z2 Each independently represents a hydrogen atom or a polyacid residue. )

[0361] The partial structure represented by the above formula (ii-2) is preferably a partial structure represented by the following formula (ii-4) from the viewpoint of developability.

[0362]

[0363] (In formula (ii-4), R c , R β has the same meaning as in formula (ii-2); R v1 , R v2 Each independently represents a hydrogen atom or a polyacid residue. )

[0364] The polyacid residue refers to a monovalent or divalent group obtained by removing one or two OH groups from a polyacid.

[0365] Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0366] Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred from the viewpoint of patterning properties, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

[0367] The partial structure represented by the above formula (ii-1), the above formula (ii-2), the above formula (ii-3), or the above formula (ii-4) contained in one molecule of the epoxy (meth)acrylate resin (A12-2) may be one kind or two or more kinds.

[0368] The number of partial structures represented by the above formula (ii-1) contained in one molecule of the epoxy (meth)acrylate resin (A12-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less.

[0369] When the number of partial structures represented by the formula (ii-1) is greater than or equal to the above lower limit, the resolution tends to be improved. When the number of partial structures represented by the formula (ii-1) is less than or equal to the above upper limit, the developability tends to be improved.

[0370] For example, the number of the partial structures represented by the formula (ii-1) contained in one molecule of the epoxy (meth)acrylate resin (A12-2) is preferably 1 to 20, more preferably 1 to 15, and even more preferably 3 to 10.

[0371] The number of partial structures represented by the above formula (ii-2) contained in one molecule of the epoxy (meth)acrylate resin (A12-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less.

[0372] When the number of partial structures represented by the formula (ii-2) is greater than or equal to the above lower limit, the resolution tends to be improved. When the number of partial structures represented by the formula (ii-2) is less than or equal to the above upper limit, the developability tends to be improved.

[0373] For example, the number of the partial structures represented by the formula (ii-2) contained in one molecule of the epoxy (meth)acrylate resin (A12-2) is preferably 1 to 20, more preferably 1 to 15, and even more preferably 3 to 10.

[0374] The number of partial structures represented by the above formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (A12-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less.

[0375] When the number of partial structures represented by the formula (ii-3) is greater than or equal to the above lower limit, the resolution tends to be improved. When the number of partial structures represented by the formula (ii-3) is less than or equal to the above upper limit, the developability tends to be improved.

[0376] For example, the number of the partial structures represented by the formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (A12-2) is preferably 1 to 20, more preferably 1 to 15, and even more preferably 3 to 10.

[0377] The number of partial structures represented by the above formula (ii-4) contained in one molecule of the epoxy (meth)acrylate resin (A12-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less.

[0378] When the number of partial structures represented by the formula (ii-4) is greater than or equal to the above lower limit, the resolution tends to be improved. When the number of partial structures represented by the formula (ii-4) is less than or equal to the above upper limit, the developability tends to be improved.

[0379] For example, the number of the partial structures represented by the formula (ii-4) contained in one molecule of the epoxy (meth)acrylate resin (A12-2) is preferably 1 to 20, more preferably 1 to 15, and even more preferably 3 to 10.

[0380] Next, the epoxy (meth)acrylate resin having a partial structure represented by the following general formula (iii) (hereinafter, sometimes referred to as “epoxy (meth)acrylate resin (A12-3)”) will be described in detail.

[0381]

[0382] (In formula (iii), R e represents a hydrogen atom or a methyl group; δ represents a single bond, -CO-, an alkylene group optionally having a substituent, or a divalent cyclic hydrocarbon group optionally having a substituent; the benzene ring in formula (iii) may be further substituted by any substituent; * represents a connecting bond. )

[0383] The partial structure represented by the above formula (iii) contained in the epoxy (meth)acrylate resin (A12-3) may be one type or two or more types.

[0384] (δ)

[0385] In the above formula (iii), δ represents a single bond, -CO-, an alkylene group which may have a substituent, or a divalent cyclic hydrocarbon group which may have a substituent.

[0386] The alkylene group in δ may be a linear chain or a branched chain, but is preferably a linear chain from the viewpoint of development solubility, and is preferably a branched chain from the viewpoint of development adhesion.

[0387] The carbon number of the alkylene group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 6 or less, preferably 4 or less.

[0388] When the carbon number is equal to or greater than the above lower limit, the film strength tends to be improved, while when the carbon number is equal to or less than the above upper limit, the developability tends to be improved.

[0389] For example, the alkylene group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 2 to 4 carbon atoms.

[0390] Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and a heptylene group. From the viewpoint of achieving both film strength and developability, an ethylene group and a propylene group are preferred, and a propylene group is more preferred.

[0391] Examples of the substituent that the alkylene group may have include alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy groups; hydroxy groups; nitro groups; cyano groups; and carboxyl groups. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

[0392] Examples of the divalent cyclic hydrocarbon group in δ include a divalent aliphatic ring group and a divalent aromatic ring group.

[0393] The number of rings of the divalent aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less.

[0394] When the number of rings in the divalent aliphatic ring group is equal to or greater than the above lower limit, the film strength tends to be improved, while when the number of rings in the divalent aliphatic ring group is equal to or less than the above upper limit, the developability tends to be improved.

[0395] For example, the number of rings possessed by the divalent aliphatic ring group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 5.

[0396] The carbon number of the divalent aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and is preferably 40 or less, more preferably 35 or less, and further preferably 30 or less.

[0397] When the carbon number is equal to or greater than the above lower limit, the film strength tends to be improved, while when the carbon number is equal to or less than the above upper limit, the developability tends to be improved.

[0398] For example, the divalent aliphatic ring group preferably has 4 to 40 carbon atoms, more preferably 6 to 35 carbon atoms, and even more preferably 8 to 30 carbon atoms.

[0399] Specific examples of the aliphatic ring in the divalent aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring. Among these, adamantane ring is preferred from the viewpoint of achieving both film strength and developability.

[0400] The number of rings in the divalent aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less.

[0401] When the number of rings in the divalent aromatic ring group is equal to or greater than the lower limit, the film strength tends to be improved, while when the number of rings in the divalent aromatic ring group is equal to or less than the upper limit, the developability tends to be improved.

[0402] For example, the number of rings possessed by the divalent aromatic ring group is preferably 1 to 10, more preferably 1 to 5, further preferably 2 to 5, and particularly preferably 3 to 5.

[0403] Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.

[0404] The carbon number of the divalent aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and is preferably 40 or less, more preferably 30 or less, further preferably 20 or less, particularly preferably 15 or less.

[0405] When the carbon number is equal to or greater than the above lower limit, the film strength tends to be improved, while when the carbon number is equal to or less than the above upper limit, the developability tends to be improved.

[0406] For example, the carbon number of the divalent aromatic ring group is preferably 4-40, more preferably 6-30, further preferably 8-20, and particularly preferably 10-15.

[0407] Specific examples of the aromatic ring in the divalent aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Among these, a benzene ring is preferred from the viewpoint of achieving both film strength and developability.

[0408] Examples of the substituents that the divalent cyclic hydrocarbon group may have include alkyl groups having 1 to 5 carbon atoms, such as hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and isopentyl; alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy; hydroxyl; nitro; cyano; and carboxyl. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

[0409] Among these, from the viewpoint of developability, δ is preferably an alkylene group which may have a substituent, and more preferably a dimethylmethylene group.

[0410] As described above, the benzene ring in formula (iii) is optionally further substituted by any substituent. As the substituent, for example, hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy can be listed. The number of substituents is also not particularly limited, and can be 1 or more than 2. Among these, from the perspective of curability, it is preferably unsubstituted.

[0411] The partial structure represented by the above formula (iii) is preferably a partial structure represented by the following formula (iii-1) from the viewpoint of development solubility.

[0412]

[0413] (In formula (iii-1), R e and δ have the same meanings as in the above formula (iii); R W represents a hydrogen atom or a polyacid residue; * represents a connecting bond; the benzene ring in formula (iii-1) may be further substituted by any substituent.

[0414] The polyacid residue refers to a monovalent or divalent group obtained by removing one or two OH groups from a polyacid.

[0415] Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0416] Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred from the viewpoint of patterning properties, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

[0417] The number of partial structures represented by the formula (iii) contained in one molecule of the epoxy (meth)acrylate resin (A12-3) is not particularly limited, but is preferably 1 or more, more preferably 5 or more, further preferably 10 or more, and is preferably 18 or less, further preferably 15 or less.

[0418] When the number of partial structures represented by the formula (iii) is equal to or greater than the lower limit, the resolution tends to be improved. When the number of partial structures represented by the formula (iii) is equal to or less than the upper limit, the developability tends to be improved.

[0419] For example, the number of the partial structures represented by the formula (iii) contained in one molecule of the epoxy (meth)acrylate resin (A12-3) is preferably 1 to 18, more preferably 5 to 15, and even more preferably 10 to 15.

[0420] The number of partial structures represented by the formula (iii-1) contained in one molecule of the epoxy (meth)acrylate resin (A12-3) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and is preferably 18 or less, further preferably 15 or less.

[0421] When the number of the partial structures represented by the formula (iii-1) is greater than or equal to the above lower limit, the resolution tends to be improved. When the number of the partial structures represented by the formula (iii-1) is less than or equal to the above upper limit, the developability tends to be improved.

[0422] For example, the number of the partial structures represented by the formula (iii-1) contained in one molecule of the epoxy (meth)acrylate resin (A12-3) is preferably 1 to 18, more preferably 3 to 15, and even more preferably 5 to 15.

[0423] Specific examples of the epoxy (meth)acrylate resin (A12-3) are given below.

[0424]

[0425] When the (a) alkali-soluble resin contains both an acrylic copolymer resin (A11) and an epoxy (meth)acrylate resin (A12), the content ratio of the acrylic copolymer resin (A11) relative to the total content of the acrylic copolymer resin (A11) and the epoxy (meth)acrylate resin (A12) is preferably 10 mass % or more, more preferably 20 mass % or more, further preferably 30 mass % or more, particularly preferably 40 mass % or more, and is preferably 90 mass % or less, more preferably 75 mass % or less, further preferably 60 mass % or less, and particularly preferably 50 mass % or less.

[0426] When the content ratio is set to be equal to or greater than the lower limit, the residue tends to be reduced, while when the content ratio is set to be equal to or less than the upper limit, the adhesion tends to be improved.

[0427] When the (a) alkali-soluble resin contains both an acrylic copolymer resin (A11) and an epoxy (meth)acrylate resin (A12), for example, the content ratio of the acrylic copolymer resin (A11) relative to the total content of the acrylic copolymer resin (A11) and the epoxy (meth)acrylate resin (A12) is preferably 10 to 90% by mass, more preferably 20 to 75% by mass, further preferably 30 to 60% by mass, and particularly preferably 40 to 50% by mass.

[0428] The (a) alkali-soluble resin in the present invention may contain other alkali-soluble resins in addition to the acrylic copolymer resin (A11) or the epoxy (meth)acrylate resin (A12).

[0429] The content ratio of the (a) alkali-soluble resin in the photosensitive resin composition of the present invention is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, still more preferably 40% by mass or more, particularly preferably 50% by mass or more, and is usually 90% by mass or less, preferably 80% by mass or less, and more preferably 70% by mass or less, relative to the total solid content of the photosensitive resin composition.

[0430] When the content ratio is set to be equal to or greater than the above lower limit, the resolution tends to be improved, while when the content ratio is set to be equal to or less than the above upper limit, the surface hardness tends to be improved.

[0431] For example, the content ratio of (a) the alkali-soluble resin relative to the total solid content of the photosensitive resin composition is preferably 5 to 90% by mass, more preferably 10 to 90% by mass, further preferably 20 to 80% by mass, further preferably 30 to 80% by mass, particularly preferably 40 to 70% by mass, and particularly preferably 50 to 70% by mass.

[0432] The sum of the content ratio of the following (c) ethylenically unsaturated compound and the content ratio of the (a) alkali-soluble resin relative to the total solid content of the photosensitive resin composition is not particularly limited, but is preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, particularly preferably 60% by mass or more, and is preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, and further preferably 75% by mass or less.

[0433] When the content ratio is set to be equal to or greater than the above lower limit, the adhesion tends to be improved, while when the content ratio is set to be equal to or less than the above upper limit, the shape of the partition walls tends to be improved.

[0434] For example, the total content of the (c) ethylenically unsaturated compound and the (a) alkali-soluble resin relative to the total solid content of the photosensitive resin composition is preferably 10 to 90% by mass, more preferably 30 to 80% by mass, further preferably 50 to 80% by mass, and particularly preferably 60 to 75% by mass.

[0435] [1-1-2] (b) Photopolymerization initiator

[0436] The photosensitive resin composition of the present invention contains (b) a photopolymerization initiator. (b) The photopolymerization initiator is a component that has the function of directly absorbing light and generating polymerization-active free radicals by decomposition reaction or hydrogen abstraction reaction. In addition to (b) the photopolymerization initiator, additives such as a polymerization accelerator (chain transfer agent) and a sensitizing pigment may be further added for use as needed.

[0437] The photosensitive resin composition of the present invention can use a photopolymerization initiator commonly used in the field as (b) a photopolymerization initiator. Examples of such photopolymerization initiators include metallocene compounds including titanocene compounds described in Japanese Patent Application Laid-Open No. 59-152396 and Japanese Patent Application Laid-Open No. 61-151197; hexaarylbiimidazole derivatives described in Japanese Patent Application Laid-Open No. 2000-56118; halogenated methylated oxadiazole derivatives, halogenated methyl s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, free radical activators such as N-aryl-α-amino acid esters, and α-aminoalkylphenone derivatives described in Japanese Patent Application Laid-Open No. 10-39503; and oxime ester compounds described in Japanese Patent Application Laid-Open No. 2000-80068 and Japanese Patent Application Laid-Open No. 2006-36750.

[0438] Specifically, for example, as the metallocene compound, there can be mentioned dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyl titanium, dicyclopentadienyl bis(2,3,4,5,6-pentafluorophenyl)titanium, dicyclopentadienyl bis(2,3,5,6-tetrafluorophenyl)titanium, dicyclopentadienyl bis(2,4,6-trifluorophenyl)titanium, dicyclopentadienyl bis(2,6-difluorophenyl)titanium, dicyclopentadienyl bis(2,4-difluorophenyl)titanium, di(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl)titanium, di(methylcyclopentadienyl)bis(2,6-difluorophenyl)titanium, and dicyclopentadienyl [2,6-di-fluoro-3-(pyrrol-1-yl)-phenyl]titanium.

[0439] Examples of the hexaarylbiimidazole derivative include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0440] Examples of the halogenated methylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furanyl-1,3,4-oxadiazole.

[0441] Examples of the halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

[0442] Examples of the α-aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one.

[0443] As the photopolymerization initiator, an oxime ester compound is particularly effective in terms of sensitivity and platemaking properties.

[0444] In the case of using an alkali-soluble resin containing a phenolic hydroxyl group, the sensitivity is disadvantageous, so oxime ester compounds with excellent sensitivity are particularly useful. Oxime ester compounds have a high quantum yield of photoreaction and high activity of generated free radicals, so they have high sensitivity and are stable to thermal reactions, and a highly sensitive photosensitive resin composition can be obtained with a small amount.

[0445] Examples of the oxime ester compound include compounds represented by the following general formula (b1).

[0446]

[0447] In the above formula (b1), R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.

[0448] R 21b represents an arbitrary substituent including an aromatic ring.

[0449] R 22a It represents an alkanoyl group which may have a substituent, or an aroyl group which may have a substituent.

[0450] nx represents an integer of 0 or 1.

[0451] R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.

[0452] R 21a The carbon number of the alkyl group in is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 20 or less, preferably 15 or less, more preferably 10 or less, from the viewpoint of solubility or sensitivity in a solvent.

[0453] Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group.

[0454] Examples of the substituent which the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, a 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl group, and an N-acetyl-N-acetoxyamino group. From the viewpoint of sensitivity, an N-acetyl-N-acetoxyamino group is preferred.

[0455] As R 21aThe aromatic ring group in the photosensitive resin composition may include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive resin composition. In addition, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and further preferably 12 or less.

[0456] Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among these, a phenyl group and a naphthyl group are preferred, and a phenyl group is more preferred from the viewpoint of developability.

[0457] Examples of the substituent that the aromatic ring group may optionally have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group formed by connecting these substituents. From the viewpoint of developability, an alkyl group, an alkoxy group, and a group formed by connecting these substituents are preferred, and a connected alkoxy group is more preferred.

[0458] R 21b represents an arbitrary substituent containing an aromatic ring.

[0459] As R 21b , preferably, an optionally substituted carbazolyl group, an optionally substituted thioxanthone group, an optionally substituted fluorenyl group, an optionally substituted diphenyl sulfide group, or an optionally substituted indolyl group. Among these, an optionally substituted carbazolyl group is preferred from the viewpoint of sensitivity.

[0460] R 22a It represents an alkanoyl group which may have a substituent, or an aroyl group which may have a substituent.

