Alkali-soluble resin containing polymerizable unsaturated group, photosensitive resin composition containing the same as essential component, and cured product thereof

Abstract

To provide a photosensitive resin composition that can improve heat resistance, and a cured product thereof.SOLUTION: The invention relates to an alkali-soluble resin which is represented by the general formula (1) in the figure and which comprises a carboxyl group and a polymerizable unsaturated group in each molecule.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polymerizable unsaturated group-containing alkali-soluble resin, a photosensitive resin composition containing the same as an essential component, and a cured product thereof.

Background Art

[0002] With the recent high performance and high definition of electronic devices, display members, etc., miniaturization and high density are required for the electronic components used therein. And, in the processability of the insulating materials used for them, miniaturization and optimization of the cross-sectional shape of the processed pattern have come to be required. As an effective means of fine processing of insulating materials, a method of patterning by exposure and development is known, and a photosensitive resin composition has been used therein, but many characteristics such as high sensitivity, adhesion to a substrate, reliability, heat resistance, and chemical resistance have come to be required.

[0003] Insulating materials made of conventional photosensitive resin compositions utilize a photocuring reaction by the reaction of an alkali-soluble resin having photoreactivity and a photoinitiator, and i-line (365 nm), which is one of the line spectra of a mercury lamp, is mainly used as the exposure light wavelength for photocuring. However, this i-line is absorbed by the photosensitive resin itself or a colorant, resulting in a decrease in the degree of photocuring. Moreover, if it is a thick film, the absorption amount increases. Therefore, a difference occurs in the crosslink density in the film thickness direction in the exposed portion. As a result, even if the surface of the coating film is sufficiently photocured, it is difficult to photocure the bottom surface of the coating film, so it is extremely difficult to create a difference in crosslink density between the exposed portion and the unexposed portion. Thereby, it is difficult to obtain an insulating material made of a photosensitive resin composition that can be developed with high resolution having desired pattern dimension stability, development margin, pattern adhesion, pattern edge shape, and cross-sectional shape.

[0004] Generally, for photosensitive resin compositions used in such applications, those containing a polyfunctional photocurable monomer having a polymerizable unsaturated bond, an alkali-soluble binder resin, a photoinitiator, etc. are used, and photosensitive resin compositions disclosed for application as materials for color filters can be applied. For example, Patent Document 1 and Patent Document 2 disclose a copolymer of (meth)acrylic acid or (meth)acrylic acid ester having a carboxy group as a binder resin, maleic anhydride, and other polymerizable monomers.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, according to the studies of the present inventors, the copolymers disclosed in Patent Document 1 and Patent Document 2 have problems such as poor heat resistance and large deformation of the cross-sectional shape of the pattern after the heat curing step after exposure and development.

[0007] For photosensitive resin compositions used in various resists for color filters and resists for insulating films of semiconductor devices, etc., it is desired that the cross-sectional shape of the pattern has little deformation after the heat curing step after exposure and development, that is, it has high heat resistance.

[0008] An object of the present invention is to provide a photosensitive resin composition and a cured product thereof that can improve heat resistance. Another object of the present invention is to provide a technique effective especially when the required characteristics for the heat resistance of the cured product are severe.

Means for Solving the Problems

[0009] As a result of intensive studies to solve the above problems, the present inventors have found that a resin in which an aromatic compound having a hydroxy group (such as a compound having a phenolic hydroxyl group) is bonded with a divalent aromatic ring-containing group (a resin analogous to a so-called phenol aralkyl resin), to which a carboxy group-containing (meth)acrylate is reacted, and a polyhydric alcohol compound having a polymerizable unsaturated group obtained by reacting a dicarboxylic acid, a tricarboxylic acid or an acid anhydride thereof, is used in a photosensitive resin composition, which is suitable for forming a cured product having excellent heat resistance and the like.

[0010] [1] An alkali-soluble resin having a carboxy group and a polymerizable unsaturated group in one molecule, represented by the following general formula (1).

Chemical formula

Chemical formula

Chemical formula

[0011] [2]Regarding the hydrocarbon group and substituent Z that V1 can take, when the number of moles of the hydrocarbon group is Mc1 and the number of moles of the substituent Z is Mz1, the value of Mc1 / Mz1 is 0.05 to 2.0. The alkali-soluble resin according to [1].[[]END]]

[0012] [3]An alkali-soluble resin represented by the following general formula (4) and having a carboxy group and a polymerizable unsaturated group in one molecule. [Chemical formula] (In formula (4), X3 is independently a tetravalent substituent represented by the following general formula (5) derived from a biphenol compound, and X4 is independently a tetravalent substituent represented by the following general formula (6) derived from a bisphenol compound. Y2 is independently a divalent substituent represented by the following general formula (7). In the following general formula (5), (6), and the following general formula (7), a part of the hydrogen atoms may be substituted with a linear or branched hydrocarbon group having 1 to 20 carbon atoms. In the following general formula (6), V2 is independently a linear or branched hydrocarbon group having 1 to 5 carbon atoms or a substituent Z represented by formula (2). However, at least two of V2 are substituent Z. m is a number from 1 to 20, and n is a number from 0 to 20. Q2 is independently a hydrogen atom or a linear or branched hydrocarbon group having 1 to 20 carbon atoms. Also, the structural unit containing X3 and the structural unit containing X4 may be arranged randomly or in a block form, and m and n indicate the introduction numbers of the respective structural units.) [Chemical formula] (In formula (5), * indicates the bonding site with the oxygen atom in formula (4), and ** indicates the bonding site with Y2 or Q2.) [Chemical formula] (In formula (6), M is a divalent substituent selected from the group consisting of linear, branched, and cyclic hydrocarbon groups having 1 to 10 carbon atoms which may be substituted with a halogen atom, aromatic hydrocarbon groups, -O-, -C(=O)-, -S-, and -SO2-. In formula (6), * indicates the bonding site with the oxygen atom in formula (4), and ** indicates the bonding site with Y2 or Q2.)

Chemical formula

Chemical formula

Chemical formula

[0013] [4]Regarding the hydrocarbon group and the substituent Z that V2 can take, when the number of moles of the hydrocarbon group is Mc2 and the number of moles of the substituent Z is Mz2, the value of Mc2 / Mz2 is 0.05 to 2.0 The alkali-soluble resin according to [3].

[0014] [5](i) The alkali-soluble resin according to any one of [1] to [4], (ii) A photopolymerizable compound having at least one polymerizable unsaturated group, and (iii) A photopolymerization initiator, A photosensitive resin composition containing these.