[0461] R 22a The carbon number of the alkanoyl group in is not particularly limited, but is preferably 2 or more from the viewpoint of solubility in a solvent or sensitivity. In addition, it is preferably 20 or less, more preferably 15 or less, further preferably 10 or less, and still more preferably 5 or less.

[0462] Specific examples of the alkanoyl group include an acetyl group, a propionyl group, and a butyryl group.

[0463] Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amide group. From the viewpoint of ease of synthesis, the alkanoyl group is preferably unsubstituted.

[0464] R 22a The carbon number of the aromatic acyl group in is not particularly limited, but is preferably 7 or more from the viewpoint of solubility in a solvent or sensitivity. Furthermore, it is preferably 20 or less, preferably 15 or less, and more preferably 10 or less.

[0465] Specific examples of the aroyl group include a benzoyl group and a naphthoyl group.

[0466] Examples of the substituent that the aroyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of ease of synthesis, the aroyl group is preferably unsubstituted.

[0467] Among these, R 22a An alkanoyl group which may have a substituent is preferred, an unsubstituted alkanoyl group is more preferred, and an acetyl group is further preferred.

[0468] As the oxime ester compound represented by the above formula (b1), for example, photopolymerization initiators described in Japanese Patent No. 4454067, International Publication No. 2002 / 100903, International Publication No. 2012 / 45736, International Publication No. 2015 / 36910, International Publication No. 2006 / 18973, International Publication No. 2008 / 78678, Japanese Patent No. 4818458, International Publication No. 2005 / 80338, International Publication No. 2008 / 75564, International Publication No. 2009 / 131189, International Publication No. 2010 / 133077, International Publication No. 2010 / 102502, and International Publication No. 2012 / 68879 can be used.

[0469] (b) The photopolymerization initiator may be used alone or in combination of two or more.

[0470] The (b) photopolymerization initiator may be mixed with a sensitizing dye or a polymerization accelerator corresponding to the wavelength of the image exposure light source, if necessary, to improve the sensing sensitivity.

[0471] As sensitizing pigments, for example, there can be mentioned: xanthene pigments described in Japanese Patent Laid-Open Nos. 4-221958 and 4-219756; coumarin pigments having a heterocyclic ring described in Japanese Patent Laid-Open Nos. 3-239703 and 5-289335; 3-ketocoumarin compounds described in Japanese Patent Laid-Open Nos. 3-239703 and 5-289335; pyrromethene pigments described in Japanese Patent Laid-Open No. 6-19240; and Japanese Patent Laid-Open Nos. 47-2528 and 54-15529 2, Japanese Patent Publication No. 45-37377, Japanese Patent Application Laid-Open No. 48-84183, Japanese Patent Application Laid-Open No. 52-112681, Japanese Patent Application Laid-Open No. 58-15503, Japanese Patent Application Laid-Open No. 60-88005, Japanese Patent Application Laid-Open No. 59-56403, Japanese Patent Application Laid-Open No. 2-69, Japanese Patent Application Laid-Open No. 57-168088, Japanese Patent Application Laid-Open No. 5-107761, Japanese Patent Application Laid-Open No. 5-210240, and Japanese Patent Application Laid-Open No. 4-288818.

[0472] Among these sensitizing dyes, a sensitizing dye containing an amino group is preferred, and a compound having an amino group and a phenyl group in the same molecule is more preferred.

[0473] In particular, preferred sensitizing dyes include, for example, benzophenone compounds such as 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis( Compounds containing a p-dialkylaminophenyl group include 2-(p-dimethylaminophenyl)-1,3,4-oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine, etc. Among them, 4,4'-dialkylaminobenzophenone is the most preferred.

[0474] Similarly, the sensitizing dye may be used alone or in combination of two or more.

[0475] As the polymerization accelerator, for example, aromatic amines such as 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, 4-dimethylaminoacetophenone, and 4-dimethylaminopropiophenone; and aliphatic amines such as n-butylamine, N-methyldiethanolamine, and 2-dimethylaminoethyl benzoate can be used.

[0476] The polymerization accelerator may be used alone or in combination of two or more.

[0477] Furthermore, a chain transfer agent may be used in combination with the above-mentioned (b) photopolymerization initiator.

[0478] As the chain transfer agent, for example, a compound containing a mercapto group or carbon tetrachloride can be cited. In terms of showing a tendency to have a higher chain transfer effect, a compound containing a mercapto group is more preferably used. This is believed to be because the SH bond energy is small, bond breaking is easy to occur, and hydrogen abstraction reaction or chain transfer reaction is easy to occur, which is effective for improving sensitivity or surface curing.

[0479] Examples of the mercapto group-containing compound include: mercapto group-containing compounds having an aromatic ring, such as 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazoline, β-mercaptonaphthalene, and 1,4-dimethylmercaptobenzene; hexanedithiol, decanedithiol, butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris(3-mercaptopropionate), and trimethylolpropane trimerthioglycolate. Aliphatic thiol-containing compounds such as trihydroxyethyl trithiopropionate, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), butanediol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; in particular, compounds having multiple thiol groups.

[0480] Among them, among the mercapto group-containing compounds having an aromatic ring, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred, and among the aliphatic mercapto group-containing compounds, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred.

[0481] These various substances can be used individually by 1 type or in mixture of 2 or more types.

[0482] Among these, from the viewpoint of sensitivity, it is preferred to use one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole and 2-mercaptobenzoxazole in combination with a photopolymerization initiator as a photopolymerization initiator system. For example, 2-mercaptobenzothiazole can be used, 2-mercaptobenzimidazole can also be used, and 2-mercaptobenzothiazole and 2-mercaptobenzimidazole can also be used in combination. In addition, as (b) a photopolymerization initiator, it is preferably used in combination with a biimidazole derivative.

[0483] In addition, from the viewpoint of sensitivity, it is preferred to use one or more selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate). Furthermore, from the viewpoint of sensitivity, it is preferred to use one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole and 2-mercaptobenzoxazole, one or more selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate), and (b) a photopolymerization initiator in combination.

[0484] The content ratio of the (b) photopolymerization initiator in the photosensitive resin composition of the present invention is not particularly limited, but is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and particularly preferably 3% by mass or more, and is usually 25% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further more preferably 7% by mass or less, and particularly preferably 5% by mass or less, relative to the total solid content of the photosensitive resin composition.

[0485] When the content ratio is set to be equal to or greater than the above lower limit, the surface smoothness tends to be improved, while when the content ratio is set to be equal to or less than the above upper limit, the resolution tends to be improved.

[0486] The blending ratio of the (b) photopolymerization initiator to the following (c) ethylenically unsaturated compound in the photosensitive resin composition is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, particularly preferably 30 parts by mass or more, and is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, further preferably 50 parts by mass or less, and particularly preferably 40 parts by mass or less, based on 100 parts by mass of the (c) ethylenically unsaturated compound.

[0487] When the mixing ratio is equal to or greater than the above lower limit, the surface smoothness tends to be improved, while when the mixing ratio is equal to or less than the above upper limit, the resolution tends to be improved.

[0488] [1-1-3] (c) Ethylenically unsaturated compounds

[0489] The photosensitive resin composition of the present invention contains (c) an ethylenically unsaturated compound. It is considered that the inclusion of (c) an ethylenically unsaturated compound improves the curability of the coating film and improves the adhesion.

[0490] The (c) ethylenically unsaturated compound in the photosensitive resin composition of the present invention includes an ethylenically unsaturated compound (c1') containing an alkylene oxide, wherein the ethylenically unsaturated compound (c1) having an alkylene oxide and having three or more ethylenically unsaturated groups is preferred, and the ethylenically unsaturated compound having an alkylene oxide in the side chain is further preferred. It is believed that, in particular, by containing an alkylene oxide in the side chain, since the oxygen atom contained in the alkylene oxide is hydrophilic, the affinity for the developer is improved, and even when the mass ratio of the above-mentioned (a) alkali-soluble resin to the above-mentioned (c) ethylenically unsaturated compound ((a) alkali-soluble resin / (c) ethylenically unsaturated compound) is large and the content of the (c) ethylenically unsaturated compound is small, the dissolution time is also shortened.

[0491] (c) The ethylenically unsaturated compound refers to a compound having one or more ethylenically unsaturated bonds in the molecule. In terms of polymerizability, crosslinking properties, and the accompanying ability to increase the difference in developer solubility between the exposed portion and the non-exposed portion, the compound preferably has two or more ethylenically unsaturated bonds in the molecule. Furthermore, a compound in which the unsaturated bonds are derived from a (meth)acryloyloxy group, i.e., a (meth)acrylate compound, is more preferably used.

[0492] From the viewpoint of sensitivity, the ethylenically unsaturated compound (c1) preferably has three or more alkylene oxide-modified ethylenically unsaturated groups.

[0493] In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenic unsaturated bonds in one molecule as the (c) ethylenic unsaturated compound.

[0494] The number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, and is preferably 15 or less, more preferably 10 or less, further preferably 8 or less, and particularly preferably 6 or less.

[0495] When the number of ethylenically unsaturated groups is equal to or greater than the above lower limit, surface smoothness tends to be improved, while when the number of ethylenically unsaturated groups is equal to or less than the above upper limit, developability tends to be further improved.

[0496] For example, the number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is preferably 2 to 15, more preferably 2 to 10, further preferably 2 to 8, still further preferably 3 to 8, particularly preferably 3 to 6.

[0497] Specific examples of the ethylenically unsaturated compound (c1) in the ethylenically unsaturated compound (c1′) include esters of an aliphatic polyhydroxy compound having an alkylene oxide group in a side chain and an unsaturated carboxylic acid.

[0498] Examples of the alkylene oxide group include polyethylene glycol and polypropylene glycol having an arbitrary repeating unit.

[0499] Examples of the aliphatic polyhydroxy compound include ethylene glycol, triethylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, and glycerol.

[0500] As said unsaturated carboxylic acid, acrylic acid and methacrylic acid are mentioned, for example.

[0501] Among these, from the viewpoint of dissolution rate, it is preferred to use a compound having the following structure as the ethylenically unsaturated compound (c1).

[0502]

[0503] These may be used alone or in combination of two or more.

[0504] Furthermore, the ethylenically unsaturated compound (c1) preferably contains an ethylenically unsaturated compound (c1-1) represented by the following general formula (c1-1-1).

[0505]

[0506] (X in formula (c1-1-1) is represented by the following general formula (c1-1-2); Xs are optionally the same or different; Y is methyl or represented by the following general formula (c1-1-4).

[0507]

[0508] (R in formula (c1-1-2) 1 represents an alkylene group having 2 to 4 carbon atoms; a represents an integer of 1 to 9; when a is 2 or more, multiple R 1 are optionally the same or different; R 2 It is represented by the following general formula (c1-1-3); * represents a connecting bond. )

[0509]

[0510] (R in formula (c1-1-3) 3 represents a hydrogen atom or a methyl group; * represents a connecting bond. )

[0511]

[0512] (In formula (c1-1-4), m is 0 or 1; * represents a connecting bond; X is represented by the above general formula (c1-1-2), and X may be the same or different.)

[0513] In terms of dissolution rate, Y in the general formula (c1-1-1) is preferably represented by the general formula (c1-1-4), and m in the general formula (c1-1-4) is preferably 1.

[0514] Furthermore, from the viewpoint of ease of synthesis, X is preferably the same.

[0515] R in formula (c1-1-2) 1 The alkylene group having 2 to 4 carbon atoms in the group may be linear, branched, cyclic, or a combination thereof. From the viewpoint of solvent solubility and solvent resistance, a linear alkylene group is preferred.

[0516] The carbon number of the alkylene group is not particularly limited if it is 2 to 4, but is preferably 2 to 3, and more preferably 2. When the carbon number is within the above range, the coating film sensitivity and solvent resistance tend to be improved.

[0517] As R 1 Examples of the alkylene group include ethylene, n-propylene, n-butylene, and isopropylene. From the viewpoint of dissolution rate, n-propylene and ethylene are preferred, and ethylene is more preferred.

[0518] In general formula (c1-1-2), a is preferably an integer of 2 to 9, more preferably an integer of 2 to 4, from the viewpoint of dissolution rate.

[0519] Among these, from the viewpoint of dissolution rate, it is preferable to use a compound having the following structure as the ethylenically unsaturated compound (c1-1).

[0520]

[0521] The (c) ethylenically unsaturated compound in the photosensitive resin composition of the present invention may contain other ethylenically unsaturated compounds in addition to the ethylenically unsaturated compound (c1) having an alkylene oxide group and having three or more ethylenically unsaturated groups.

[0522] The other ethylenically unsaturated compound used herein refers to a compound having one or more ethylenically unsaturated bonds in the molecule. In terms of polymerizability, crosslinking, and the accompanying ability to increase the difference in developer solubility between the exposed portion and the non-exposed portion, it is preferably a compound having two or more ethylenically unsaturated bonds in the molecule. Furthermore, it is more preferably a compound in which the unsaturated bonds are derived from a (meth)acryloyloxy group, that is, a (meth)acrylate compound.

[0523] In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenic unsaturated bonds in one molecule as the other ethylenic unsaturated compound.

[0524] The number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, and is preferably 15 or less, more preferably 10 or less, further preferably 8 or less, and particularly preferably 6 or less.

[0525] When the number of ethylenically unsaturated groups is equal to or greater than the above lower limit, surface smoothness tends to be improved, while when the number of ethylenically unsaturated groups is equal to or less than the above upper limit, developability tends to be further improved.

[0526] For example, the number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is preferably 2 to 15, more preferably 2 to 10, further preferably 2 to 8, still further preferably 3 to 8, particularly preferably 3 to 6.

[0527] Specific examples of other ethylenically unsaturated compounds include: esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; and esters obtained by esterification of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polycarboxylic acids.

[0528] Examples of the esters of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include acrylates of aliphatic polyhydroxy compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate; methacrylates obtained by replacing the acrylates of these exemplified compounds with methacrylates; itaconates obtained by replacing the acrylates of these exemplified compounds with itaconates; crotonates obtained by replacing the acrylates of these exemplified compounds with crotonates; or maleates obtained by replacing the acrylates of these exemplified compounds with maleates.

[0529] Examples of the esters of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylates and methacrylates of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate.

[0530] The esters obtained by the esterification reaction of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polycarboxylic acids are not necessarily single substances. Representative specific examples include: condensates of acrylic acid, phthalic acid, and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; condensates of methacrylic acid, terephthalic acid, and pentaerythritol; condensates of acrylic acid, adipic acid, butanediol, and glycerol.

[0531] In addition, examples of other multifunctional olefinic monomers used in the present invention include: urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl-containing (meth)acrylate or a polyisocyanate compound with a polyol and a hydroxyl-containing (meth)acrylate; epoxy acrylates such as addition reaction products of a polyvalent epoxy compound with a hydroxyl (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl-containing compounds such as divinyl phthalate.

[0532] Examples of the urethane (meth)acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, and UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, and UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), and UV-1700B, UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Nippon Synthetic Chemical Co., Ltd.).

[0533] Among these, from the viewpoint of resolution, as other ethylenically unsaturated compounds, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids or urethane (meth)acrylates are preferably used, and trimethylolpropane triacrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2,2,2-tri(meth)acryloyloxymethylethyl phthalate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dibasic acid anhydride adducts of dipentaerythritol penta(meth)acrylate, and dibasic acid anhydride adducts of pentaerythritol tri(meth)acrylate are more preferably used.

[0534] These may be used alone or in combination of two or more.

[0535] In the present invention, the molecular weight of the (c) ethylenically unsaturated compound is not particularly limited, but is preferably 100 or more, more preferably 300 or more, particularly preferably 400 or more, and is preferably 2000 or less, more preferably 1500 or less, from the viewpoint of resolution.

[0536] For example, the molecular weight of the (c) ethylenically unsaturated compound is preferably 100 to 2,000, more preferably 300 to 2,000, and particularly preferably 400 to 1,500.

[0537] The carbon number of the (c) ethylenically unsaturated compound is not particularly limited, but from the viewpoint of resolution, it is preferably 7 or more, more preferably 10 or more, further preferably 15 or more, and is preferably 50 or less, more preferably 40 or less, further preferably 30 or less, and particularly preferably 20 or less.

[0538] For example, the carbon number of the (c) ethylenically unsaturated compound is preferably 7-50, more preferably 10-40, further preferably 15-30, and still further preferably 15-20.

[0539] The content ratio of the (c) ethylenically unsaturated compound in the photosensitive resin composition of the present invention is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, and usually 20% by mass or less, more preferably 10% by mass or less, relative to the total solid content of the photosensitive resin composition.

[0540] When the content ratio is set to be equal to or greater than the above lower limit, the dissolution rate tends to be improved, and when the content ratio is set to be equal to or less than the above upper limit, the taper angle tends to be improved.

[0541] For example, the content ratio of the (c) ethylenically unsaturated compound to the total solid content of the photosensitive resin composition is preferably 1 to 20% by mass, and more preferably 5 to 10% by mass.

[0542] In addition, the content ratio of the ethylenically unsaturated compound (c1) in the (c) ethylenically unsaturated compound is not particularly limited, and is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 80% by mass or more, and particularly preferably 100% by mass, relative to the total solid content of the (c) ethylenically unsaturated compound. By setting the content ratio to be above the above lower limit, a tendency of faster dissolution rate is shown.

[0543] [Ratio of content of (a) alkali-soluble resin to (c) ethylenically unsaturated compound]

[0544] In one embodiment of the present invention, the mass ratio of the (a) alkali-soluble resin to the (c) ethylenically unsaturated compound in the photosensitive resin composition ((a) alkali-soluble resin / (c) ethylenically unsaturated compound) is 5 or more, preferably 6 or more, and more preferably 8 or more. The mass ratio is preferably 15 or less, and more preferably 12 or less.

[0545] When the ratio of (a) alkali-soluble resin / (c) ethylenically unsaturated compound is set to be equal to or greater than the above lower limit, the taper angle tends to be smaller, while when the ratio of (a) alkali-soluble resin / (c) ethylenically unsaturated compound is set to be equal to or less than the above upper limit, the dissolution rate tends to be faster.

[0546] For example, the mass ratio of the (a) alkali-soluble resin to the (c) ethylenically unsaturated compound ((a) alkali-soluble resin / (c) ethylenically unsaturated compound) is preferably 5-15, more preferably 6-12, and even more preferably 8-12.

[0547] In another embodiment of the present invention, the total double bond equivalent of the above-mentioned (a) alkali-soluble resin and (c) ethylenically unsaturated compound, which is the weighted average of the values ​​obtained by dividing the content (mass) of the above-mentioned (a) alkali-soluble resin and the above-mentioned (c) ethylenically unsaturated compound in the photosensitive resin composition by the mole number of each ethylenically unsaturated bond, is 350 g / mol or more, preferably 380 g / mol or more, and more preferably 410 g / mol or more. On the other hand, the total double bond equivalent is 600 g / mol or less, preferably 550 g / mol or less, and more preferably 500 g / mol or less.

[0548] When the total double bond equivalent is greater than or equal to the above lower limit, the taper angle tends to be low, while when the total double bond equivalent is less than or equal to the above upper limit, sufficient crosslinking density can be obtained and the solubility of the resist tends to be ensured.

[0549] For example, the total double bond equivalent is preferably 350 to 600 g / mol, more preferably 380 to 550 g / mol, and further preferably 410 to 500 g / mol.

[0550] The photosensitive resin composition of the present invention preferably satisfies both the (a) alkali-soluble resin / (c) ethylenically unsaturated compound mass ratio and the total double bond equivalent.

[0551] [1-1-4] (d) Colorants

[0552] The photosensitive resin composition of the present invention may contain (d) a colorant. By containing the (d) colorant, appropriate light absorption can be obtained, and in particular, appropriate light shielding properties can be obtained when used for forming a light shielding member such as a colored partition.

[0553] The content ratio of the colorant (d) is not particularly limited, but from the viewpoint of light-shielding properties, it is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more relative to the total solid content of the photosensitive resin composition. On the other hand, from the viewpoint of surface smoothness and developability, it is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less.

[0554] The (d) colorant used in the present invention is not particularly limited, but preferably contains an organic pigment from the viewpoint of relative dielectric constant and resolution.

[0555] As the kind of organic pigment, there is no particular limitation, and from the viewpoint of light-shielding, organic black pigment or organic coloring pigment, further preferred organic black pigment.Herein, so-called organic coloring pigment refers to an organic pigment showing a color other than black, for example, red pigment, orange pigment, blue pigment, purple pigment, green pigment, yellow pigment.One organic coloring pigment can be used alone, or two or more can be used in combination.

[0556] In particular, when used for light-shielding purposes, it is more preferred to use organic coloring pigments of different colors in combination, and it is further preferred to use a combination of organic coloring pigments that exhibit a color close to black.

[0557] The chemical structure of these organic pigments is not particularly limited, and examples thereof include: azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. Specific examples of usable pigments are shown below using pigment numbers. The terms "CI Pigment Red 2" and the like listed below refer to the Color Index (CI).

[0558] Examples of the red pigment include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 1 49, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232 2, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276.

[0559] Among them, from the viewpoint of light-shielding property and dispersibility, preferably CI Pigment Red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, and 254 are mentioned, and more preferably CI Pigment Red 177, 209, 224, and 254 are mentioned.

[0560] From the viewpoint of dispersibility and light shielding property, CI Pigment Red 177, 254, and 272 are preferably used.

[0561] When the photosensitive resin composition is cured by ultraviolet rays, it is preferred to use a red pigment having a low ultraviolet absorption rate. From this viewpoint, CI Pigment Red 254 and 272 are more preferably used.

[0562] Examples of the orange pigment include CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79.

[0563] Among them, CI Pigment Orange 13, 43, 64, and 72 are preferably used from the viewpoint of dispersibility and light-shielding property.

[0564] When the photosensitive resin composition is cured by ultraviolet rays, it is preferable to use an orange pigment having a low ultraviolet absorption rate. From this viewpoint, CI Pigment Orange 64 and 72 are more preferably used, and CI Pigment Orange 64 is more preferably used.

[0565] Examples of the blue pigment include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79.

[0566] Among these, from the viewpoint of light-shielding property, preferably, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60 are mentioned, and more preferably, CI Pigment Blue 15:6 is mentioned.

[0567] From the viewpoint of dispersibility and light shielding property, CI Pigment Blue 15:6, 16, 60 is preferably used.

[0568] When the photosensitive resin composition is cured by ultraviolet rays, it is preferred to use a blue pigment having a low ultraviolet absorption rate. From this viewpoint, CI Pigment Blue 60 is more preferably used.

[0569] Examples of the violet pigment include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among them, from the viewpoint of light-shielding properties, CI Pigment Violet 19 and 23 are preferably used, and CI Pigment Violet 23 is more preferably used.

[0570] From the viewpoint of dispersibility and light-shielding property, CI Pigment Violet 23 and 29 are preferably used.

[0571] When the photosensitive resin composition is cured by ultraviolet rays, it is preferred to use a pigment having a low ultraviolet absorption rate as the violet pigment. From this viewpoint, CI Pigment Violet 29 is more preferably used.

[0572] Examples of the organic coloring pigment that can be used in addition to the red pigment, the orange pigment, the blue pigment, and the violet pigment include a green pigment and a yellow pigment.

[0573] Examples of the green pigment include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, and 55. Among them, CI Pigment Green 7 and 36 are preferably used.

[0574] As yellow pigments, for example, CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 1 34, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208.

[0575] Among them, preferably, CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185 are mentioned, and more preferably, CI Pigment Yellow 83, 138, 139, 150, and 180 are mentioned.

[0576] Among these, from the viewpoint of light-shielding properties and shape control, it is preferred to contain at least one selected from the group consisting of the following red pigments and orange pigments and at least one selected from the group consisting of the following blue pigments and violet pigments.

[0577] Red pigment: CI Pigment Red 177, 254, 272

[0578] Orange pigment: CI Pigment Orange 43, 64, 72

[0579] Blue pigment: CI Pigment Blue 15:6, 60

[0580] Violet Pigment: CI Pigment Violet 23, 29

[0581] The organic black pigment is not particularly limited, but from the viewpoint of light-shielding properties, it is preferred to use an organic black pigment comprising at least one selected from the group consisting of a compound represented by the following general formula (d1) (hereinafter also referred to as “compound (d1)”), a geometric isomer of the compound (d1), a salt of the compound (d1), and a salt of a geometric isomer of the compound (d1) (hereinafter sometimes referred to as “organic black pigment represented by general formula (d1)”).

[0582]

[0583] (In formula (d1), R 11 and R 16 Each independently represents a hydrogen atom, CH3, CF3, a fluorine atom or a chlorine atom;

[0584] R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 and R 20 Each independently represents a hydrogen atom, a halogen atom, R 21 、COOH、COOR 21 、COO - ,CONH2,CONHR 21 ,CONR 21 R 22 、CN、OH、OR 21 、COCR 21 、OOCNH2、OOCNHR 21 、OOCNR 21 R 22 、NO2、NH2、NHR 21 NR 21 R 22 、NHCOR 22 NR 21 COR 22 、N=CH2、N=CHR 21 、N=CR 21 R 22, SH, SR 21 , SOR 21 、SO2R 21 、SO3R 21 、SO3H、SO3 - 、SO2NH2、SO2NHR 21 or SO2NR 21 R 22 ;

[0585] Choose from R 12 With R 13 , R 13 With R 14 , R 14 With R 15 , R 17 With R 18 , R 18 With R 19 , and R 19 With R 20 At least one of the groups consisting of the above may be directly bonded to each other, or may be bonded to each other via an oxygen atom, a sulfur atom, NH or NR 21 Bridge and bond to each other;

[0586] R 21 and R 22 each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms)

[0587] Compound (d1) and the geometrical isomers of compound (d1) have the following core structure (wherein the substituents in the structural formula are omitted), and the trans-trans isomer is likely to be the most stable.

[0588]

[0589] When compound (d1) is anionic, it is preferably a salt obtained by compensating its charge with any known suitable cation, such as metal, organic, inorganic or metal organic cation, specifically alkali metal, alkaline earth metal, transition metal, primary ammonium, secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium or an organic metal complex. In addition, when the geometrical isomers of compound (d1) are anionic, they are preferably the same salts.

[0590] Among the substituents in formula (d1) and their definitions, the following are preferred in that they tend to increase the shielding rate. This is because the following substituents are considered to have no absorption and have no influence on the hue of the pigment.

[0591] R 12 , R 14 , R15 , R 17 , R 19 and R 20 Each of them independently is preferably a hydrogen atom, a fluorine atom or a chlorine atom, and more preferably a hydrogen atom.

[0592] R 13 and R 18 Preferably, each is independently a hydrogen atom, NO2, OCH3, OC2H5, a bromine atom, a chlorine atom, CH3, C2H5, N(CH3)2, N(CH3)(C2H5), N(C2H5)2, SO3H or SO3 - , further preferably a hydrogen atom or SO3H, particularly preferably a hydrogen atom.

[0593] R 11 and R 16 Each of them independently is preferably a hydrogen atom, CH 3 or CF 3 , and more preferably a hydrogen atom.

[0594] Preferably selected from R 11 With R 16 , R 12 With R 17 , R 13 With R 18 , R 14 With R 19 , and R 15 With R 20 At least one of the combinations in the group is the same, and more preferably R 11 With R 16 Same, R 12 With R 17 Same, R 13 With R 18 Same, R 14 With R 19 Same, and R 15 With R 20 same.

[0595] R 21 and R 22 The alkyl group having 1 to 12 carbon atoms is exemplified by methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, undecyl and dodecyl.

[0596] R 21 and R 22Examples of the cycloalkyl group having 3 to 12 carbon atoms include cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, trimethylcyclohexyl, thujyl, norbornyl, bornyl, norcaryl, caryl, menthyl, norpinyl, pinyl, adamantane-1-yl and adamantane-2-yl.

[0597] R 21 and R 22 Examples of the alkenyl group having 2 to 12 carbon atoms include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl, hexenyl, octenyl, nonenyl, decenyl, and dodecenyl.

[0598] R 21 and R 22 Examples of the cycloalkenyl group having 3 to 12 carbon atoms include 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, 1-p-menthene-8-yl, 4(10)-thuja-10-yl, 2-norbornene-1-yl, 2,5-norbornadien-1-yl, 7,7-dimethyl-2,4-norcarbadien-3-yl and camphenyl.

[0599] R 21 and R 22 Examples of the alkynyl group having 2 to 12 carbon atoms include 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyne-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl and 1-dodecyn-12-yl.

[0600] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0601] The organic black pigment represented by formula (d1) is preferably an organic black pigment comprising at least one selected from the group consisting of a compound represented by the following structural formula (2) (hereinafter also referred to as “compound (2)”) and geometric isomers of compound (2).

[0602]

[0603] Specific examples of the organic black pigment of the compound (2) include, as a trade name, Irgaphor (registered trademark) Black S 0100CF (manufactured by BASF Corporation).

[0604] The organic black pigment is preferably dispersed by the following dispersant, solvent, and method. In addition, if a sulfonic acid derivative of compound (d1), particularly a sulfonic acid derivative of compound (2), is present during dispersion, dispersibility or storage stability may be improved, so the organic black pigment preferably contains these sulfonic acid derivatives.

[0605] Examples of organic black pigments other than the compound (d1) include aniline black and perylene black.

[0606] Furthermore, in addition to these organic pigments, an inorganic pigment may be contained. As the inorganic pigment, it is preferable to contain an inorganic black pigment from the viewpoint of light-shielding property.

[0607] Examples of the inorganic black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, and titanium black.

[0608] Among these, carbon black can be preferably used from the viewpoint of light shielding property and image characteristics. Examples of carbon black include the following carbon blacks.

[0609] Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, #960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #2650, #3030, #3050, #31 50, #3250, #3400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B

[0610] Manufactured by Degussa: Printex (registered trademark, the same applies hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, PrintexV, Printex G, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

[0611] Cabot Corporation: Monarch (registered trademark, the same below) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademark, the same below) 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 550R, REGAL 660R, BLACK PEARLS 480, PEARLS 130, VULCAN (registered trademark, the same below) XC72R, ELFTEX (registered trademark) -8

[0612] Birla: RAVEN (registered trademark, the same applies hereinafter) 11, RAVEN 14, RAVEN 15, RAVEN 16, RAVEN 22, RAVEN 30, RAVEN 35, RAVEN 40, RAVEN 410, RAVEN 420, RAVEN 450, RAVEN 500, RAVEN 780, RAVEN 850, RAVEN 890H, RAVEN 1000, RAVEN 1020, RAVEN 1040, RAVEN 1060U, RAVEN 1080U, RAVEN 1170, RAVEN 1190U, RAVEN 1250, RAVEN 1500, RAVEN 2000, RAVEN 2500U, RAVEN 3500, RAVEN 5000, RAVEN 5250, RAVEN 5750, RAVEN 7000

[0613] Carbon black coated with a resin may also be used. When carbon black coated with a resin is used, there is an effect of improving adhesion to a glass substrate and volume resistance value.

[0614] As the carbon black coated with resin, for example, carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be preferably used. In terms of volume resistance and dielectric constant, the resin-coated carbon black can be preferably used.

[0615] As carbon black for coating treatment using resin, the total content of Na and Ca is preferably 100 ppm or less. Carbon black usually contains ash composed of Na, Ca, K, Mg, Al, Fe, etc. mixed from raw oil or fuel (or gas) during manufacturing, reaction termination water or granulation water, and then furnace materials of the reactor. Among them, Na and Ca usually contain more than several hundred ppm respectively. By reducing these, it is possible to inhibit penetration into the transparent electrode (ITO) or other electrodes, thereby preventing electrical short circuits.

[0616] As a method for reducing the content of ash containing these Na and Ca, it is possible to strictly select substances with very low content of these substances as raw oil or fuel oil (or gas) and reaction termination water when manufacturing carbon black, and to minimize the amount of alkaline substances added for adjusting the structure. As another method, a method of washing the carbon black produced from the furnace with water or hydrochloric acid to dissolve and remove Na or Ca can be cited.

[0617] Specifically, carbon black is mixed and dispersed in water, hydrochloric acid, or hydrogen peroxide water, and then a solvent that is poorly soluble in water is gradually added. At this time, the carbon black is transferred to the solvent side and completely separated from the water. At the same time, almost all of the Na or Ca present in the carbon black is dissolved in the water or acid and removed. In order to reduce the total amount of Na and Ca to less than 100 ppm, there are cases where it can be achieved only by a single carbon black manufacturing process of strictly selecting raw materials or a single method of dissolving in water or acid, but by combining these two methods, it is easier to reduce the total amount of Na and Ca to less than 100 ppm.

[0618] In addition, the resin-coated carbon black is preferably a so-called acidic carbon black with a pH of 6 or less. Since the dispersion diameter (agglomerate diameter) in water becomes smaller, it is possible to coat even fine units, which is preferred. It is further preferred that the average particle diameter is 40 nm or less and the dibutyl phthalate (DBP) absorption is 140 mL / 100 g or less. By setting it within the above range, there is a tendency to obtain a coating film with good light-shielding properties. The average particle size refers to the number-average particle size, which refers to the circle equivalent diameter obtained by particle image analysis. The particle image analysis is obtained by observing with an electron microscope and photographing at tens of thousands times to obtain photographs of multiple fields of view, and measuring about 2,000 to 3,000 particles in these photographs using an image processing device.

[0619] The method for preparing the carbon black coated with the resin is not particularly limited, and for example, after appropriately adjusting the blending amounts of the carbon black and the resin, the following methods 1 to 4 may be employed.