[0015] [6] The content of the (iii) photoinitiator is 0.1 part by mass to 10.0 parts by mass with respect to a total of 100 parts by mass of the (i) alkali-soluble resin and the (ii) photopolymerizable compound. The photosensitive resin composition according to [5].

[0016] [7] The photosensitive resin composition according to [5] or [6], containing (iv) an epoxy compound.

[0017] [8] The content of the (iv) epoxy compound is 10 parts by mass to 40 parts by mass with respect to a total of 100 parts by mass of the (i) alkali-soluble resin and the (ii) photopolymerizable compound. The photosensitive resin composition according to [7].

[0018] [9] The photosensitive resin composition according to any one of [5] to [8], containing (v) a dispersion medium.

[0019]

[10] A cured product obtained by curing the photosensitive resin composition according to any one of [5] to [9]. [Advantages of the Invention]

[0020] According to the present invention, it is possible to provide a photosensitive resin composition capable of improving heat resistance and a cured product thereof. In particular, it is possible to provide an effective technique when the required characteristics for the heat resistance of the cured product are severe. [Embodiments for Carrying Out the Invention]

[0021] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. In the present invention, when the content of each component has a first decimal place of 0, the notation after the decimal point may be omitted.

[0022] In addition, the numerical range represented by "~" in this specification means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value.

[0023] The photosensitive resin composition according to this embodiment contains, as essential components, (i) an alkali-soluble resin represented by General Formula (1) or General Formula (4), (ii) a photopolymerizable compound having at least one polymerizable unsaturated group, and (iii) a photopolymerization initiator. Hereinafter, each component will be described.

[0024] [Alkali-soluble resin] The alkali-soluble resin represented by General Formula (1) or General Formula (4) will be described below.

[0025] The alkali-soluble resin represented by the following General Formula (1) or General Formula (4) has a carboxy group and a polymerizable unsaturated group in one molecule. The above alkali-soluble resin is a resin in which an aromatic compound having a hydroxy group (such as a compound having a phenolic hydroxyl group) is bonded by a divalent aromatic ring-containing group (a resin analogous to a so-called phenol aralkyl resin), and an epoxy compound having two or more glycidyl ether groups obtained by reacting with a cyclic ether compound such as epichlorohydrin, and a carboxylic acid compound having an unsaturated group such as (meth)acrylic acid are reacted, and the resulting polyhydric alcohol compound having a polymerizable unsaturated group is reacted with dicarboxylic acids, tricarboxylic acids or their acid anhydrides to obtain it.

[0026] Note that the “(meth)acryloyl group” is a general term for an acryloyl group and a methacryloyl group, the “(meth)acrylic acid” is a general term for acrylic acid and methacrylic acid, the “(meth)acrylate” is a general term for acrylate and methacrylate, and all of them mean one or both of these.

[0027] [Chemical formula]

[0028] In formula (1), X1 and X2 each independently represent different tetravalent aromatic ring-containing groups, and Y1 independently represents a divalent aromatic ring-containing group. A part of the hydrogen atoms of X1, X2, and Y1 may be substituted with a linear or branched hydrocarbon group having 1 to 20 carbon atoms.

[0029] X1 and X2 preferably contain 2 to 4 aromatic rings, and more preferably contain 2 aromatic rings. When the number of aromatic rings is 2 or more, the heat resistance is likely to increase, and when the number of aromatic rings is 4 or less, the solubility in an alkaline developer is likely to increase.

[0030] Y1 preferably contains 2 to 4 aromatic rings, more preferably contains 2 aromatic rings, and further preferably contains a biphenyl structure. When the number of aromatic rings of Y1 is 2 or more, the heat resistance is likely to increase, and when the number of aromatic rings is 4 or less, the solubility in an alkaline developer is likely to increase.

[0031] V1 is independently a linear or branched hydrocarbon group having 1 to 5 carbon atoms or a substituent Z represented by the following general formula (2). However, at least two of V1 are the substituent Z. Q1 is independently a hydrogen atom or a linear or branched hydrocarbon group having 1 to 20 carbon atoms.

[0032] k is a number from 1 to 20, and l is a number from 0 to 20. The structural units containing X1 and the structural units containing X2 may be arranged randomly or in blocks, and k and l represent the number of introductions of the respective structural units. When producing the resin of general formula (1), it is usually obtained as a mixture of molecules with different numerical values of k and l, but the introduction ratio k / (k + l) of each structural unit is preferably 0.05 to 0.95. When k / (k + l) is within the above range, it is possible to easily increase the solubility in a solvent and an alkaline developer while maintaining the heat resistance. Also, the structural units containing X1 and the structural units containing X2 are preferably introduced in blocks. When the structural units containing X1 and the structural units containing X2 are introduced in blocks, it is possible to easily increase the solubility in a solvent and an alkaline developer while maintaining the heat resistance.

[0033] [Chem.]

[0034] In formula (2), R1 represents a hydrogen atom or a methyl group. J represents a substituent represented by the following general formula (3). * represents the bonding site with the oxygen atom in formula (1).

[0035] [Chem.]

[0036] In formula (3), L represents a divalent or trivalent residue derived from a dicarboxylic acid, a tricarboxylic acid or their acid anhydrides, and p is a number of 1 or 2. * represents the bonding site with the oxygen atom in formula (2).

[0037] Also, regarding the hydrocarbon group and the substituent Z that V1 can take, when a part of V1 is a linear or branched hydrocarbon group having 1 to 5 carbon atoms, if the number of moles of the hydrocarbon group of V1 is Mc1 and the number of moles of the substituent Z is Mz1, the value of Mc1 / Mz1 is preferably 0.01 to 2.0, more preferably 0.05 to 2.0, and even more preferably 0.05 to 1.0. When Mc1 / Mz1 is within the above range, the curing shrinkage after exposure can be suppressed while maintaining the curability.

[0038] Generally, when heat resistance is improved, the solubility in solvents and alkaline developers tends to decrease. When the solubility in solvents decreases, not only the solvents to be used are limited, but also the compounding ratios in the photosensitive resin composition are restricted. When the solubility in alkaline developers decreases, residues are generated after development, or a desired pattern shape cannot be formed. However, an alkali-soluble resin having a structure represented by the general formula (1) has high heat resistance and is likely to have improved solubility in solvents and alkaline developers. The reason for this is not necessarily clear, but it is considered as follows. The alkali-soluble resin of the general formula (1) contains aromatic ring-containing groups such as X1 and Y1 in a straight chain, thereby increasing the glass transition temperature of the alkali-soluble resin and enhancing the heat resistance. Further, since the alkali-soluble resin of the general formula (1) contains X2, which is an aromatic group-containing group different from X1, the crystallinity is moderately decreased, and thus the solubility in solvents and alkaline developers is improved.