[0620] 1. A method of mixing a resin with a solvent such as cyclohexanone, toluene, or xylene and heating to dissolve the mixture to obtain a resin solution, mixing carbon black with water to obtain a suspension, mixing and stirring the resin solution and the suspension to separate the carbon black from the water, removing the water, and heating and kneading the mixture to obtain a composition, forming the obtained composition into a sheet, pulverizing the sheet, and drying the sheet

[0621] 2. A method of mixing and stirring the resin solution and the suspension prepared in the same manner as above to granulate the carbon black and the resin, and then separating and heating the obtained granules to remove the remaining solvent and water

[0622] 3. A method of dissolving a carboxylic acid such as maleic acid or fumaric acid in the solvent exemplified above, adding carbon black, mixing, and drying, removing the solvent to obtain carbon black impregnated with the carboxylic acid, and then adding a resin thereto for dry mixing

[0623] 4. A method of preparing a suspension by stirring a monomer component containing a reactive group constituting a resin for coating with water at high speed, cooling after polymerization to obtain a resin containing a reactive group from the polymer suspension, then adding carbon black thereto for kneading, reacting the carbon black with the reactive group (grafting the carbon black), and cooling and pulverizing

[0624] The type of the resin to be coated is not particularly limited, but is generally a synthetic resin. A resin having a benzene ring in its structure is preferred from the viewpoint of dispersibility and dispersion stability because its function as an amphoteric surfactant is stronger.

[0625] As specific synthetic resins, there can be used thermosetting resins such as phenolic resins, melamine resins, xylene resins, diallyl phthalate resins, glyphthalate resins, epoxy resins, and alkylbenzene resins, and thermoplastic resins such as polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfone polyphenylsulfone, polyarylate, and polyetheretherketone.

[0626] The amount of the coating resin is preferably 1 to 30% by mass based on the total amount of the carbon black and the resin.

[0627] When the coating resin amount is set to be equal to or greater than the above lower limit, sufficient coating tends to be achieved. When the coating resin amount is set to be equal to or less than the above upper limit, adhesion between resins can be prevented, thereby improving dispersibility.

[0628] The carbon black that utilizes resin to carry out coating treatment like this can be used as the coloring agent of colored partition wall according to conventional method.If use such carbon black, then present the tendency that can form high light shielding rate and the lower colored partition wall of surface reflectivity with low cost.In addition, also can infer, by utilizing resin coating carbon black surface, have the effect that the ash content that comprises Na, Ca is enclosed in the carbon black.

[0629] The average primary particle size of the pigment is usually 0.2 μm or less, preferably 0.1 μm or less, and more preferably 0.05 μm or less. The average primary particle size of the pigment can be measured by directly measuring the size of the primary particles from the electron micrograph using a transmission electron microscope (TEM) or a scanning electron microscope (SEM).

[0630] In addition, as (d) coloring agent, in addition to the above-mentioned organic coloring pigments and black pigments, dyes can also be used. Examples of dyes that can be used as coloring agents include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

[0631] Examples of the azo dye include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, and CI Mordant Black 7.

[0632] Examples of the anthraquinone dye include CI Vat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, and CI Disperse Blue 60.

[0633] As a phthalocyanine dye, CI Vat Blue 5 is mentioned, for example.

[0634] As a quinoneimine dye, CI Basic Blue 3 and CI Basic Blue 9 are mentioned, for example.

[0635] As a quinoline dye, CI solvent yellow 33, CI acid yellow 3, CI disperse yellow 64 are mentioned, for example.

[0636] As a nitro-based dye, CI Acid Yellow 1, CI Acid Orange 3, and CI Disperse Yellow 42 are mentioned, for example.

[0637] [1-1-5] Dispersant

[0638] The photosensitive resin composition of the present invention preferably contains a dispersant in order to finely disperse the (d) colorant and stabilize the dispersion state thereof.

[0639] As the dispersant in the present invention, a polymer dispersant having a functional group is preferred, and further, from the viewpoint of dispersion stability, a polymer dispersant having functional groups such as a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a salt group thereof; a primary, secondary or tertiary amino group; a quaternary ammonium salt group; a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine, pyrazine, etc. is preferred. Among them, a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium salt group; a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine, pyrazine, etc. is particularly preferred from the viewpoint that a small amount of dispersant can be used to disperse the pigment.

[0640] Examples of the polymer dispersant include carbamate dispersants, acrylic acid dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants containing monomers and macromonomers having an amino group, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

[0641] Specific examples of such dispersants include, for example, EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK-Chemie), Disparlon (registered trademark, manufactured by Kusumoto Chemicals Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and Ajisper (registered trademark, manufactured by Ajinomoto Co., Ltd.).

[0642] These polymer dispersants may be used alone or in combination of two or more.

[0643] The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100000 or less, preferably 50000 or less. For example, the weight average molecular weight (Mw) of the polymer dispersant is preferably 700 to 100000, more preferably 1000 to 50000.

[0644] Among these, from the viewpoint of the dispersibility of the pigment, the dispersant preferably contains any one or both of a urethane polymer dispersant and an acrylic polymer dispersant having a functional group, and particularly preferably contains an acrylic polymer dispersant.

[0645] In addition, from the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having either or both of a polyester bond and a polyether bond is preferred.

[0646] Examples of urethane-based and acrylic-based polymer dispersants include DISPERBYK-160 to 167, 182 series (all urethane-based), DISPERBYK-2000, 2001, BYK-LPN21116, etc. (all acrylic-based) (all manufactured by BYK-Chemie).

[0647] If the chemical structure preferred as the carbamate polymer dispersant is specifically exemplified, for example, a dispersing resin with a weight average molecular weight of 1000 to 200000 obtained by reacting a polyisocyanate compound, a compound having one or two hydroxyl groups in the same molecule and a number average molecular weight of 300 to 10000, and a compound having active hydrogen and a tertiary amino group in the same molecule, etc. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino groups can be converted into quaternary ammonium salt groups.

[0648] Examples of the polyisocyanate compound include aromatic diisocyanates such as p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, and tolidine diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and dimer acid diisocyanate; isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), ω,ω'-diisocyanate, and the like. alicyclic diisocyanates such as ester dimethylcyclohexane; aliphatic diisocyanates having aromatic rings such as xylylene diisocyanate, α,α,α',α'-tetramethylxylylene diisocyanate; triisocyanates such as lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, dicycloheptane triisocyanate, tris(isocyanate phenylmethane), tris(isocyanate phenyl)thiophosphate; and trimers, hydrates, and polyol adducts thereof. Preferred polyisocyanates are trimers of organic diisocyanates, and trimers of toluene diisocyanate and trimers of isophorone diisocyanate are most preferred.

[0649] These may be used alone or in combination of two or more.

[0650] As a method for producing a trimer of isocyanate, the following method can be cited: using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc., the above-mentioned polyisocyanate compound is partially trimerized with isocyanate groups, the trimerization is terminated by adding a catalyst poison, and then the unreacted polyisocyanate compound is subjected to solvent extraction and thin film distillation to remove it, thereby obtaining the target polyisocyanate containing isocyanurate groups.

[0651] Examples of the compound having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the same molecule include polyether diols, polyester diols, polycarbonate diols, polyolefin diols, and the like, compounds obtained by alkoxylating a single terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbon atoms, and mixtures of two or more thereof.

[0652] Examples of the polyether diol include polyether diol, polyether ester diol, and a mixture of two or more thereof.

[0653] Examples of the polyether diol include those obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, ethylene glycol-propylene glycol copolymers, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and mixtures of two or more thereof.

[0654] Examples of the polyetherester diol include polyetherester diols obtained by reacting a diol containing an ether group or a mixture of other diols with dicarboxylic acid or anhydrides thereof, or reacting an alkylene oxide with a polyester diol, such as poly(polyoxytetramethylene) adipate.

[0655] The most preferred polyether diol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound obtained by alkoxylating one terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbon atoms.

[0656] Examples of the polyester diol include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and diols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1, Polyester diols obtained by polycondensation of aliphatic diols such as bishydroxymethylcyclohexane, bishydroxyethoxybenzene, bis(2,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, and 1,9-nonanediol; alicyclic diols such as bishydroxymethylcyclohexane; aromatic diols such as benzyl alcohol and bishydroxyethoxybenzene; N-alkyldialkanolamines such as N-methyldiethanolamine, such as polyethylene adipate, polybutylene adipate, polyhexane adipate, polyethylene adipate / propylene adipate, etc.; or polylactone diols or polylactone monools obtained by using the above diols or monools with 1 to 25 carbon atoms as initiators, such as polycaprolactone diol, polymethylvalerolactone, and mixtures of two or more thereof.

[0657] The most preferred polyester diol is polycaprolactone diol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator.

[0658] Examples of the polycarbonate diol include poly(1,6-hexanediol) carbonate and poly(3-methyl-1,5-pentanediol) carbonate.

[0659] Examples of the polyolefin diol include polybutadiene diol, hydrogenated polybutadiene diol, and hydrogenated polyisoprene diol.

[0660] These may be used alone or in combination of two or more.

[0661] The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

[0662] The compound having active hydrogen and a tertiary amino group in the same molecule is described.

[0663] Examples of active hydrogen, that is, hydrogen atoms directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom include hydrogen atoms in functional groups such as hydroxyl groups, amino groups and thiol groups. Among them, hydrogen atoms in amino groups are preferred, and hydrogen atoms in primary amino groups are particularly preferred.

[0664] The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, and more specifically, an imidazole ring or a triazole ring.

[0665] Examples of such compounds having active hydrogen and a tertiary amino group in the same molecule include N,N-dimethyl-1,3-propylenediamine, N,N-diethyl-1,3-propylenediamine, N,N-dipropyl-1,3-propylenediamine, N,N-dibutyl-1,3-propylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N-dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, and N,N-dibutyl-1,4-butanediamine.

[0666] In addition, as the nitrogen-containing heterocyclic structure of the tertiary amino group, the nitrogen-containing heterocyclic ring includes: a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, a benzimidazole ring, a benzotriazole ring, a benzoxazole ring, a benzothiazole ring, a benzothiadiazole ring and other nitrogen-containing heterocyclic five-membered rings; a pyridine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an acridine ring, an isoquinoline ring and other nitrogen-containing heterocyclic six-membered rings. Among these nitrogen-containing heterocyclic rings, an imidazole ring or a triazole ring is preferred.

[0667] Specific examples of compounds having these imidazole rings and amino groups include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, 1-(2-aminoethyl)imidazole, etc. Specific examples of compounds having triazole rings and amino groups include 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1,4-diphenyl-1,2,3-triazole, and 3-amino-1-benzyl-1H-2,4-triazole. Among them, N,N-dimethyl-1,3-propylenediamine, N,N-diethyl-1,3-propylenediamine, 1-(3-aminopropyl)imidazole, and 3-amino-1,2,4-triazole are preferred.

[0668] These may be used alone or in combination of two or more.

[0669] The preferred blending ratio of the raw materials when producing the urethane polymer dispersant is, relative to 100 parts by mass of the polyisocyanate compound, 10 to 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass of the compound having one or two hydroxyl groups in the same molecule and a number average molecular weight of 300 to 10,000, and 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass of the compound having active hydrogen and a tertiary amino group in the same molecule.

[0670] The urethane-based polymer dispersant is produced by a known method for producing a polyurethane resin.

[0671] As the solvent used in the production, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone; esters such as ethyl acetate, butyl acetate, and cellosolve acetate; hydrocarbons such as benzene, toluene, xylene, and hexane; some alcohols such as diacetone alcohol, isopropanol, sec-butyl alcohol, and tert-butyl alcohol; chlorides such as dichloromethane and chloroform; ethers such as tetrahydrofuran and diethyl ether; aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide; etc. These may be used alone or in combination of two or more.

[0672] In the above production, a urethanization reaction catalyst can usually be used. Examples of the catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stannous octoate; iron-based catalysts such as ferric acetylacetonate and ferric chloride; and tertiary amine-based catalysts such as triethylamine and triethylenediamine. These catalysts may be used alone or in combination of two or more.

[0673] The amount of the compound having active hydrogen and tertiary amino groups in the same molecule is preferably controlled within the range of 1 to 100 mgKOH / g, more preferably within the range of 5 to 95 mgKOH / g, as measured by the amine value after the reaction. The amine value is a value expressed in mg of KOH corresponding to the acid value obtained by neutralization titration of the basic amino group with an acid.

[0674] When the amine value is equal to or greater than the above lower limit, the dispersibility tends to be good, while when the amine value is equal to or less than the above upper limit, the developability tends to be good.

[0675] In addition, when isocyanate groups remain in the polymer dispersant due to the above reaction, it is preferable to further deactivate the isocyanate groups with an alcohol or an amino compound because the temporal stability of the product is improved.

[0676] The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000.

[0677] When the Mw of the urethane polymer dispersant is greater than or equal to the above lower limit, dispersibility and dispersion stability tend to be improved. When the Mw of the urethane polymer dispersant is less than or equal to the above upper limit, solubility tends to be improved and dispersibility tends to be improved.

[0678] As the acrylic polymer dispersant, it is preferred to use a random copolymer, a graft copolymer, or a block copolymer of an unsaturated group-containing monomer having a functional group (the functional group referred to herein is the functional group described above as the functional group contained in the polymer dispersant) and an unsaturated group-containing monomer having no functional group. These copolymers can be produced by a known method.

[0679] Examples of the unsaturated group-containing monomer having a functional group include: unsaturated monomers having a carboxyl group such as (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, and acrylic acid dimer, and unsaturated monomers having a tertiary amino group or a quaternary ammonium salt group such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and quaternary ammonium compounds thereof. These may be used alone or in combination of two or more.

[0680] Examples of the unsaturated group-containing monomer having no functional group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, tris( ... Cyclodecane (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinyl pyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide and other N-substituted maleimides, acrylonitrile, vinyl acetate and polymethyl (meth)acrylate macromonomers, polystyrene macromonomers, poly2-hydroxyethyl (meth)acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, polycaprolactone macromonomers and other macromonomers.

[0681] These may be used alone or in combination of two or more.

[0682] The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer comprising an A block having a functional group and a B block not having a functional group. In this case, in the A block, in addition to the partial structure derived from the above-mentioned monomer containing an unsaturated group containing a functional group, the partial structure derived from the above-mentioned monomer containing an unsaturated group not containing a functional group may also be included, and these can be included in the A block in any manner of random copolymerization or block copolymerization. The content of the partial structure not containing a functional group in the A block is usually 80% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less.

[0683] The B block contains a partial structure derived from the above-mentioned unsaturated group-containing monomer having no functional group, and one B block may contain partial structures derived from two or more monomers, which may be contained in the B block in any form of random copolymerization or block copolymerization.

[0684] The AB or BAB block copolymer can be prepared, for example, by the living polymerization method shown below.

[0685] Living polymerization methods include anionic living polymerization, cationic living polymerization, and free radical living polymerization.

[0686] When synthesizing acrylic polymer dispersants, for example, Japanese Patent Application Publication No. 9-62002 or P. Lutz, P. Masson et al., Polym. Bull. 12, 79 (1984), BC Anderson, GD Andrews et al., Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al. can be used. The known methods described in al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Yuhei, Koichi Hata, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Collected Papers on Polymers, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertler et al, Macromolecules, 20, 1473 (1987).

[0687] The acrylic polymer dispersant that can be used in the present invention can be an AB block copolymer or a BAB block copolymer. The A block / B block ratio constituting the copolymer is preferably 1 / 99 to 80 / 20, and particularly preferably 5 / 95 to 60 / 40 (mass ratio). By setting it within this range, a balance between dispersibility and storage stability is achieved.

[0688] The amount of the quaternary ammonium salt group in 1 g of the AB block copolymer or BAB block copolymer that can be used in the present invention is usually preferably 0.1 to 10 mmol. When the amount is within this range, good dispersibility tends to be ensured.

[0689] Such block copolymers usually contain amino groups generated during the manufacturing process, and their amine value is about 1 to 100 mgKOH / g. From the perspective of dispersibility, it is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, and more preferably 50 mgKOH / g or more, and is preferably 90 mgKOH / g or less, more preferably 80 mgKOH / g or less, and more preferably 75 mgKOH / g or less. For example, the amine value of the block copolymer is preferably 10 to 90 mgKOH / g, more preferably 30 to 80 mgKOH / g, and more preferably 50 to 75 mgKOH / g.

[0690] Here, the amine value of acrylic polymer dispersants such as these block copolymers is expressed as the mass of KOH equivalent to the amount of alkali per 1 gram of the solid content excluding the solvent in the dispersant sample, and is measured by the following method.

[0691] Accurately weigh 0.5-1.5g of the dispersant sample in a 100mL beaker and dissolve it in 50mL of acetic acid. Use an automatic titrator equipped with a pH electrode to neutralize and titrate the solution with 0.1mol / L HClO4 acetic acid solution. The inflection point of the titration pH curve is taken as the titration endpoint and the amine value is calculated using the following formula.

[0692] Amine value [mgKOH / g] = (561×V) / (W×S)

[0693] [W represents the amount of the dispersant sample weighed [g], V represents the titration amount at the titration endpoint [mL], and S represents the solid content concentration of the dispersant sample [mass %]]

[0694] The acid value of the acrylic polymer dispersant is related to the presence or absence and type of the acidic group that is the source of the acid value, but generally the lower the acid value, the better, and is usually 10 mgKOH / g or less, and the weight average molecular weight (Mw) is preferably in the range of 1000 to 100000. By setting it within the above range, it tends to be possible to ensure good dispersibility.