[0039] [Chemical formula]

[0040] In formula (4), X3 is independently a tetravalent substituent represented by the following general formula (5) derived from a biphenol compound, and X4 is a tetravalent substituent represented by the following general formula (6) derived from a bisphenol compound. Y2 is independently a divalent substituent represented by the following general formula (7). In the following general formulas (5), (6) and the following general formula (7), a part of the hydrogen atoms may be substituted with a linear or branched hydrocarbon group having 1 to 20 carbon atoms. In the following general formula (6), V2 is independently a linear or branched hydrocarbon group having 1 to 5 carbon atoms or a substituent Z represented by the general formula (2). However, at least two of V2 are the substituent Z.

[0041] m is a number from 1 to 20, and n is a number from 0 to 20. Q2 is independently a hydrogen atom or a linear or branched hydrocarbon group having 1 to 20 carbon atoms. Further, the structural unit containing X3 and the structural unit containing X4 may be arranged randomly or in a block form, and m and n indicate the number of introduced units of each structural unit. The introduction ratio m / (m + n) of each structural unit is preferably from 0.50 to 0.95, more preferably from 0.70 to 0.95. When m / (m + n) is within the above range, it is possible to easily increase the solubility in a solvent and an alkali developer while maintaining heat resistance. Further, the structural unit containing X3 and the structural unit containing X4 are preferably introduced in a block form. When the structural unit containing X3 and the structural unit containing X4 are introduced in a block form, it is possible to easily increase the solubility in a solvent and an alkali developer while maintaining heat resistance.

[0042] In the above general formula (4), when X3 and X4 are bonded to two Y2s, the two bonds may be only on one of the benzene rings as represented by the following general formula (5) or general formula (6), or there may be one bond on each of the two benzene rings and they may be bonded to Y2. In this embodiment, the form in which the two bonds are bonded to one benzene ring is typically described.

[0043]

Chemical formula

[0044] In formula (5), * indicates the bonding site with the oxygen atom in formula (4), and ** indicates the bonding site with Y2 or Q2.

[0045]

Chemical formula

[0046] In formula (6), M represents a divalent substituent represented by a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, an aromatic hydrocarbon group, -O-, -C(=O)-, -S-, -SO2-. Among these, M is preferably a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrocarbon group having 1 to 3 carbon atoms, and even more preferably a hydrocarbon group having 1 carbon atom. When M is such a substituent, it is possible to easily enhance the solubility in a solvent and an alkaline developer without impairing the heat resistance. In formula (6), * indicates the bonding site with the oxygen atom in formula (4), and ** indicates the bonding site with Y2 or Q2.

[0047]

Chemical formula

[0048] In formula (7), * indicates the bonding site with X3 or X4 in formula (4).

[0049]

Chemical formula

[0050]

Chemical formula

[0051] In formula (3), L represents a divalent or trivalent residue derived from a dicarboxylic acid, a tricarboxylic acid or their acid anhydrides, and p is a number of 1 or 2. * indicates the bonding site with the oxygen atom in formula (2).

[0052] Although the reason why an alkali-soluble resin having a structure such as general formula (4) can have high heat resistance and improved solubility in solvents and alkali developers is not necessarily clear, it is considered as follows. Since the main chain of the alkali-soluble resin of general formula (4) contains a rigid biphenyl skeleton such as general formula (7), the glass transition temperature of the alkali-soluble resin can be increased, and the heat resistance can be enhanced. Further, since the alkali-soluble resin of general formula (4) contains not only the structure of general formula (5) but also the structure of general formula (6), the crystallinity can be moderately decreased while maintaining the heat resistance. Thereby, the solubility of the alkali-soluble resin of general formula (4) in solvents and alkali developers is improved.

[0053] Regarding the hydrocarbon group and the substituent Z that V2 can take, when the number of moles of the hydrocarbon group is Mc2 and the number of moles of the substituent Z is Mz2, the value of Mc2 / Mz2 is preferably from 0.01 to 2.0, more preferably from 0.05 to 2.0, and even more preferably from 0.05 to 1.0. When Mc2 / Mz2 is within the above range, it becomes easier to suppress the curing shrinkage after exposure while maintaining the curability.

[0054] The alkali-soluble resin represented by general formula (1) or general formula (4) preferably has an acid value of 35 mgKOH / g to 140 mgKOH / g, more preferably 50 mgKOH / g to 130 mgKOH / g. When the acid value is 35 mgKOH / g or more, the solubility in the alkali developer is likely to increase, and the residue is likely to be suppressed. When the acid value is 140 mgKOH / g or less, the pattern adhesion is likely to increase. The acid value was determined by dissolving the resin solution in tetrahydrofuran and titrating it with a 1 / 10N - KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by HIRANUMA), and taking the amount of KOH required per 1 g of the solid content as the acid value.

[0055] The weight average molecular weight (Mw) in terms of polystyrene, measured by gel permeation chromatography (GPC) (HLC-8220GPC, manufactured by Tosoh Corporation) of the alkali-soluble resin represented by the general formula (1) or the general formula (4), is preferably from 3,000 to 20,000, more preferably from 3,500 to 15,000. When the weight average molecular weight (Mw) is 3,000 or more, the pattern adhesion tends to increase. Further, when the weight average molecular weight (Mw) is 20,000 or less, the solubility in an alkali developer tends to increase, and it becomes easy to suppress residues. The molecular weight was measured by gel permeation chromatography (GPC) ("HLC-8420GPC", manufactured by Tosoh Corporation, column: TSKgel Super H2000 (2 pieces) + TSKgel Super H3000 (1 piece) + TSKgel Super H4000 (1 piece) + TSKgel Super H5000 (1 piece) (all manufactured by Tosoh Corporation), solvent: tetrahydrofuran, temperature: 40 ° C, speed: 0.6 ml / min), and the value obtained as a conversion value in terms of standard polystyrene ("PS-oligomer kit", manufactured by Tosoh Corporation) was defined as the weight average molecular weight (Mw).

[0056] Since the alkali-soluble resin represented by the general formula (1) or the general formula (4) according to the present embodiment has both a polymerizable unsaturated group and a carboxy group, the photosensitive resin composition containing the alkali-soluble resin has excellent photocurability, good developability, and patterning characteristics.

[0057] [Method for producing a photosensitive resin composition] (Method for producing an alkali-soluble resin) First, the method for producing the alkali-soluble resin represented by the general formula (1) or the general formula (4) will be described in detail.

[0058] The alkali-soluble resin represented by the general formula (1) is an alkali-soluble resin having a polymerizable unsaturated bond and a carboxy group in one molecule, wherein X1 and X2 are tetravalent aromatic ring-containing groups, Y1 is a divalent aromatic ring-containing group, Q1 is a hydrogen atom, and at least two of V1 are a substituent Z represented by the general formula (2) (hereinafter referred to as a biphenol aralkyl-based alkali-soluble resin).

[0059] The alkali-soluble resin represented by the general formula (4) is an alkali-soluble resin having a polymerizable unsaturated bond and a carboxy group in one molecule, wherein X3 is a tetravalent substituent represented by the general formula (5) derived from a biphenol compound, X4 is a tetravalent substituent represented by the general formula (6) derived from a bisphenol compound. Y2 is a divalent substituent represented by the general formula (7), Q2 is a hydrogen atom, and at least two of V2 are a substituent Z represented by the general formula (2) (hereinafter referred to as a biphenol aralkyl-based alkali-soluble resin).

[0060] The alkali-soluble resin represented by the general formula (1) or the general formula (4) is obtained by reacting an epoxy compound obtained by reacting an aromatic compound having a hydroxy group with a resin in a form bonded by an aromatic ring-containing group with a cyclic ether compound such as epichlorohydrin, with a carboxylic acid compound containing an unsaturated group such as (meth)acrylic acid, and then reacting the obtained polyhydric alcohol compound having a polymerizable unsaturated group with dicarboxylic acids, tricarboxylic acids or acid anhydrides thereof.

[0061] Specifically, the alkali-soluble resin represented by the general formula (1) or the general formula (4) is obtained by reacting a polyhydric alcohol compound containing a polymerizable unsaturated group, which is obtained by reacting an epoxy compound having a biphenyl skeleton represented by the following general formula (9), which has two or more glycidyl ether groups in which the hydrogen atom of the phenolic hydroxyl group of the biphenyl aralkyl resin represented by the following general formula (8) is substituted with a glycidyl group or a linear or branched hydrocarbon group having 1 to 5 carbon atoms, with (meth)acrylic acid, with a polyvalent carboxylic acid or its anhydride. The production method of the epoxy compound having this biphenyl skeleton can refer to, for example, the production method described in International Publication No. 2011 / 74517. The compound represented by the following general formula (8) is usually a mixture of molecules with different numerical values о and q in the formula (8), and when producing the resin represented by the following general formula (9), it is usually obtained as a mixture of molecules with different numerical values r and s in the formula (9).

[0062]

Chemical formula

[0063] In the formula (8), M2 is a divalent substituent represented by a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group, -O-, -C(=O)-, -S-, -SO2-, which may be substituted with a halogen atom. о represents a number from 1 to 20, and q represents a number from 0 to 20.

[0064]

Chemical formula

[0065] In formula (9), M2 is a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, an aromatic hydrocarbon group, a divalent substituent represented by ―O―, -C(=O)-, ―S―, ―SO2―. r represents a number from 1 to 20, and s represents a number from 0 to 20. W independently represents a linear or branched hydrocarbon group having 1 to 5 carbon atoms, or a glycidyl group G. The hydrocarbon group that W can take is preferably a methyl group or an ethyl group. It is preferable that at least two of W are glycidyl groups G, and all of W may be glycidyl groups G. Further, regarding the hydrocarbon group or glycidyl group G that W can take, when the number of moles of the hydrocarbon group is Mc3 and the number of moles of the glycidyl group G is Mg3, the value of Mc3 / Mg3 is preferably 0.05 to 2.0. The epoxy equivalent of the epoxy compound represented by general formula (9) is preferably 150 g / eq to 300 g / eq.

[0066] The polymerization method of the biphenol aralkyl resin can refer to the general production methods of phenolic resins and phenol aralkyl resins. However, as a production method for deriving a compound of general formula (9) having a linear or branched hydrocarbon group with 1 to 5 carbon atoms as W, a known method of reacting an epoxy moiety, a phenol moiety, and alcohols under an alkali catalyst such as sodium hydroxide can be used.

[0067] Specifically, the epoxy compound represented by general formula (9) can be obtained by reacting the biphenol aralkyl resin represented by general formula (8) with epichlorohydrin. In the above reaction, the biphenol aralkyl resin represented by general formula (8) may be reacted with alcohols in addition to epichlorohydrin. This will be explained from the production method of the polyhydroxy resin used as the raw material of the epoxy resin.

[0068] In the first step, a polyhydroxy resin can be obtained by condensing biphenols and a crosslinking agent in the absence or presence of an acidic catalyst.

[0069] Examples of the above-mentioned biphenols include 4,4'-dihydroxybiphenyl and the like.

[0070] Examples of the above-mentioned crosslinking agents include 4,4'-bis(hydroxymethyl)biphenyl, 4,4'-bis(chloromethyl)biphenyl, 4,4'-bis(bromomethyl)biphenyl, 4,4'-bis(methoxymethyl)biphenyl, 4,4'-bis(ethoxymethyl)biphenyl and the like. Among the above-mentioned crosslinking agents, 4,4'-bis(chloromethyl)biphenyl, 4,4'-bis(hydroxymethyl)biphenyl, and 4,4'-bis(methoxymethyl)biphenyl are preferred.

[0071] As a second step, a polyhydric hydroxy resin can be obtained by further reacting the above-mentioned first-step reaction product with biphenols.

[0072] Examples of the above-mentioned biphenols include 4,4'-dihydroxydiphenylmethane, 2,2'-dihydroxydiphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenyl ether, bis(4-hydroxyphenyl)sulfone and the like. Among the biphenols, 4,4'-dihydroxydiphenylmethane, 2,2'-dihydroxydiphenylmethane, and 2,2-bis(4-hydroxyphenyl)propane are preferred. The ratio of the biphenols in the general formula (8) can be changed within an arbitrary range, but the molar ratio represented by o / (o + q) in o and q in the general formula (8) is preferably 0.50 to 0.95, more preferably 0.70 to 0.95. When it is less than 0.5, the heat resistance decreases, and when it is greater than 0.95, the crystallinity increases and the solvent solubility decreases.