[0695] When the acrylic polymer dispersant has a quaternary ammonium salt group as a functional group, its specific structure is not particularly limited, but from the viewpoint of dispersibility, it preferably has a repeating unit represented by the following formula (e1) (hereinafter sometimes referred to as "repeating unit (e1)").

[0696]

[0697] (In formula (e1), R 31 ~R 33 R each independently represents a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent; 31 ~R 33 Two or more of them may be bonded to each other to form a ring structure; 34 is a hydrogen atom or a methyl group; X 31 is a divalent linking group; E - is the counter anion.)

[0698] R in the above formula (e1) 31 ~R 33 The carbon number of the alkyl group which may have a substituent is not particularly limited, but is preferably 1 or more and 10 or less, and more preferably 6 or less. For example, the carbon number of the alkyl group is preferably 1-10, and more preferably 1-6.

[0699] The alkyl group may be straight chain or branched. In addition, the alkyl group may include a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

[0700] Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups. Among these, methyl, ethyl, propyl, butyl, pentyl and hexyl groups are preferred, and methyl, ethyl, propyl and butyl groups are more preferred.

[0701] R in the above formula (e1) 31 ~R 33 The carbon number of the aryl group which may have a substituent is not particularly limited, but is usually preferably 6 or more and 16 or less, and more preferably 12 or less. For example, the carbon number of the aryl group is preferably 6-16, and more preferably 6-12.

[0702] Specific examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl. Among these, phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl are preferred, and phenyl, methylphenyl, and ethylphenyl are more preferred.

[0703] R in the above formula (e1) 31 ~R 33 The carbon number of the aralkyl group which may have a substituent is not particularly limited, but is usually preferably 7 or more and 16 or less, and more preferably 12 or less. For example, the carbon number of the aralkyl group is preferably 7-16, and more preferably 7-12.

[0704] Specific examples of the aralkyl group include benzyl, phenethyl, phenylpropyl, phenylbutyl, and phenylisopropyl. Among these, benzyl, phenethyl, phenylpropyl, and phenylbutyl are preferred, and benzyl and phenethyl are more preferred.

[0705] Among these, R 31 ~R 33 are independently alkyl or aralkyl, and more preferably R 31 and R 33 are independently methyl, ethyl and R 32 is benzyl or phenethyl, and more preferably R 31 and R 33 is methyl and R 32 It is benzyl.

[0706] Furthermore, when the polymer dispersant has a tertiary amine as a functional group, it preferably has a repeating unit represented by the following formula (e2) (hereinafter, sometimes referred to as “repeating unit (e2)”) from the viewpoint of dispersibility.

[0707]

[0708] (In formula (e2), R35 and R 36 are each independently a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent; R 35 and R 36 They can also bond with each other to form a ring structure; R 37 is a hydrogen atom or a methyl group; X 32 is a divalent linking group.)

[0709] As R of the above formula (e2) 35 and R 36 The alkyl group optionally having a substituent in the formula (e1) can preferably be used as R 31 ~R 33 exemplified.

[0710] As R of the above formula (e2) 35 and R 36 The aryl group which may have a substituent may preferably be used as R in the above formula (e1): 31 ~R 33 exemplified.

[0711] As R of the above formula (e2) 35 and R 36 The aralkyl group which may have a substituent may preferably be used as R in the above formula (e1). 31 ~R 33 exemplified.

[0712] Among these, R 35 and R 36 Each independently is preferably an alkyl group which may have a substituent, and more preferably a methyl group or an ethyl group.

[0713] As R of the above formula (e1) 31 ~R 33 and R of the above formula (e2) 35 and R 36 Examples of the substituent that the alkyl group, aralkyl group or aryl group in the group may have include a halogen atom, an alkoxy group, a benzoyl group and a hydroxyl group.

[0714] In the above formulae (e1) and (e2), the divalent linking group X 31 and X 32 , for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R 43 -base, -COO-R 44 -base [where R 43 and R 44 is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkoxyalkyl group) having 2 to 10 carbon atoms, preferably -COO-R44 -base.

[0715] In the above formula (e1), the counter anion E - , for example: Cl - Br - ,I - 、ClO4 - 、BF4 - 、CH3COO - PF6 - .

[0716] The content ratio of the repeating unit represented by the above formula (e1) in the acrylic polymer dispersant is not particularly limited. From the viewpoint of dispersibility, the total content ratio of the repeating unit represented by the above formula (e1) and the repeating unit represented by the above formula (e2) in all the repeating units of the polymer dispersant is preferably 60 mol% or less, more preferably 50 mol% or less, further preferably 40 mol% or less, particularly preferably 35 mol% or less, and is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, and particularly preferably 30 mol% or more.

[0717] For example, the content ratio of the repeating unit represented by the above formula (e1) relative to the total content ratio of the repeating unit represented by the above formula (e1) and the content ratio of the repeating unit represented by the above formula (e2) is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, further preferably 20 to 40 mol%, and particularly preferably 30 to 35 mol%.

[0718] The content ratio of the repeating unit represented by the above formula (e1) in the total repeating units of the acrylic polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, and is preferably 50 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, and particularly preferably 15 mol% or less.

[0719] For example, the content ratio of the repeating unit represented by the above formula (e1) in all repeating units of the acrylic polymer dispersant is preferably 1 to 50 mol %, more preferably 5 to 30 mol %, further preferably 10 to 20 mol %, particularly preferably 10 to 15 mol %.

[0720] The content ratio of the repeating unit represented by the above formula (e2) in the total repeating units of the acrylic polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 15 mol% or more, particularly preferably 20 mol% or more, and is preferably 60 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, and particularly preferably 25 mol% or less.

[0721] For example, the content ratio of the repeating unit represented by the above formula (e2) in all repeating units of the acrylic polymer dispersant is preferably 5 to 60 mol%, more preferably 10 to 40 mol%, further preferably 15 to 30 mol%, and particularly preferably 20 to 25 mol%.

[0722] The acrylic polymer dispersant preferably has a repeating unit represented by the following formula (e3) (hereinafter sometimes referred to as “repeating unit (e3)”) from the viewpoint of improving compatibility with binder components such as solvents and improving dispersion stability.

[0723]

[0724] (In the above formula (e3), R 40 is ethylene or propylene; R 41 is an alkyl group which may have a substituent; R 42 is a hydrogen atom or a methyl group; k is an integer from 1 to 20. )

[0725] R in the above formula (e3) 41 The carbon number of the alkyl group which may have a substituent is not particularly limited, but is 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 6 or less. For example, the carbon number of the alkyl group is preferably 1-10, more preferably 2-6.

[0726] The alkyl group may be straight chain or branched. In addition, the alkyl group may include a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

[0727] Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups. Among these, methyl, ethyl, propyl, butyl, pentyl and hexyl groups are preferred, and methyl, ethyl, propyl and butyl groups are more preferred.

[0728] In terms of compatibility and dispersibility with binder components such as solvents, k in the formula (e3) is 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 5 or less. For example, k is preferably 1-10, more preferably 2-5.

[0729] The content ratio of the repeating unit represented by the above formula (e3) in the total repeating units of the acrylic polymer dispersant is not particularly limited, and is preferably 1 mol% or more, more preferably 2 mol% or more, and further preferably 4 mol% or more, and is preferably 30 mol% or less, more preferably 20 mol% or less, and further preferably 10 mol% or less. When the content ratio is within the above range, there is a tendency to be able to take into account both compatibility with binder components such as solvents and dispersion stability.

[0730] For example, the content ratio of the repeating unit represented by the formula (e3) in all the repeating units of the acrylic polymer dispersant is preferably 1 to 30 mol %, more preferably 2 to 20 mol %, and even more preferably 4 to 10 mol %.

[0731] The acrylic polymer dispersant preferably has a repeating unit represented by the following formula (e4) (hereinafter sometimes referred to as "repeating unit (e4)") from the viewpoint of improving compatibility with binder components such as the solvent of the dispersant and improving dispersion stability.

[0732]

[0733] (In the above formula (e4), R 38 is an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent; R 39 is a hydrogen atom or a methyl group.)

[0734] R in the above formula (e4) 38 The carbon number of the alkyl group which may have a substituent is not particularly limited, and is 1 or more, preferably 2 or more, more preferably 4 or more, and is preferably 10 or less, more preferably 8 or less. For example, the carbon number of the alkyl group is preferably 1-10, more preferably 2-8, and further preferably 4-8.

[0735] The alkyl group may be straight chain or branched. In addition, the alkyl group may include a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

[0736] Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups. Among these, methyl, ethyl, propyl, butyl, pentyl and hexyl groups are preferred, and methyl, ethyl, propyl and butyl groups are more preferred.

[0737] R in the above formula (e4) 38 The carbon number of the aryl group which may have a substituent is not particularly limited, but is usually 6 or more, preferably 16 or less, more preferably 12 or less, and further preferably 8 or less. For example, the carbon number of the aryl group is preferably 6-16, more preferably 6-12, and further preferably 8-12.

[0738] Specific examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl. Among these, phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl are preferred, and phenyl, methylphenyl, and ethylphenyl are more preferred.

[0739] R in the above formula (e4) 38 The carbon number of the aralkyl group which may have a substituent is not particularly limited, but is usually 7 or more, preferably 16 or less, more preferably 12 or less, and further preferably 10 or less. For example, the carbon number of the aralkyl group is preferably 7-16, more preferably 7-12, and further preferably 7-10.

[0740] Specific examples of the aralkyl group include benzyl, phenethyl, phenylpropyl, phenylbutyl, and phenylisopropyl. Among these, benzyl, phenethyl, phenylpropyl, and phenylbutyl are preferred, and benzyl and phenethyl are more preferred.

[0741] Among these, R 38 Preferred are alkyl groups and aralkyl groups, and more preferred are methyl groups, ethyl groups and benzyl groups.

[0742] As R 38 Examples of the substituent that the alkyl group in the group may have include a halogen atom and an alkoxy group. Examples of the substituent that the aryl group and the aralkyl group may have include an alkyl group, a halogen atom and an alkoxy group.

[0743] The content ratio of the repeating unit represented by the above formula (e4) in all repeating units of the acrylic polymer dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more, and is preferably 80 mol% or less, more preferably 70 mol% or less, from the viewpoint of dispersibility.

[0744] For example, the content ratio of the repeating unit represented by the above formula (e4) in all the repeating units of the polymer dispersant is preferably 30 to 80 mol %, more preferably 40 to 70 mol %, and even more preferably 50 to 70 mol %.

[0745] The acrylic polymer dispersant may have repeating units other than the repeating units (e1), (e2), (e3) and (e4). Examples of such repeating units include repeating units derived from styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acryloyl chloride; (meth)acrylamide monomers such as N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and N-methacryloylmorpholine.

[0746] Regarding acrylic polymer dispersants, from the perspective of further improving dispersibility, preferably a block copolymer having an A block and a B block, wherein the A block has repeating units (e1) and repeating units (e2), and the B block does not have repeating units (e1) and repeating units (e2). The block copolymer is preferably an AB block copolymer or a BAB block copolymer. By introducing not only a quaternary ammonium salt group but also a tertiary amino group into the A block, a tendency is shown that the dispersing ability of the dispersant is significantly improved. In addition, the B block preferably has a repeating unit (e3), and more preferably has a repeating unit (e4).

[0747] Repeating units (e1) and repeating units (e2) may be included in the A block in any form of random copolymerization or block copolymerization. In addition, repeating units (e1) and repeating units (e2) may each contain two or more in one A block, in which case, each repeating unit may be included in the A block in any form of random copolymerization or block copolymerization.

[0748] In addition, the A block may contain repeating units other than the repeating units (e1) and the repeating units (e2), and examples of such repeating units include repeating units derived from the above-mentioned (meth)acrylate monomers, etc. The content of repeating units other than the repeating units (e1) and the repeating units (e2) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but it is most preferred that the A block does not contain such repeating units.

[0749] The B block may contain repeating units other than the repeating units (e3) and (e4). Examples of such repeating units include repeating units derived from styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acryloyl chloride; (meth)acrylamide monomers such as N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and N-methacryloylmorpholine. The content of repeating units other than the repeating units (e3) and (e4) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but it is most preferred that the B block does not contain such repeating units.

[0750] When the photosensitive resin composition of the present invention contains a dispersant, the content ratio thereof is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 4% by mass or more relative to the total solid content of the photosensitive resin composition. In addition, it is preferably 12% by mass or less, more preferably 10% by mass or less, and particularly preferably 9% by mass or less.

[0751] When the content ratio is set to be equal to or greater than the above lower limit, the generation of residues due to aggregates tends to be suppressed, while when the content ratio is set to be equal to or less than the above upper limit, the developability tends to be improved.

[0752] For example, when the photosensitive resin composition contains a dispersant, the content ratio of the dispersant to the total solid content of the photosensitive resin composition is preferably 1 to 12 mass %, more preferably 2 to 10 mass %, and particularly preferably 4 to 9 mass %.

[0753] [1-1-6] Pigment derivatives

[0754] The photosensitive resin composition of the present invention may contain a pigment derivative as a dispersing aid to improve dispersibility and storage properties.

[0755] Examples of the pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, pyrenone, diketopyrrolopyrrole, and dioxazine derivatives, among which phthalocyanine and quinophthalone derivatives are preferred.

[0756] Examples of substituents of the pigment derivative include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc., which are directly or via alkyl groups, aryl groups, heterocyclic groups, etc., bonded to the pigment skeleton, preferably sulfonic acid groups. In addition, these substituents may be substituted with multiple groups on one pigment skeleton.

[0757] Specific examples of pigment derivatives include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of dionepyrrolopyrrole, and sulfonic acid derivatives of dioxazine. These may be used alone or in combination of two or more.

[0758] [1-1-7] Surfactants

[0759] The photosensitive resin composition of the present invention may contain a surfactant to improve coating properties.

[0760] As the surfactant, various surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants can be used. Among them, nonionic surfactants are preferably used because they are less likely to have adverse effects on various properties, and fluorine-based or silicone-based surfactants are effective in terms of coating properties.

[0761] Commercially available products of fluorine-based surfactants include, for example, "BM-1000" and "BM-1100" manufactured by BM Chemie; "MEGAFAC F-142D", "MEGAFAC F-172", "MEGAFAC F-173", "MEGAFAC F-183", "MEGAFAC F-470", "MEGAFAC F-475", "MEGAFAC F-478", "MEGAFAC F-554", and "MEGAFAC F-559" manufactured by DIC Corporation; "FC430" manufactured by 3M Japan; and "DFX-18" manufactured by NEOS.

[0762] Examples of the silicone-based surfactant include "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032Additive", and "SH8400" manufactured by Dow Corning Toray Co., Ltd.; "BYK300", "BYK323", "BYK325", and "BYK330" manufactured by BYK-Chemie; and commercially available products such as "KP340" manufactured by Shin-Etsu Silicone Co., Ltd.

[0763] Surfactants other than fluorine-based surfactants and silicone-based surfactants may be contained as surfactants. Examples of other surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.

[0764] The surfactant may be used alone or in any combination and ratio. Preferably, a combination of a silicone surfactant and a fluorine surfactant is used. For example, a combination of a silicone surfactant and a fluorine surfactant may be used. Examples of the silicone surfactant and the fluorine surfactant include "BYK-300" or "BYK-330" manufactured by BYK-Chemie and "F-475", "F-478", "F-554" or "F-559" manufactured by DIC.

[0765] When the photosensitive resin composition of the present invention contains a surfactant, the content ratio of the surfactant in the photosensitive resin composition of the present invention is usually 0.01% by mass or more, preferably 0.03% by mass or more, more preferably 0.05% by mass or more, relative to the total solid content of the photosensitive resin composition, and is usually 2% by mass or less, preferably 1.5% by mass or less, and more preferably 1% by mass or less. By setting the content ratio to be above the lower limit, the coating property tends to be improved. By setting the content ratio to be below the upper limit, the residue tends to be less likely to be generated.

[0766] [1-1-8] Liquid repellent

[0767] The photosensitive resin composition of the present invention may also contain a liquid repellent. In particular, when the photosensitive resin composition of the present invention is used to make a partition wall and an organic electroluminescent element is made by an inkjet method, it is preferred to contain a liquid repellent. By containing a liquid repellent, the liquid repellent can impart liquid repellency to the surface of the partition wall, and therefore, the obtained partition wall can prevent the color mixing of each pixel of the organic layer.

[0768] Examples of the liquid repellent include silicone-containing compounds and fluorine-based compounds, and preferably, a liquid repellent having a crosslinking group (hereinafter, sometimes referred to as a “crosslinking group-containing liquid repellent”) is used.

[0769] Examples of the crosslinking group include an epoxy group and an ethylenically unsaturated group. From the viewpoint of suppressing outflow of liquid repellent components of a developer, an ethylenically unsaturated group is preferred.

[0770] It is considered that when a liquid repellent containing a crosslinking group is used, the crosslinking reaction on the surface of the formed coating film can be accelerated when the formed coating film is exposed to light, and the liquid repellent is less likely to flow out by development treatment, resulting in that the obtained partition wall can exhibit high liquid repellency.