[0073] The above-mentioned acidic catalyst can be appropriately selected from well-known inorganic acids and organic acids. Examples of the above-mentioned acidic catalyst include inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as formic acid, oxalic acid, and p-toluenesulfonic acid, Lewis acids such as aluminum chloride, and solid acids such as activated clay and zeolite.

[0074] In general formula (9), the alkali-soluble resin having a linear or branched hydrocarbon group with 1 to 5 carbon atoms for W is obtained by alkoxylating a part of the hydroxyl groups of the biphenol aralkyl resin represented by general formula (8), which is obtained by reacting the above-mentioned biphenols with the above-mentioned crosslinking agent. For example, it can be obtained by reacting the above-mentioned polyhydroxy resin with alcohols under an acidic catalyst. Examples of the above-mentioned alcohols include methanol, ethanol, propanol, butanol, pentanol and the like. Further, the above-mentioned acidic catalyst can be the above-mentioned catalyst.

[0075] Alternatively, when condensing biphenols and a crosslinking agent in the presence of an acidic catalyst, a production method may be used in which a biphenyl compound having an alkoxy group and a phenolic hydroxyl group is used in combination as a part of the biphenols.

[0076] As a third step, a hydrogen atom of the phenolic hydroxyl group of the biphenol aralkyl resin represented by general formula (8) is substituted with a glycidyl group or a linear or branched hydrocarbon group with 1 to 5 carbon atoms to obtain an epoxy compound having a biphenyl skeleton represented by general formula (9) and having two or more glycidyl ether groups. The production method can be carried out in the same manner as a normal epoxidation reaction of a hydroxy group. For example, there is a method in which a biphenol aralkyl resin is dissolved in excess epichlorohydrin and then reacted at 20°C to 150°C for 1 hour to 10 hours in the presence of an alkali metal hydroxide such as sodium hydroxide.

[0077] Next, a known method can be used for the reaction of such an epoxy compound with (meth)acrylic acid. For example, 1 mole of (meth)acrylic acid is used per 1 mole of epoxy groups. In order to react (meth)acrylic acid with all the epoxy groups, it is preferable to add (meth)acrylic acid in a slight excess over the equimolar amount of epoxy groups and carboxyl groups. It is also possible to use a resin obtained by reacting a part of (meth)acrylic acid by replacing it with a carboxyl group-containing (meth)acrylate. The carboxyl group-containing (meth)acrylate is a compound having one carboxyl group and one or more (meth)acrylate groups in the molecule. Examples of the carboxyl group-containing (meth)acrylate include 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxyethyl succinate, 2-acryloyloxyhexanoic acid, and 2-methacryloyloxyhexanoic acid, etc.

[0078] The reaction product obtained in the above reaction is an epoxy (meth)acrylate represented by the following general formula (10).

[0079]

Chemical formula

[0080] In formula (10), M2 is a divalent substituent represented by a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, an aromatic hydrocarbon group, —O—, —C(═O)—, —S—, or —SO2—. Among these, M2 is preferably a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrocarbon group having 1 to 2 carbon atoms, and even more preferably a hydrocarbon group having 1 carbon atom. When M2 is such a substituent, it is possible to easily enhance the solubility in a solvent and an alkali developer without impairing the heat resistance. t represents a number from 1 to 20, and u represents a number from 0 to 20. The introduction ratio t / (t + u) of each structural unit is preferably from 0.50 to 0.95, and more preferably from 0.70 to 0.95. When t / (t + u) is within the above range, it is possible to easily enhance the solubility in a solvent and an alkali developer while maintaining the heat resistance. Further, the repeating constitutional unit not containing M2 and the repeating constitutional unit containing M2 are preferably introduced in a block form. When the repeating constitutional unit not containing M2 and the repeating constitutional unit containing M2 are introduced in a block form, it is possible to easily enhance the solubility in a solvent and an alkali developer while maintaining the heat resistance. W1 is independently a linear or branched hydrocarbon group having 1 to 5 carbon atoms or a substituent having a polymerizable unsaturated group in the molecule represented by the following general formula (11). However, at least two of W1 are substituents represented by the following general formula (11), and all of W1 may be substituents represented by the following general formula (11). When the number of moles of the hydrocarbon group that W1 can take is Mc4 and the number of moles of the glycidyl group G is Mg4, the value of Mc4 / Mg4 is preferably from 0.05 to 2.0. The hydrocarbon group that W1 can take is preferably a methyl group or an ethyl group.

[0081] [Chemical formula]

[0082] In formula (11), R2 represents a hydrogen atom or a methyl group. * indicates the bonding site with the oxygen atom in formula (4).

[0083] The solvent, catalyst, and other reaction conditions used at this time are not particularly limited. For example, the solvent preferably has no hydroxyl group and has a boiling point higher than the reaction temperature. Examples of such solvents include cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate; high-boiling ether-based or ester-based solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; and ketone-based solvents such as cyclohexanone and diisobutyl ketone. Examples of the catalyst include known catalysts such as ammonium salts including tetraethylammonium bromide and triethylbenzylammonium chloride; and phosphines including triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine.

[0084] By reacting the hydroxyl group of the compound represented by the general formula (10) with a dicarboxylic acid, tricarboxylic acid, or their acid anhydrides, an alkali-soluble resin represented by the general formula (1) or general formula (4) can be obtained.

[0085] Examples of the above dicarboxylic acid, tricarboxylic acid, or their acid anhydrides include saturated chain hydrocarbon dicarboxylic acids or tricarboxylic acids, saturated cyclic hydrocarbon dicarboxylic acids or tricarboxylic acids, unsaturated dicarboxylic acids or tricarboxylic acids, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids, or their acid anhydrides. In addition, each hydrocarbon residue (structure excluding the carboxy group) of these acid anhydrides may be substituted with substituents such as alkyl groups, cycloalkyl groups, and aromatic groups. Among these dicarboxylic acids, tricarboxylic acids, or their acid anhydrides, compounds having cyclic substituents are preferred from the viewpoint of easily enhancing heat resistance.

[0086] Examples of acid monoanhydrides of saturated chain hydrocarbon dicarboxylic acids or tricarboxylic acids include acid monoanhydrides such as succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid.

[0087] Examples of acid monoanhydrides of saturated cyclic hydrocarbon dicarboxylic acids or tricarboxylic acids include acid monoanhydrides such as hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornanedicarboxylic acid, and hexahydrotrimellitic acid.