[0771] When a fluorine compound is used as a liquid repellent, the fluorine compound is oriented on the surface of the partition wall, thereby showing a tendency to prevent the penetration or color mixing of the ink. More specifically, the group having fluorine atoms repels the ink, thereby showing a tendency to prevent the penetration or color mixing of the ink caused by the ink overflowing over the partition wall to the adjacent area.

[0772] As specific examples of crosslinking group-containing liquid repellents, particularly fluorinated compounds containing ethylenically unsaturated groups, for example, perfluoroalkyl sulfonic acid, perfluoroalkyl carboxylic acid, perfluoroalkyl alkylene oxide adduct, perfluoroalkyl trialkyl ammonium salt, oligomers comprising perfluoroalkyl and hydrophilic groups, oligomers comprising perfluoroalkyl and lipophilic groups, oligomers comprising perfluoroalkyl, hydrophilic groups and lipophilic groups, carbamates comprising perfluoroalkyl and hydrophilic groups, perfluoroalkyl esters, perfluoroalkyl phosphates and other fluorinated organic compounds.

[0773] As commercial products of these fluorine-containing compounds, for example, fluorine-containing compounds commercially available under the following trade names can be used: "DEFENSAMCF-300", "DEFENSAMCF-310", "DEFENSAMCF-312", "DEFENSAMCF-323", and "MEGAFAC RS-72-K" manufactured by DIC Corporation; "Fluorad FC-431", "Fluorad FC-4430", and "Fluorad FC-4432" manufactured by 3M Japan; "AsahiGuard AG710", "Surflon S-382", "Surflon SC-101", "Surflon SC-102", "Surflon SC-103", "Surflon SC-104", "Surflon SC-105", and "Surflon SC-106" manufactured by Asahi Glass Co., Ltd.; and "OPTOOL DAC-HP" and "HP-650" manufactured by Daikin Industries, Ltd.

[0774] When a fluorine-based compound is used as a liquid repellent, the content ratio of fluorine atoms in the liquid repellent is not particularly limited. Preferably, the content ratio of fluorine atoms is preferably 1% by mass or more, more preferably 5% by mass or more, and preferably 50% by mass or less, more preferably 25% by mass or less.

[0775] When the content ratio is set to be equal to or greater than the above lower limit, a high contact angle tends to be exhibited, and when the content ratio is set to be equal to or less than the above upper limit, outflow to the pixel portion tends to be suppressed.

[0776] The molecular weight of the liquid repellent is not particularly limited.

[0777] When the photosensitive resin composition of the present invention contains a liquid repellent, the content ratio of the liquid repellent in the photosensitive resin composition of the present invention is, for example, 0.01 mass % or more and 1 mass % or less relative to the total solid content of the photosensitive resin composition.

[0778] When the content ratio is set to be equal to or greater than the lower limit, a higher liquid repellency tends to be exhibited, while when the content ratio is set to be equal to or less than the upper limit, outflow of the liquid repellent to the pixel portion tends to be suppressed.

[0779] [1-1-9] Ultraviolet light absorber

[0780] The photosensitive resin composition of the present invention may also contain an ultraviolet absorber. The ultraviolet absorber is added for the following purpose: by utilizing the ultraviolet absorber to absorb the specific wavelength of the light source used for exposure, the photocuring distribution is controlled. By adding the ultraviolet absorber, the verticality of the side of the partition wall after development can be improved, or the residue remaining in the non-exposed part after development can be eliminated.

[0781] As the ultraviolet absorber, from the viewpoint of suppressing the interference with the light absorption of the (b) photopolymerization initiator, for example, a compound having a maximum absorption at a wavelength of 250 nm to 400 nm can be used.

[0782] As the ultraviolet absorber, it is desirable to include any one or both of a benzotriazole compound and a triazine compound. It is believed that by including any one or both of a benzotriazole compound and a triazine compound, the light absorption rate of the (b) photopolymerization initiator is reduced, and the photocurability is reduced, thereby obtaining an effect of increasing the melt flow during the baking of the film and reducing the taper angle.

[0783] Examples of the benzotriazole compound include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate octyl, 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate ethylhexyl, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)-3-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate. 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, octyl 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, nonyl 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate.

[0784] Examples of commercially available benzotriazole compounds include SUMISORB (registered trademark, the same below) 200, SUMISORB 250, SUMISORB 300, SUMISORB 340, and SUMISORB 350 (manufactured by Sumitomo Chemical Co., Ltd.); JF77, JF78, JF79, JF80, and JF83 (manufactured by Johoku Chemical Industry Co., Ltd.); TINUVIN (registered trademark, the same below) PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, and TINUVIN 326, TINUVIN900, TINUVIN928, TINUVIN1130 (manufactured by BASF); EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (manufactured by Taiwan Everlight Chemical Industry Co., Ltd.); Tomissorb (registered trademark, the same below) 100, Tomissorb 600 (manufactured by API Corporation); SEESORB (registered trademark, the same below) 701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB709 (manufactured by SHIPRO KASEI); RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.).

[0785] Examples of the triazine compound include 2-[4,6-di(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-octyloxyphenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, a reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-ethylhexyl glycidyl ether, and 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3-5-triazine. Among these, hydroxyphenyl triazine compounds are preferred from the viewpoint of the perpendicularity of the side surfaces of the partition walls and the resolution.

[0786] As a commercially available triazine compound, TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, and TINUVIN479 (made by BASF) are mentioned, for example.

[0787] As other ultraviolet absorbers, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, binaphthyl compounds, phenanthroline compounds, and dyes are mentioned, for example.

[0788] More specifically, for example, SUMISORB130 (manufactured by Sumitomo Chemical Co., Ltd.), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Everlight Chemical Industry Co., Ltd., Taiwan, China), Tomissorb800 (manufactured by API Corporation), SEESORB100, SEESORB101, SEESORB101S, SEESORB102, SEESORB103, SEESORB105, SEESORB106, SEESORB107, SEESORB151 (manufactured by SHIPRO Benzophenone compounds such as benzoyl peroxide (produced by KASEI Co., Ltd.); benzoate compounds such as SUMISORB400 (produced by Sumitomo Chemical Co., Ltd.) and phenyl salicylate; cinnamic acid derivatives such as 2-ethylhexyl cinnamate, 2-ethylhexyl p-methoxycinnamate, isopropyl methoxycinnamate, and isoamyl methoxycinnamate; α-naphthol, β-naphthol, α-naphthol methyl ether, α-naphthol ethyl ether, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene Hydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and other naphthalene derivatives; anthracene and its derivatives such as anthracene and 9,10-dihydroxyanthracene; dyes such as azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes, and p-aminobenzoic acid dyes. Among these, from the perspective of resolution, cinnamic acid derivatives and naphthalene derivatives are preferably used, and cinnamic acid derivatives are particularly preferably used. These light absorbers can be used alone or in combination of two or more.

[0789] Among these, from the viewpoint of the tapered shape, either or both of a benzotriazole compound and a hydroxyphenyltriazine compound are preferred, and a benzotriazole compound is particularly preferred.

[0790] As the ultraviolet absorber, one compound may be used alone or two or more compounds may be used in combination.

[0791] When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the content ratio thereof is not particularly limited, but is, for example, 0.01 to 15% by mass based on the total solid content of the photosensitive resin composition.

[0792] In addition, when the photosensitive resin composition of the present invention contains an ultraviolet absorber, the blending ratio of the ultraviolet absorber to the (b) photopolymerization initiator is usually 1 part by mass or more, preferably 10 parts by mass or more, more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, and is usually 500 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, further preferably 100 parts by mass or less, based on the blending amount of the ultraviolet absorber relative to 100 parts by mass of the (b) photopolymerization initiator.

[0793] When the mixing ratio is equal to or greater than the above lower limit, the resolution tends to be good, while when the mixing ratio is equal to or less than the above upper limit, the adhesion tends to be high.

[0794] When the photosensitive resin composition of the present invention contains a UV absorber, the amount of the UV absorber blended relative to 100 parts by mass of the (b) photopolymerization initiator is, for example, preferably 1 to 500 parts by mass, more preferably 10 to 300 parts by mass, further preferably 30 to 200 parts by mass, still more preferably 50 to 100 parts by mass, and particularly preferably 80 to 100 parts by mass.

[0795] [1-1-10] Inhibitor

[0796] The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor. By containing a polymerization inhibitor, the radical polymerization is inhibited, and thus the tapered shape of the partition wall to be obtained tends to be adjusted.

[0797] Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-methylphenol (BHT). Among these, hydroquinone and methoxyphenol are preferred, and methyl hydroquinone is more preferred from the viewpoint of polymerization inhibition ability.

[0798] It is preferable to contain 1 type or 2 or more types of polymerization inhibitors.

[0799] Usually, when producing (a) the alkali-soluble resin, the resin may contain a polymerization inhibitor, which may be used as it is, or when producing the photosensitive resin composition, a polymerization inhibitor which is the same as or different from the polymerization inhibitor contained in the resin may be added.

[0800] When the photosensitive resin composition of the present invention contains a polymerization inhibitor, the content ratio thereof is not particularly limited, but is usually 0.0005% by mass or more, preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and is usually 0.1% by mass or less, preferably 0.08% by mass or less, more preferably 0.05% by mass or less, relative to the total solid content of the photosensitive resin composition.

[0801] When the content ratio is equal to or greater than the above lower limit, the resolution tends to be improved, while when the content ratio is equal to or less than the above upper limit, the curability tends to be improved.

[0802] For example, when the photosensitive resin composition contains a polymerization inhibitor, the content ratio of the polymerization inhibitor relative to the total solid content of the photosensitive resin composition is preferably 0.0005 to 0.1% by mass, more preferably 0.001 to 0.08% by mass, and further preferably 0.01 to 0.05% by mass.

[0803] [1-1-11] Thermal polymerization initiator

[0804] Furthermore, the photosensitive resin composition of the present invention may contain a thermal polymerization initiator. By containing a thermal polymerization initiator, there is a tendency that the degree of crosslinking of the coating film can be increased.

[0805] Specific examples of such thermal polymerization initiators include azo compounds, organic peroxides, and hydrogen peroxide. These may be used alone or in combination of two or more.

[0806] When a thermal polymerization initiator is used in combination with a photopolymerization initiator in order to expect an improvement in resolution or an increase in the crosslinking density of the coating film, it is preferred that the total of their content ratios be the content ratio of the photopolymerization initiator in the photosensitive resin composition. In addition, as the ratio of the photopolymerization initiator and the thermal polymerization initiator used in combination, from the viewpoint of reducing residues, it is preferred that the thermal polymerization initiator be set to 5 to 300 parts by mass relative to 100 parts by mass of the photopolymerization initiator.

[0807] [1-1-12] Amino compounds

[0808] The photosensitive resin composition of the present invention may also contain an amino compound to promote thermal curing.

[0809] Examples of the amino compound include amino compounds having at least two methylol groups and alkoxymethyl groups as functional groups obtained by condensing the methylol groups with an alcohol having 1 to 8 carbon atoms. Specifically, examples include: melamine resins obtained by polycondensing melamine with formaldehyde; benzoguanamine resins obtained by polycondensing benzoguanamine with formaldehyde; glycoluril resins obtained by polycondensing glycoluril with formaldehyde; urea resins obtained by polycondensing urea with formaldehyde; resins obtained by co-condensing two or more of melamine, benzoguanamine, glycoluril or urea with formaldehyde; and modified resins obtained by condensing the methylol groups of the above resins with alcohols.

[0810] These may be used alone or in combination of two or more.

[0811] Among them, the amino compound is preferably a melamine resin and a modified resin thereof, more preferably a modified resin having a modification ratio of 70% or more of a methylol group, and particularly preferably a modified resin having a modification ratio of 80% or more of a methylol group.

[0812] Specific examples of the amino compounds include melamine resins and modified resins thereof, such as "Cymel" (registered trademark, the same below) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158 manufactured by Cytec, and "NIKALAC" (registered trademark, the same below) MW-390, MW-100LM, MX-750LM, MW-30M, MX-45, MX-302 manufactured by Sanwa Chemical Co., Ltd. In addition, examples of benzoguanamine resins and modified resins thereof include "Cymel" 1123, 1125, 1128 manufactured by Cytec. Examples of the glycoluril resin and its modified resin include Cymel 1170, 1171, 1174, and 1172 manufactured by Cytec and Nikalac MX-270 manufactured by Sanwa Chemical Co., Ltd. Examples of the urea resin and its modified resin include UFR (registered trademark) 65 and 300 manufactured by Cytec and Nikalac MX-290 manufactured by Sanwa Chemical Co., Ltd.

[0813] When the photosensitive resin composition of the present invention contains an amino compound, the content of the amino compound is usually 40% by mass or less, preferably 30% by mass or less, and usually 0.5% by mass or more, preferably 1% by mass or more, relative to the total solid content of the photosensitive resin composition.

[0814] When the content ratio is set to be less than or equal to the upper limit, storage stability tends to be maintained, while when the content ratio is set to be greater than or equal to the lower limit, sufficient thermosetting properties tend to be ensured.

[0815] For example, when the photosensitive resin composition contains an amino compound, the content ratio of the amino compound relative to the total solid content of the photosensitive resin composition is preferably 0.5 to 40% by mass, and more preferably 1 to 30% by mass.

[0816] [1-1-13] Silane coupling agent

[0817] It is also preferred to add a silane coupling agent to the photosensitive resin composition of the present invention to improve adhesion to the substrate. As the type of silane coupling agent, various substances such as epoxy, methacrylic, amino, and imidazole can be used. From the perspective of improving adhesion, epoxy and imidazole silane coupling agents are particularly preferred.

[0818] When the photosensitive resin composition of the present invention contains a silane coupling agent, the content thereof is preferably, for example, 0.1% by mass to 1% by mass relative to the total solid content of the photosensitive resin composition from the viewpoint of adhesion.

[0819] [1-1-14] Inorganic fillers

[0820] The photosensitive resin composition of the present invention may further contain an inorganic filler to improve the strength of the cured product and to improve the excellent verticality and taper angle of the coating film through appropriate interaction with the alkali-soluble resin (formation of a matrix structure). Examples of such inorganic fillers include talc, silica, alumina, barium sulfate, magnesium oxide, titanium oxide, and those obtained by surface-treating these with various silane coupling agents.

[0821] The average particle size of these inorganic fillers is usually 0.005 to 2 μm, preferably 0.01 to 1 μm. Here, the average particle size in this embodiment refers to the value measured by a laser diffraction scattering particle size distribution measuring device manufactured by Beckman Coulter, etc. Among these inorganic fillers, silica sol and silica sol modified products are particularly preferred because they tend to show excellent dispersion stability and cone angle improvement effects.

[0822] When the photosensitive resin composition of the present invention contains these inorganic fillers, the content of these inorganic fillers is, for example, 5 mass % or more and 80 mass % or less relative to the total solid content of the photosensitive resin composition from the viewpoint of resolution.

[0823] [1-1-15] Adhesion enhancer

[0824] The photosensitive resin composition of the present invention may contain a phosphoric acid-based olefinic monomer to impart adhesion to the substrate. The phosphoric acid-based olefinic monomer is preferably a (meth)acryloyloxy-containing phosphate ester, preferably a monomer represented by the following general formula (g1), (g2), or (g3).

[0825]

[0826] (In formula (g1), (g2) and (g3), R 51 represents a hydrogen atom or a methyl group; e and e' are each independently an integer of 1 to 10; and f is 1, 2 or 3.

[0827] These phosphoric acid-based ethylenic monomers may be used alone or in combination of two or more.

[0828] When the photosensitive resin composition of the present invention contains these phosphoric acid-based ethylenic monomers, the content ratio thereof is, for example, 0.02 to 4% by mass relative to the total solid content of the photosensitive resin composition.

[0829] [1-1-16] Solvents

[0830] The photosensitive resin composition of the present invention usually contains a solvent, and is used in a state where the above-mentioned components are dissolved or dispersed in the solvent. The solvent is not particularly limited, and examples thereof include the organic solvents described below.

[0831] Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

[0832] Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether and dipropylene glycol dimethyl ether;

[0833] Glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, 3-methoxy-1-butyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

[0834] Glycol diacetates such as ethylene glycol diacetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,4-butylene glycol diacetate, and 1,6-hexanol diacetate;

[0835] Alkyl acetates such as cyclohexyl acetate;

[0836] Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether;

[0837] Ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl amyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl amyl ketone;

[0838] Monohydric or polyhydric alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol;

[0839] Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;

[0840] Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and dicyclohexane;

[0841] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

[0842] Chain or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl isobutyrate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone;

[0843] Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

[0844] Halogenated hydrocarbons such as chlorobutane and chloropentane;

[0845] Ether ketones such as methoxymethylpentyl ketone;

[0846] Nitriles such as acetonitrile and benzonitrile;

[0847] Tetrahydrofurans such as tetrahydrofuran, dimethyltetrahydrofuran and dimethoxytetrahydrofuran.