[0088] Examples of acid monoanhydrides of unsaturated dicarboxylic acids or tricarboxylic acids include acid monoanhydrides such as maleic acid, itaconic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, and chlorendic acid.

[0089] Examples of acid monoanhydrides of aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids include acid anhydrides such as phthalic acid and trimellitic acid.

[0090] Among the above acid monoanhydrides of dicarboxylic acids or tricarboxylic acids, those that are acid monoanhydrides of succinic acid, hexahydrophthalic acid, hexahydrotrimellitic acid, maleic acid, itaconic acid, tetrahydrophthalic acid, phthalic acid, and trimellitic acid are preferred, and those that are acid monoanhydrides of succinic acid, hexahydrotrimellitic acid, maleic acid, itaconic acid, tetrahydrophthalic acid, phthalic acid, and trimellitic acid are more preferred. Note that the above acid monoanhydrides of dicarboxylic acids or tricarboxylic acids may be used alone or in combination of two or more.

[0091] When reacting the hydroxyl group of the compound represented by the general formula (10) with a dicarboxylic acid, a tricarboxylic acid, or their acid anhydrides to synthesize an alkali-soluble resin represented by the general formula (1) or the general formula (4), the reaction temperature is preferably 20°C to 120°C, more preferably 40°C to 90°C. The molar ratio of the acid anhydride when synthesizing the compound represented by the general formula (1) or the general formula (4) can be arbitrarily changed for the purpose of adjusting the acid value of the alkali-soluble resin represented by the general formula (1) or the general formula (4).

[0092] (i) The content of the alkali-soluble resin represented by the general formula (1) or the general formula (4) according to this embodiment is preferably 30% by mass to 80% by mass in the solid content of the photosensitive resin composition (the solid content excluding the solvent (the solid content includes the photopolymerizable compound that becomes a solid content after curing)).

[0093] In this way, an alkali-soluble resin represented by the general formula (1) or the general formula (4) can be obtained.

[0094] (Method for producing a photosensitive resin composition) Next, the method for producing the photosensitive resin composition according to this embodiment will be described. The photosensitive resin composition according to this embodiment contains, in addition to the above-mentioned (i) alkali-soluble resin, (ii) a photopolymerizable compound having at least one polymerizable unsaturated group, and (iii) a photopolymerization initiator. Each component will be described below.

[0095] (ii) Examples of the photopolymerizable compound having at least one polymerizable unsaturated group as a component include photopolymerizable compounds having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate; ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerol (meth)acrylate, etc. When it is necessary to form a crosslinked structure between molecules of the alkali-soluble resin, it is preferable to use a photopolymerizable compound having two or more polymerizable unsaturated groups, and more preferably to use a photopolymerizable compound having three or more polymerizable unsaturated groups. These compounds may be used alone or in combination of two or more.

[0096] The blending ratio [(total mass of (i)) / (total mass of (ii))] of the above-mentioned component (ii) and the alkali-soluble resin ((i) component) (i) is preferably 20 / 80 to 90 / 10, and more preferably 40 / 60 to 80 / 20. Here, when the blending ratio of the alkali-soluble resin is sufficiently high, the cured product after the photocuring reaction becomes sufficiently hard. Also, since the acid value of the coating film becomes sufficiently high, it dissolves sufficiently in the alkali developer, and in the unexposed part, the pattern edge is less likely to rattle and is likely to become sharp. On the contrary, by not having too much blending ratio of the alkali-soluble resin, the ratio of the photoreactive functional groups in the resin can be made sufficiently high, and a crosslinked structure by the photocuring reaction can be sufficiently formed. Also, since the acid value in the resin component is not too high, it is easy to suppress the solubility in the alkali developer within a predetermined range, and in the exposed part, it is easy to form a pattern having a line width of a target thickness, and it is possible to make it less likely to cause pattern dropout.

[0097] (iii) Examples of the photoinitiator, which is a component, include acetophenones such as acetophenone, 2,2 - diethoxyacetophenone, p - dimethylacetophenone, p - dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p - tert - butylacetophenone; α - hydroxyalkylphenones such as 1 - hydroxycyclohexyl phenyl ketone, 2 - hydroxy - 2 - methyl - 1 - phenylpropanone; benzophenones such as benzophenone, 2 - chlorobenzophenone, p,p’ - bisdimethylaminobenzophenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; imidazole - based compounds such as 2 - (O - chlorophenyl) - 4,5 - diphenylimidazole, 2 - (O - chlorophenyl) - 4,5 - di(m - methoxyphenyl))imidazole, 2 - (O - fluorophenyl) - 4,5 - diphenylimidazole, 2 - (O - methoxyphenyl) - 4,5 - diphenylimidazole, 2,4,5 - triarylimidazole; halomethylthiazole compounds such as 2 - trichloromethyl - 5 - styryl - 1,3,4 - oxadiazole, 2 - trichloromethyl - 5 - (p - cyanostyryl) - 1,3,4 - oxadiazole, 2 - trichloromethyl - 5 - (p - methoxystyryl) - 1,3,4 - oxadiazole;Halogenomethyl-s-triazine compounds such as 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthio-styryl)-4,6-bis(trichloromethyl)-1,3,5-triazine; O-acyl oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butan-1-one oxime-O-acetate; Sulfur compounds such as benzyldimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone; Anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone; Organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, cumene peroxide; Thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole; Tertiary amines such as triethanolamine, triethylamine are included. It is preferably contains α-hydroxyalkylphenones, and more preferably contains 1-hydroxycyclohexyl phenyl ketone. In addition, these photoinitiators may be used alone or in combination of two or more kinds.;

[0098] (iii) The content of the photopolymerization initiator, which is a component, is preferably 0.1 part by mass to 10.0 parts by mass, and more preferably 2 parts by mass to 5 parts by mass with respect to 100 parts by mass of the total amount of (i) the alkali-soluble resin and (ii) the photopolymerizable compound. Here, when the addition amount of the photopolymerization initiator is 0.1 part by mass or more, the sensitivity becomes sufficiently high. When the addition amount of the photopolymerization initiator is 10.0 parts by mass or less, it is less likely that the taper shape (the film thickness direction shape of the development pattern cross section) will not become sharp and halation will occur in a state where the tail is trailing. Furthermore, the possibility of generating decomposition gas when exposed to high temperature in a subsequent process is also reduced.

[0099] Further, the photosensitive resin composition according to the present embodiment may contain an epoxy compound of (iv).