[0848] Examples of commercially available solvents corresponding to the above-mentioned solvents include mineral spirits, Varsol #2, Apco #18 solvent, Apco thinner, Socal solvents No. 1 and No. 2, Solvesso #150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diethylene glycol dimethyl ether (all trade names).

[0849] The above-mentioned solvent is a solvent that can dissolve or disperse the components in the photosensitive resin composition, and can be selected according to the method of using the photosensitive resin composition of the present invention. From the viewpoint of coating properties, it is preferred to select a solvent having a boiling point in the range of 60 to 280° C. under atmospheric pressure. More preferably, a solvent having a boiling point of 70° C. or higher and 260° C. or lower is preferred, for example, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate are preferred.

[0850] These solvents may be used alone or in combination of two or more.

[0851] These solvents are preferably used in a manner such that the ratio of the total solid content of the photosensitive resin composition is usually 1% by mass or more, preferably 5% by mass or more, more preferably 7% by mass or more, and further preferably 10% by mass or more, and is usually 90% by mass or less, preferably 50% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less.

[0852] When the total solid content of the photosensitive resin composition is greater than or equal to the above lower limit, the occurrence of coating unevenness tends to be suppressed. When the total solid content of the photosensitive resin composition is less than or equal to the above upper limit, the occurrence of foreign matter, repulsion, etc. tends to be suppressed.

[0853] For example, the solvent is preferably used in an amount of preferably 1 to 90% by mass, more preferably 5 to 50% by mass, further preferably 7 to 45% by mass, particularly preferably 10 to 40% by mass based on the total solid content of the photosensitive resin composition.

[0854] [1-2] Preparation method of photosensitive resin composition

[0855] The photosensitive resin composition of the present invention can be prepared by mixing the above-mentioned components using a stirrer.

[0856] For example, when a component insoluble in a solvent such as a pigment is included as the colorant (d), it is preferably dispersed in advance using a paint conditioner, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, etc. The dispersion treatment can micronize the colorant (d), thereby improving the coating properties of the photosensitive resin composition.

[0857] The dispersion treatment is usually preferably performed using a system that uses a dispersion aid and part or all of the (a) alkali-soluble resin in combination with (d) a colorant, a solvent, and a dispersant (hereinafter, the mixture subjected to the dispersion treatment and the composition obtained by the treatment may be referred to as "ink" or "pigment dispersion"). In particular, it is preferred to use a polymer dispersant as the dispersant because the thickening of the obtained ink and photosensitive resin composition over time is suppressed (excellent dispersion stability).

[0858] As described above, in the step of producing the photosensitive resin composition, it is preferred to produce a pigment dispersion containing at least (d) a colorant, a solvent, and a dispersant.

[0859] As the (d) colorant, solvent, and dispersant that can be used in the pigment dispersion, the substances described as the (d) colorant, solvent, and dispersant that can be used in the photosensitive resin composition can be preferably used. In addition, the content ratio of each colorant as the (d) colorant in the pigment dispersion can also be preferably used as the ratio described as the content ratio in the photosensitive resin composition.

[0860] When the colorant (d) is dispersed by a sand mill, glass beads or zirconium oxide beads having a particle size of about 0.1 to 8 mm can be preferably used. The temperature of the dispersion treatment conditions is usually 0°C to 100°C, preferably in the range of room temperature to 80°C. Regarding the dispersion time, since the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment device, it should be adjusted appropriately. The goal of dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the photosensitive resin composition is in the range of 50 to 300.

[0861] The dispersed particle size of the pigment dispersed in the ink is usually 0.03 to 0.3 μm, and can be measured by a dynamic light scattering method or the like.

[0862] The dispersed particle size measurement by dynamic light scattering (DLS) is performed on a sufficiently diluted ink (usually diluted to prepare a pigment concentration of about 0.005 to 0.2 mass %; however, if the measuring machine has a recommended concentration, it is used) and the measurement is performed at 25°C.

[0863] After the above dispersion treatment, the obtained ink is mixed with other components contained in the photosensitive resin composition except the above to prepare a uniform solution. In the manufacturing process of the photosensitive resin composition, sometimes fine dirt is mixed into the liquid, so it is ideal to filter the obtained photosensitive resin composition through a filter or the like.

[0864] [2] Cured article, partition wall and method for forming the same

[0865] The cured product of the present invention can be obtained by curing the photosensitive resin composition of the present invention.

[0866] For example, according to the method for forming a cured product of the present invention, a cured product can be formed by performing at least the following steps (1) to (4) using the following photosensitive resin composition, wherein the above-mentioned photosensitive resin composition contains (a) an alkali-soluble resin, (b) a photopolymerization initiator and (c) an ethylenically unsaturated compound, and the above-mentioned (c) ethylenically unsaturated compound contains an ethylenically unsaturated compound (c1') having an alkylene oxide group, and preferably contains the above-mentioned ethylenically unsaturated compound (c1).

[0867] Step (1): a step of forming a coating film of the photosensitive resin composition on a substrate.

[0868] Step (2): a step of exposing at least a portion of the coating film formed in step (1) to light.

[0869] Step (3): A step of developing the coating film exposed in step (2).

[0870] Step (4): a step of baking the coating film developed in step (3) in an inert atmosphere.

[0871] Furthermore, the photosensitive resin composition of the present invention can be used to form partition walls, and can be used preferably to form partition walls for partitioning an organic layer of an organic electroluminescent element, in particular.

[0872] That is, the partition walls are formed by the cured product of the present invention, and the photosensitive resin composition of the present invention itself serves as a material for the partition walls.

[0873] The method for forming the partition walls using the photosensitive resin composition described above is not particularly limited, and a conventionally known method can be employed.

[0874] As a method for forming a partition wall, for example, there can be mentioned a method including a coating step (step (1)) of coating a photosensitive resin composition on a substrate to form a photosensitive resin composition layer, and an exposure step (step (2)) of exposing the photosensitive resin composition layer. Specific examples of such a method for forming a bank include an inkjet method and a photolithography method.

[0875] In the inkjet method, a photosensitive resin composition having a viscosity adjusted by dilution with a solvent is used as ink, and ink droplets are ejected onto a substrate by an inkjet method according to a predetermined pattern of partition walls, thereby applying the photosensitive resin composition onto the substrate to form a pattern of uncured partition walls. Then, the pattern of the uncured partition walls is exposed to form cured partition walls on the substrate. The exposure of the pattern of the uncured partition walls is performed in the same manner as the exposure step in the following photolithography method, except that a mask is not used.

[0876] In the photolithography method, a photosensitive resin composition is applied to the entire surface of a region of a substrate where partitions are to be formed to form a photosensitive resin composition layer. The formed photosensitive resin composition layer is exposed according to a predetermined pattern of partitions, and then the exposed photosensitive resin composition layer is developed to form partitions on the substrate.

[0877] In the coating step of coating a photosensitive resin composition on a substrate in the photolithography method, a contact transfer coating device such as a roll coater, a reverse coater, or a rod coater, or a non-contact coating device such as a spin coater (spin coating device) or a curtain flow coater is used to coat the photosensitive resin composition on the substrate on which the partition walls are to be formed, and the solvent is removed by drying as needed to form a photosensitive resin composition layer.

[0878] Next, in the exposure step, the photosensitive resin composition is irradiated with active energy rays such as ultraviolet rays or excimer lasers using a negative mask, and the photosensitive resin composition layer is partially exposed according to the pattern of the bank. During exposure, a light source that emits ultraviolet rays, such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, or a carbon arc lamp, can be used. The exposure dose also varies depending on the composition of the photosensitive resin composition, and is preferably 10 to 400 mJ / cm 2 about.

[0879] Next, in the development step (step (3)), the photosensitive resin composition layer exposed according to the pattern of the partition wall is developed with a developer, thereby forming the partition wall. The development method is not particularly limited, and an immersion method, a spray method, etc. can be used. Specific examples of the developer include organic developers such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine, or aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. In addition, a defoamer or a surfactant can also be added to the developer.

[0880] Thereafter, the developed partition walls are post-baked to heat and cure them (step (4)). The post-baking is preferably performed at 150 to 250° C. for 15 to 60 minutes. In addition, the post-baking is usually performed in air. When there are electrodes formed on the substrate or layers other than the partition walls, the post-baking is preferably performed in an inert atmosphere such as a nitrogen atmosphere or in a vacuum to reduce oxidation damage caused to them at high temperatures.

[0881] The substrate used for forming the partition walls is not particularly limited, and can be appropriately selected according to the type of organic electroluminescent element to be manufactured using the substrate on which the partition walls are formed, for example.

[0882] As suitable materials for the substrate, glass or various resin materials can be cited. Specific examples of resin materials include: polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; polycarbonate; poly(meth)acrylic resins; polysulfone; polyimide. Among these substrate materials, glass and polyimide are preferred in terms of excellent heat resistance. In addition, depending on the type of organic electroluminescent element to be manufactured, a transparent electrode layer such as ITO or ZnO can also be pre-set on the surface of the substrate where the partition is to be formed.

[0883] The thickness of the partition wall of the present invention is usually 0.1 μm or more, preferably 0.5 μm or more, more preferably 1 μm or more, further preferably 1.5 μm or more, and usually 10 μm or less, preferably 8 μm or less, more preferably 4 μm or less, further preferably 3 μm or less, particularly preferably 2 μm or less.

[0884] When the film thickness of the partition wall is set to be equal to or greater than the above lower limit, the light shielding property tends to be improved. When the film thickness of the partition wall is set to be equal to or less than the above upper limit, the adhesion tends to be improved.

[0885] The film thickness of the partition wall can be measured by a height difference-surface roughness-fine shape measuring device, a scanning white interference microscope, an ellipsometer, a reflection spectroscopic film thickness meter, or an electron microscope.

[0886] [3] Image display device

[0887] The image display device of the present invention includes the partition wall of the present invention.

[0888] The image display device is not particularly limited as long as it is a device that displays images or videos, and examples thereof include a liquid crystal display device and an organic EL display device.

[0889] For example, the image display device of the present invention can be formed by the method described in "Organic EL Display" (Ohmsha, Ltd., published on August 20, 2004, written by Shizuo Tokito, Chibashi Andachi, and Eiyuki Murata). An organic electroluminescent element emitting white light can be combined with a color filter to display an image, or an organic electroluminescent element emitting different colors such as RGB can be combined to display an image.

[0890] Example

[0891] The present invention will be described in more detail below with reference to synthesis examples, examples and comparative examples. The present invention is not limited to the following examples unless it exceeds the gist of the present invention.

[0892] [Synthesis example]

[0893] The constituent components of the photosensitive resin composition used in the following Examples and Comparative Examples were synthesized by the following methods.

[0894] <Synthesis Example 1: Alkali-soluble resin-I>

[0895] 155 parts by mass of EPICLON HP7200HH (polyglycidyl ether of dicyclopentadiene-phenol polymer, weight average molecular weight of 1000, epoxy equivalent of 270) manufactured by DIC Corporation, 49 parts by mass of methacrylic acid, 0.1 parts by mass of p-methoxyphenol, 2.5 parts by mass of triphenylphosphine and 280 parts by mass of propylene glycol monomethyl ether acetate were added to a reaction vessel, and heated and stirred at 100°C until the acid value became 3.0 mgKOH / g or less. It took 9 hours for the acid value to reach the target value (the acid value was 2.9 mgKOH / g). Then, 77 g of tetrahydrophthalic anhydride was added, and the mixture was reacted at 120°C for 4 hours to obtain an alkali-soluble resin-I having an acid value of 100 mgKOH / g and a weight average molecular weight of 3500.

[0896] Alkali-soluble resin-I does not belong to the resin having a Cardo skeleton.

[0897] <Synthesis Example 2: Alkali-soluble resin-II>

[0898]

[0899] 230 parts by mass of the epoxy compound represented by the above structural formula (epoxy equivalent: 230), 72 parts by mass of acrylic acid, 300 parts by mass of methoxybutyl acetate, 5 parts by mass of triphenylphosphine, and 0.13 parts by mass of p-methoxyphenol were added to a flask equipped with a thermometer, a stirrer, and a condenser, and reacted at 90° C. for 15 hours while stirring until the acid value became 5 mgKOH / g or less.

[0900] Next, 82.4 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), 30.4 parts by mass of tetrahydrophthalic anhydride (THPA), and 120 parts by mass of methoxybutyl acetate were added, and the mixture was slowly heated to 105° C. while being stirred to allow the mixture to react, thereby obtaining an alkali-soluble resin-II having an acid value of 110 mgKOH / g and a weight average molecular weight (Mw) of 5200 in terms of polystyrene as measured by GPC.

[0901] Alkali-soluble resin-II has a Cardo skeleton and has a partial structure represented by the above formula (a1-0).

[0902] <Synthesis Example 3: Alkali-soluble resin-III>

[0903]

[0904] 50 g of the epoxy compound represented by the above structural formula (epoxy equivalent 264), 13.65 g of acrylic acid, 60.5 g of methoxybutyl acetate, 0.936 g of triphenylphosphine, and 0.032 g of p-methoxyphenol were added to a flask equipped with a thermometer, a stirrer, and a condenser, and reacted at 90° C. while stirring until the acid value became 5 mgKOH / g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.

[0905] 25 parts by mass of the epoxy acrylate solution, 0.74 parts by mass of trimethylolpropane (TMP), 3.95 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 2.7 parts by mass of tetrahydrophthalic anhydride (THPA) were added to a flask equipped with a thermometer, a stirrer, and a condenser, and the mixture was slowly heated to 105° C. while being stirred to allow the mixture to react.

[0906] After the resin solution became transparent, it was diluted with methoxybutyl acetate to prepare a solid content of 50 mass %, thereby obtaining an alkali-soluble resin-III having an acid value of 112 mgKOH / g and a polystyrene-equivalent weight average molecular weight (Mw) of 4100 as measured by GPC.

[0907] The alkali-soluble resin-III does not have a Cardo skeleton and does not have the partial structure represented by the above formula (a1-0).

[0908] <Synthesis Example 4: Photopolymerization Initiator-I>

[0909] (Diketone)

[0910] Ethyl carbazole (5g, 25.61mmol) and o-naphthoyl chloride (5.13g, 26.89mmol) were dissolved in 30ml of dichloromethane, cooled to 2°C in an ice-water bath and stirred, and AlCl3 (3.41g, 25.61mmol) was added. Furthermore, after stirring at room temperature for 3 hours, a 15ml dichloromethane solution of crotonyl chloride (2.81g, 26.89mmol) was added to the reaction solution, and AlCl3 (4.1g, 30.73mmol) was added, and then stirred for 1 hour and 30 minutes. The reaction solution was poured into 200ml of ice water, 200ml of dichloromethane was added, and the organic layer was separated. The recovered organic layer was dried with anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a diketone body as a white solid (10g).

[0911] (oxime)

[0912] The diketone (3.00 g, 7.19 mmol), NH2OH·HCl (1.09 g, 15.81 mmol) and sodium acetate (1.23 g, 15.08 mmol) were used as solvents and 30 ml of isopropanol was used, and the mixture was refluxed for 3 hours.

[0913] After the reaction was completed, the reaction solution was concentrated, 30 ml of ethyl acetate was added to the obtained residue, and the mixture was washed with 30 ml of saturated sodium bicarbonate aqueous solution and 30 ml of saturated saline solution, and then dried with anhydrous magnesium sulfate. After filtration, the organic layer was concentrated under reduced pressure to obtain 1.82 g of solid. The mixture was purified by column chromatography to obtain 2.22 g of oxime as a light yellow solid.

[0914] (oxime ester)

[0915] The oxime (2.22 g, 4.77 mmol) and acetyl chloride (1.34 g, 17.0 mmol) were added to 20 ml of dichloromethane and cooled to 2 ° C in an ice bath, triethylamine (1.77 g, 17.5 mmol) was added dropwise, and then reacted for 1 hour in this state. After confirming the disappearance of the raw materials by thin layer chromatography, water was added to stop the reaction. The reaction solution was washed twice with 5 ml of saturated sodium bicarbonate aqueous solution and twice with 5 ml of saturated saline, and then dried with anhydrous sodium sulfate. After filtration, the organic layer was concentrated under reduced pressure, and the obtained residue was purified by column chromatography (ethyl acetate / hexane=2 / 1) to obtain 0.79 g of photopolymerization initiator-I (oxime ester) as a light yellow solid.

[0916] The structure of the photopolymerization initiator-I is as follows.

[0917]

[0918] [Constituents of the photosensitive resin composition]

[0919] The constituent components of the photosensitive resin composition used in the following Examples and Comparative Examples are as follows.

[0920] <Coloring agent>

[0921] Organic black pigment, manufactured by BASF, Irgaphor (registered trademark) Black S0100 CF (equivalent to the above compound (2))

[0922] <Dispersant-I>

[0923] An acrylic AB block copolymer comprising an A block having a quaternary ammonium salt group and a tertiary amino group in a side chain and a B block having no quaternary ammonium salt group and no tertiary amino group.