[0100] (iv) The epoxy compound can be any known compound commercially available as an epoxy resin or the like without particular limitation. Examples of epoxy resins include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy resins, biphenyl type epoxy resins, bisphenol fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polycarboxylic acids, polymers containing glycidyl (meth)acrylate as a unit, alicyclic epoxy compounds typified by [(3,4-epoxycyclohexyl)methyl] 3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., "EHPE3150", manufactured by Daicel Corporation), phenyl glycidyl ether, p-butylphenyl glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, epoxidized polybutadiene (e.g., "NISSO-PB·JP-100", manufactured by Nippon Soda Co., Ltd.), and epoxy compounds having a silicone skeleton. These components are preferably compounds having an epoxy equivalent of 100 g / eq to 300 g / eq and a number average molecular weight of 100 to 5000. The component (iv) may use only one type of compound or may use two or more types in combination. When it is necessary to increase the crosslink density of the alkali-soluble resin, a compound having at least two or more epoxy groups is preferred.

[0101] The content of the epoxy compound in (iv) is preferably 10 to 40 parts by mass with respect to 100 parts by mass in total of components (i) and (ii). Here, as one of the purposes of adding the epoxy compound, the amount of carboxy groups remaining when the cured product after patterning is formed may be reduced in order to enhance the reliability of the cured product. By setting the addition amount of the epoxy compound to 10 parts by mass or more, the moisture resistance reliability when used as an insulating film can be further enhanced. Further, by setting the blending amount of the epoxy compound to 40 parts by mass or less, the amount of photosensitive groups in the resin component in the photosensitive resin composition can be made sufficiently large, and the sensitivity for patterning can be made sufficient.

[0102] The photosensitive resin composition according to the present embodiment may contain a dispersoid as the component (v).

[0103] As the dispersoid of the component (v), any known dispersoid used in the photosensitive resin composition can be used without particular limitation as long as it is dispersed with an average particle size of 1 nm to 1000 nm (average particle size measured by a laser diffraction / scattering method particle size distribution meter or a dynamic light scattering method particle size distribution meter). Examples of the dispersoid include organic pigments such as azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, thioindigo pigments; inorganic pigments such as titanium oxide pigments, composite oxide pigments; pigments such as carbon black pigments (coloring agents that are substantially insoluble in the medium); organic fillers such as acrylic polymer particles, urethane polymer particles; inorganic fillers such as silica, talc, mica, glass fibers, carbon fibers, calcium silicate, magnesium carbonate, calcium carbonate, calcium sulfate, barium sulfate; and metal or metal oxide nanoparticles.

[0104] These (v) dispersoids can be used alone or in combination of multiple types according to the function of the target photosensitive resin composition. Examples of light-shielding resists used in the production of black matrices of color filters include carbon black, titanium black, and black organic pigments. Examples of colored resists used in the production of pixels of color filters include organic pigments in red, orange, yellow, green, blue, and purple. Examples of solder resists used in the production of insulating films of printed wiring boards include organic pigments, inorganic pigments, and inorganic fillers. Examples of decorative resists used in the design of the front glass of touch panels include carbon black, titanium black, black organic pigments, and white pigments. Examples of transparent resists with high hardness, high refractive index, and high durability include transparent fillers such as silica and titania. These (v) dispersoids can be appropriately selected and used respectively.

[0105] Also, examples of cases where the (v) dispersoid is a light-shielding material include black organic pigments, mixed-color organic pigments, and black inorganic pigments. In this case, the (v) dispersoid (light-shielding material) is preferably excellent in insulation, heat resistance, light resistance, and solvent resistance depending on the application. Here, examples of black organic pigments as light-shielding materials include perylene black, aniline black, cyanine black, and lactam black. Examples of mixed-color organic pigments as light-shielding materials include those pseudo-blackened by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta, etc. Examples of black inorganic pigments as light-shielding materials include carbon black, chromium oxide, iron oxide, and titanium black. These (v) dispersoids can be used singly or in combination of two or more.

[0106] In addition, examples of organic pigments that can be used as the (v) component include those with the following numbers by Color Index name, but are not limited thereto. Pigment Red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279, etc. Pigment Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc. Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc. Pigment Green 7, 36, 58, etc. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc. Pigment Violet 19, 23, 37, etc.

[0107] Furthermore, as other dispersoids, known rubber components may be added for improving impact resistance, adhesion to plating metals during processing, etc. The rubber component is preferably a crosslinked elastic polymer having a carboxyl group to ensure developability. Examples of the rubber component include crosslinked acrylic rubber having a carboxyl group, crosslinked NBR having a carboxyl group, and crosslinked MBS having a carboxyl group. When using the rubber component, it is preferable to add those having an average particle size of 0.1 μm or less in an amount of 3 to 10 parts by mass based on 100 parts by mass of the resin component.

[0108] (v) The dispersoid is preferably dispersed in a solvent together with a dispersant in advance to form a dispersion, and then incorporated as a photosensitive resin composition. As the solvent used in this case, those exemplified as the solvents that dissolve the photosensitive resin composition according to the present embodiment may be used alone, or two or more of them may be used in combination.

[0109] The blending ratio of the dispersoid forming the dispersoid dispersion can be 1 part by mass to 95% by mass based on the total solid content of the photosensitive resin composition according to the present embodiment. The solid content means the components excluding the solvent in the composition. The solid content includes the component (ii) that becomes a solid content after photocuring. The wide addition amount range of 1 part by mass to 95% by mass of the dispersoid is, for example, from the case of using a dispersoid with a small specific gravity of organic substances such as acrylic resin particles and rubber particles to the case of using a dispersoid with a large specific gravity such as metal particles and metal oxide particles. Further, when the dispersoid is added for the purpose of coloring, it is preferably 5 parts by mass to 80% by mass. By making it more than 5% by mass in the solid content, desired coloring can be achieved, and functions such as imparting desired light-shielding properties that the dispersoid should impart can be easily imparted. By making it 80% by mass or less in the solid content, the content of the photosensitive resin that originally serves as a binder can be made sufficiently large to ensure developability and film-forming ability. Therefore, when the component (v) in the solid content is a colorant (including a light-shielding material), its content is preferably 10% by mass to 70% by mass, and more preferably 20% by mass to 60% by mass.

[0110] Further, the dispersoid dispersion may contain a known dispersant such as a polymer dispersant in order to stably disperse the dispersoid. As the dispersant, known compounds used for pigment dispersion (compounds commercially available under names such as dispersants, dispersion wetting agents, dispersion accelerators, etc.) can be used.