[0924] Amine value: 70mgKOH / g

[0925] Acid value: 1mgKOH / g or less

[0926] The A block of the dispersant-I contains repeating units of the following formulae (1a) and (2a), and the B block contains repeating units of the following formulae (3a). The content ratios of the repeating units of the following formulae (1a), (2a), and (3a) in the total repeating units of the dispersant-I are 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively.

[0927]

[0928] <Solvent>

[0929] PGMEA: Propylene glycol monomethyl ether acetate

[0930] MB: 3-methoxy-1-butanol

[0931] <Alkali-soluble resin>

[0932] Alkali-soluble resin-I: the resin described in Synthesis Example 1

[0933] Alkali-soluble resin-II: the resin described in Synthesis Example 2

[0934] Alkali-soluble resin-III: the resin described in Synthesis Example 3

[0935] <Ethylenically unsaturated compounds>

[0936] DPEA-12: "KAYARAD DPEA-12" (multifunctional acrylate) manufactured by Nippon Kayaku Co., Ltd. Equivalent to the ethylenically unsaturated compound (c1).

[0937] ATM-4E: "NK ESTETR ATM-4E" (multifunctional acrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. Corresponds to the ethylenically unsaturated compound (c1).

[0938] A-9550: "A-9550" (polyfunctional acrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. It does not correspond to the ethylenically unsaturated compound (c1).

[0939] DPHA-40H: "KAYARAD DPHA-40H" (multifunctional acrylate) manufactured by Nippon Kayaku Co., Ltd. It does not correspond to the ethylenically unsaturated compound (c1).

[0940] TMP-A: "Light acrylate TMP-A" (multifunctional acrylate) manufactured by Kyoeisha Chemical Co., Ltd. It does not correspond to the ethylenically unsaturated compound (c1).

[0941] <Photopolymerization initiator>

[0942] Photopolymerization initiator-I: the photopolymerization initiator described in Synthesis Example 4

[0943] Photopolymerization initiator-II: Oxime ester compound having the following chemical structure

[0944]

[0945] <Surfactant>

[0946] BYK-330: BYK-Chemie's "BYK-330" (silicone-based surfactant)

[0947] [Preparation of Pigment Dispersion Liquid 1]

[0948] The mixed solution was obtained by mixing in the following manner in the mixed solution: in terms of mass ratio, the organic black pigment became 100 mass parts, the dispersant-I became 24.1 mass parts, the alkali-soluble resin-I became 50 mass parts, the PGMEA became 557 mass parts, and the MB became 139 mass parts. It should be noted that the mixing ratio of the solvent also includes the amount of the solvent derived from the dispersant and the alkali-soluble resin.

[0949] The mixed solution was dispersed for 3 hours at 25 to 45° C. using a paint shaker. Zirconia beads of 0.5 mm φ were used as beads, and 2.5 times the mass of the dispersion was added. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare a pigment dispersion 1.

[0950] [Examples 1 to 7, Comparative Examples 1 to 6]

[0951] <Preparation of photosensitive resin composition>

[0952] Using the pigment dispersion 1 prepared above, each component was added in such a manner that the ratio of the solid content of each component to the total solid content became the mixing ratio of Tables 1A and 1B, and further PGMEA and MB were added in such a manner that the content ratio of the total solid content became 17% by mass and the ratio in the solvent became 80 / 20% by mass of PGMEA / MB, and stirred to dissolve them, thereby preparing compositions 1 to 13 as photosensitive resin compositions.

[0953] Compositions 1 to 13 were evaluated by the following methods.

[0954] <Preparation of a substrate for taper angle evaluation and evaluation of dissolution time during development>

[0955] On an electrode substrate formed by sequentially depositing ITO with a film thickness of 8 nm, silver with a film thickness of 120 nm, and ITO with a film thickness of 10 nm on the entire surface of a glass substrate, a photosensitive resin composition was applied using a spin coater so that the film thickness after heat curing became 1.5 μm, and after drying under reduced pressure for 1 minute, it was dried at 100° C. for 120 seconds using a hot plate. A mask having a lattice-shaped opening was used, and an intensity of 500 mW / cm at 365 nm was used. 2 The exposure amount is 100mJ / cm 2 The obtained coating film is subjected to exposure treatment in a manner of

[0956] Next, a developer consisting of a 2.38 mass % TMAH (tetramethylammonium hydroxide) aqueous solution was used to perform shower development at a water pressure of 0.05 MPa at 24°C, and then development was stopped with pure water and washed with a water washing spray. At this time, the time for the coating film of the unexposed part to be dissolved and removed was set as the dissolution time, and the shower development time was set to twice the dissolution time. The dissolution time during development is shown in Tables 1A and 1B.

[0957] Thereafter, the substrate was cured by heating at 230° C. for 30 minutes in a vacuum-reduced oven to form lattice-shaped partition walls, thereby obtaining a substrate for taper angle evaluation.

[0958] The reason why the taper angle is made vertical by firing in an inert atmosphere such as a nitrogen atmosphere or in a vacuum is considered as follows.

[0959] Usually, after the start of calcination, the initiator becomes active and reacts with the unsaturated bonds to gradually crosslink. However, when calcining is performed in an oxygen-containing atmosphere such as air, there are also a lot of oxygen and other components that hinder the activity of free radicals. Therefore, the reaction proceeds while resisting the melt flow of the resin caused by heat.

[0960] However, when calcining is performed in an inert atmosphere or in a vacuum, the presence of oxygen or the like that would hinder the solidification of the film is extremely small, so it is believed that the solidification of the film proceeds before the melt flow of the film caused by heating occurs, compared with an oxygen-containing atmosphere such as air.

[0961] Therefore, even when the same photosensitive resin composition is fired under the same temperature and time conditions, it is found that the taper angle tends to be more vertical when fired in an inert atmosphere or in a vacuum. This is believed to be the cause of the technical problem of the present invention.

[0962] <Evaluation of the taper angle of the partition wall>

[0963] The obtained substrate for taper angle evaluation was cut in the thickness direction to prepare a sample for cross-sectional observation, and the cross-sectional shape was observed using a scanning electron microscope (SEM, manufactured by KEYENCE Corporation) to measure the taper angle of the partition walls.

[0964] That is, if the taper angle evaluation substrate is cut, Figure 1 As shown, the side of the partition wall 1 formed on the ITO film 2 of the glass substrate 3 presents a gentle taper. On the side of the partition wall 1, the intersection angle of the interface S between the partition wall 1 and the ITO film 2 and the tangent line T of the oblique side connected to the interface S is measured as the taper angle of the partition wall 1. H is the height of the partition wall 1, H = 1.5μm.

[0965] The measurement results of the taper angle are shown in Tables 1A and 1B.

[0966] In Tables 1A and 1B, “alkali-soluble resin / ethylenically unsaturated compound” is the mass ratio of (a) alkali-soluble resin to (c) ethylenically unsaturated compound in the photosensitive resin composition ((a) alkali-soluble resin / (c) ethylenically unsaturated compound).

[0967] The "double bond equivalent" is the weighted average of the values ​​obtained by dividing the contents (mass) of (a) the alkali-soluble resin and (c) the ethylenically unsaturated compound by the molar numbers of their respective ethylenically unsaturated bonds, that is, the total double bond equivalent of (a) the alkali-soluble resin and (c) the ethylenically unsaturated compound.

[0968] [Table 1A]

[0969]

[0970]

[0971] [Table 1B]

[0972]

[0973]

[0974] According to Comparative Examples 2 to 5 shown in Tables 1A and 1B, it is effective to increase the mass ratio of (a) the alkali-soluble resin to (c) the ethylenically unsaturated compound in order to reduce the taper angle, but there is a problem that the dissolution time becomes longer. The reason is that the molecular weight of the (a) alkali-soluble resin is greater than that of the (c) ethylenically unsaturated compound, and therefore it is difficult to dissolve in the developer.

[0975] Comparison of Examples 1 and 2 with Comparative Example 1 shows that even when the mass ratio of (a) alkali-soluble resin / (c) ethylenically unsaturated compound is large, by using an ethylenically unsaturated compound (c1) containing an alkylene oxide group, a cured product having a short dissolution time and a small cone angle can be formed.

[0976] When the mass ratio of (a) alkali-soluble resin / (c) ethylenically unsaturated compound is large, the content of (c) ethylenically unsaturated compound in the photosensitive resin composition is small and the influence thereof is small.

[0977] However, in Examples 1 and 2, the oxygen atom contained in the alkylene oxide of the ethylenically unsaturated compound (c1) is hydrophilic, and therefore it is considered that the affinity for the developer is increased, and the dissolution time is shortened. Furthermore, it is considered that the oxygen atom contained in the alkylene oxide forms a hydrogen bond with the hydroxyl group or carboxyl group of the alkali-soluble resin (a), and the ethylenically unsaturated compound (c1) and the alkali-soluble resin (a) form a complex, and even if the content of the ethylenically unsaturated compound (c) is small, there is an effect of shortening the dissolution time.

[0978] Although the present invention has been described in detail using specific embodiments, it will be apparent to one skilled in the art that various modifications can be made without departing from the spirit and scope of the present invention.

[0979] This application is based on Japanese patent application No. 2022-100020 filed on June 22, 2022, the entire contents of which are incorporated herein by reference.

[0980] Description of Reference Numerals

[0981] 1: Next door

[0982] 2: ITO film

[0983] 3: Glass substrate

[0984] T: Tangent line of the hypotenuse connected to the interface S

[0985] H: Height of the partition wall

[0986] S: Interface between partition wall and ITO film

Claims

1. A photosensitive resin composition, characterized in that Containing (a) an alkali-soluble resin, (b) a photopolymerization initiator and (c) an ethylenically unsaturated compound, The mass ratio of the (a) alkali-soluble resin to the (c) ethylenically unsaturated compound, i.e., (a) alkali-soluble resin / (c) ethylenically unsaturated compound, is 5 or more. The (c) ethylenically unsaturated compound includes an ethylenically unsaturated compound (c1) having an alkylene oxide group and having three or more ethylenically unsaturated groups.

2. A photosensitive resin composition, characterized in that: Containing (a) an alkali-soluble resin, (b) a photopolymerization initiator and (c) an ethylenically unsaturated compound, The total double bond equivalent of the (a) alkali-soluble resin and the (c) ethylenically unsaturated compound, which is a weighted average of the values ​​obtained by dividing the contents by mass of the (a) alkali-soluble resin and the (c) ethylenically unsaturated compound by the molar number of the respective ethylenically unsaturated bonds, is 350 g / mol or more, The (c) ethylenically unsaturated compound includes an ethylenically unsaturated compound (c1) having an alkylene oxide group and having three or more ethylenically unsaturated groups.

3. The photosensitive resin composition according to claim 2, wherein The total double bond equivalent of the (a) alkali-soluble resin and the (c) ethylenically unsaturated compound is 380 g / mol or more.

4. The photosensitive resin composition according to claim 3, wherein The total double bond equivalent of the (a) alkali-soluble resin and the (c) ethylenically unsaturated compound is 410 g / mol or more.

5. The photosensitive resin composition according to claim 1, wherein The mass ratio of the (a) alkali-soluble resin to the (c) ethylenically unsaturated compound, ie, (a) alkali-soluble resin / (c) ethylenically unsaturated compound, is 6 or more.

6. The photosensitive resin composition according to claim 5, wherein The mass ratio of the (a) alkali-soluble resin to the (c) ethylenically unsaturated compound, ie, (a) alkali-soluble resin / (c) ethylenically unsaturated compound, is 8 or more.

7. The photosensitive resin composition according to claim 1 or 2, wherein The content ratio of the ethylenically unsaturated compound (c1) in the (c) ethylenically unsaturated compound is 50% by mass or more.

8. The photosensitive resin composition according to claim 1 or 2, wherein The ethylenically unsaturated compound (c1) has an alkylene oxide group in a side chain.

9. The photosensitive resin composition according to claim 1 or 2, wherein The ethylenically unsaturated compound (c1) has three or more ethylenically unsaturated groups modified with an alkylene oxide.

10. The photosensitive resin composition according to claim 1 or 2, wherein The ethylenically unsaturated compound (c1) includes a compound (c1-1) represented by the following general formula (c1-1-1): X in formula (c1-1-1) is represented by the following general formula (c1-1-2); X is optionally the same or different; Y is methyl or represented by the following general formula (c1-1-4), R in formula (c1-1-2) 1 represents an alkylene group having 2 to 4 carbon atoms; a represents an integer of 1 to 9; when a is 2 or more, multiple R 1 Optionally the same or different; R 2 It is represented by the following general formula (c1-1-3); * represents a connecting bond, R in formula (c1-1-3) 3 represents a hydrogen atom or a methyl group; * represents a connecting bond, In formula (c1-1-4), m is 0 or 1; * represents a connecting bond; X is represented by the general formula (c1-1-2); and X are optionally the same or different.

11. The photosensitive resin composition according to claim 10, wherein In the above formula (c1-1-2), a represents an integer of 2 to 9.

12. The photosensitive resin composition according to claim 10, wherein Y in the formula (c1-1-1) is represented by the formula (c1-1-4), and m in the formula (c1-1-4) is 1.

13. The photosensitive resin composition according to claim 1 or 2, wherein The (a) alkali-soluble resin contains an alkali-soluble resin (a1) having a cardo skeleton.

14. The photosensitive resin composition according to claim 13, wherein The alkali-soluble resin (a1) has a partial structure represented by the following general formula (a1-0): The benzene ring in formula (a1-0) may be further substituted by any substituent; Q represents O, S, CO or a direct bond; and * represents a connecting bond.

15. The photosensitive resin composition according to claim 14, wherein The alkali-soluble resin (a1) has a partial structure represented by the following general formula (a1-1): The benzene ring in formula (a1-1) may be further substituted by any substituent; R 9 Each independently represents a hydrogen atom or a methyl group; Q represents O, S, CO or a direct bond; n represents an integer of 0 to 4; a plurality of Qs may be the same or different; and * represents a connecting bond. 16 . The photosensitive resin composition according to claim 1 , further comprising (d) a colorant.

17. The photosensitive resin composition according to claim 16, wherein The (d) colorant contains an organic black pigment.

18. The photosensitive resin composition according to claim 17, wherein The organic black pigment comprises at least one selected from the group consisting of a compound represented by the following general formula (d1), a geometric isomer of the compound, a salt of the compound, and a salt of a geometric isomer of the compound, In formula (d1), R 11 and R 16 Each independently represents a hydrogen atom, CH3, CF3, a fluorine atom or a chlorine atom; R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 and R 20 Each independently represents a hydrogen atom, a halogen atom, R 21 、COOH、COOR 21 、COO - ,CONH2,CONHR 21 ,CONR 21 R 22 、CN、OH、OR 21 、COCR 21 、OOCNH2、OOCNHR 21 、OOCNR 21 R 22 、NO2、NH2、NHR 21 NR 21 R 22 、NHCOR 22 NR 21 COR 22 、N=CH2、N=CHR 21 、N=CR 21 R 22 , SH, SR 21 , SOR 21 、SO2R 21 、SO3R 21 、SO3H、SO3 - 、SO2NH2、SO2NHR 21 or SO2NR 21 R 22 ; Choose from R 12 With R 13 , R 13 With R 14 , R 14 With R 15 , R 17 With R 18 , R 18 With R 19 , and R 19 With R 20 At least one of the groups consisting of the above may be directly bonded to each other, or may be bonded to each other via an oxygen atom, a sulfur atom, NH or NR 21 Bridge and bond to each other; R 21 and R 22 Each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.

19. A cured product obtained by curing the photosensitive resin composition according to claim 1 or 2. 20 . A partition wall formed from the cured product according to claim 19 . An image display device comprising the partition wall according to claim 20.

22. A method for forming a solidified product, characterized in that: At least the following steps (1) to (4) are performed using the following photosensitive resin composition, wherein the photosensitive resin composition contains (a) an alkali-soluble resin, (b) a photopolymerization initiator, and (c) an ethylenically unsaturated compound, and the (c) ethylenically unsaturated compound contains: an ethylenically unsaturated compound (c1′) having an alkylene oxide group; Step (1): forming a coating film of the photosensitive resin composition on a substrate, Step (2): a step of exposing at least a portion of the coating film formed in step (1) to light. Step (3): a step of developing the coating film exposed in step (2). Step (4): A step of baking the coating film developed in step (3) in an inert atmosphere.

23. The method for forming a cured product according to claim 22, wherein: The step (4) is a step of baking the coating film developed in the step (3) under an inert atmosphere or in a vacuum.

24. The method for forming a cured product according to claim 22, wherein: The ethylenically unsaturated compound (c1′) has three or more ethylenically unsaturated groups.

25. The method for forming a cured product according to claim 22, wherein: The mass ratio of the (a) alkali-soluble resin to the (c) ethylenically unsaturated compound in the photosensitive resin composition, that is, (a) alkali-soluble resin / (c) ethylenically unsaturated compound, is 5 or more.

26. The method for forming a cured product according to claim 22, wherein: The ethylenically unsaturated compound (c1′) has an alkylene oxide group in a side chain.

27. The method for forming a cured product according to claim 22, wherein: The ethylenically unsaturated compound (c1′) has three or more ethylenically unsaturated groups modified with an alkylene oxide.

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