[0111] Examples of the dispersant include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative dispersants (dispersion aids). In particular, the dispersant preferably has a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary, secondary, or tertiary amino group as an adsorption point to a dispersion medium such as a pigment, and is a cationic polymer dispersant with an amine value in the range of 1 mgKOH / g to 100 mgKOH / g and a number average molecular weight in the range of 1,000 to 100,000. The blending amount of this dispersant is preferably 1% by mass to 35% by mass, more preferably 2% by mass to 25% by mass, based on the dispersion medium. Note that high-viscosity substances such as resins generally have an effect of stabilizing dispersion, but those without dispersion-promoting ability are not treated as dispersants. However, it is not limited to use for the purpose of stabilizing dispersion.

[0112] The dispersion medium dispersion liquid thus obtained can be made into a photosensitive resin composition containing a dispersion medium by mixing with (i) component (when the (i) component is co-dispersed when preparing the dispersion medium dispersion liquid, the remaining (i) component), (ii) component, (iii) component, and optionally added (iv) component, and adding a solvent as necessary to obtain an appropriate solution viscosity.

[0113] Further, the photosensitive resin composition according to this embodiment may contain a solvent.

[0114] Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; and acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. From the viewpoint of facilitating the dissolution of a resin having a highly polar alkali-soluble site such as a carboxy group and enhancing the drying property, it is preferable to contain acetate esters, and more preferable to contain propylene glycol monomethyl ether acetate. By dissolving and mixing these alone or in combination of two or more, a uniform solution composition can be obtained.

[0115] In addition, the photosensitive resin composition according to this embodiment can be blended with additives such as a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a leveling agent, an antifoaming agent, a coupling agent, and a surfactant, if necessary.

[0116] As the curing accelerator, for example, known compounds known as curing accelerators, curing catalysts, latent curing agents, etc., which are usually applied to epoxy compounds, can be used. Examples of the curing accelerator include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borate esters, Lewis acids, organometallic compounds, imidazoles, diazabicyclo compounds, etc. Examples of the thermal polymerization inhibitor and antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol-based antioxidants, phosphorus-based heat stabilizers. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. Examples of the defoaming agent and leveling agent include silicone-based, fluorine-based, acrylic-based compounds, etc. Examples of the coupling agent include vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(glycidyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-ureidopropyltriethoxysilane, etc. Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, etc.

[0117] The photosensitive resin composition according to this embodiment preferably contains, in the solid content excluding the solvent (the solid content includes a photopolymerizable compound that becomes a solid content after curing), (i) an alkali-soluble resin represented by the general formula (1) or the general formula (4), (ii) a photopolymerizable compound, (iii) a photoinitiator, and optionally (iv) an epoxy compound and (v) a dispersoid, in a total amount of 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. The amount of the solvent varies depending on the target viscosity, but is preferably 10% by mass to 80% by mass, and more preferably 20% by mass to 70% by mass, based on the total mass of the photosensitive resin composition.

[0118] In this way, the photosensitive resin composition according to this embodiment can be obtained.

[0119] The photosensitive resin composition containing an alkali-soluble resin represented by the general formula (1) or general formula (4) produced as described above can provide a cured product with excellent heat resistance, excellent dimensional accuracy, and a pattern cross-sectional shape, which is formed by a photolithography method such as a solder resist, a plating resist, an etching resist for circuit board production, a color filter, a light-shielding film, etc. of a liquid crystal display device, an organic EL display device, a μLED display device, an image sensor, etc.

[0120] Each step of the film formation method of the coating film (cured product) by coating and drying the photosensitive resin composition will be specifically exemplified. In the present application, the cured product refers to at least the film subjected to the following pre-baking or the following exposure, and the coating film refers to the film without pre-baking or exposure.

[0121] In addition, the coating film (cured product) according to the present embodiment can be obtained, for example, by applying a solution of the photosensitive resin composition to a substrate or the like, drying it, irradiating it with light (including ultraviolet rays, radiation, etc.), and curing it. By using a photomask or the like to provide a portion irradiated with light and a portion not irradiated with light, only the portion irradiated with light is cured, and the other portion is dissolved with an alkaline solution to obtain a coating film with a desired pattern.

[0122] Specifically exemplified, each step of the film formation method by coating and drying the photosensitive resin composition can adopt any method such as a known solution dipping method, a spray method, a roller coater machine, a land coater machine, a slit coater machine, or a method using a spinner machine when applying the photosensitive resin composition to a substrate. After coating to a desired thickness by these methods, a film is formed by removing the solvent (pre-baking). Pre-baking is performed by heating with an oven, a hot plate, etc., vacuum drying, or a combination thereof. The heating temperature and heating time in pre-baking are appropriately selected according to the solvent used, and are, for example, performed at 80°C to 120°C for 1 minute to 10 minutes.

[0123] The radiation used for exposure can be, for example, visible light, ultraviolet light, far ultraviolet light, electron beams, X-rays, etc., but the wavelength range of the radiation is preferably 250 nm to 450 nm. Examples of the developer suitable for this alkali development include aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. These developers can be appropriately selected according to the characteristics of the resin layer, and it is also effective to add a surfactant if necessary. The development temperature is preferably 20°C to 35°C, and a fine image can be precisely formed using a commercially available developing machine, ultrasonic cleaner, etc. After alkali development, it is usually washed with water. As the development treatment method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid-filled) development method, etc. can be applied.

[0124] After development in this way, heat treatment (post-baking) is performed at 180°C to 250°C for 20 minutes to 100 minutes. This post-baking is performed for the purpose of enhancing the adhesion between the patterned cured product and the substrate, etc. This is performed by heating with an oven, hot plate, etc., similar to pre-baking. The patterned coating film according to this embodiment is formed through the above steps by the photolithography method. Then, polymerization or curing (sometimes referred to as curing together) is completed by heat to form a cured product pattern. The curing temperature at this time is preferably 160°C to 250°C.

[0125] The glass transition temperature (Tg) of the cured product obtained by curing the photosensitive resin composition according to this embodiment can be measured by dynamic viscoelasticity measurement (DMA). When determining the glass transition temperature (Tg) by dynamic viscoelasticity measurement (DMA), it is applied so that the film thickness after post-baking becomes 30 μm, pre-baked at 90°C for 3 minutes, and then 500 W / cm 2Irradiate with ultraviolet light of wavelength 365 nm using a high-pressure mercury lamp, subject the exposed coating film to alkali treatment by shower development with a 0.8 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 °C, perform spray water washing, and for the cured product after post-baking at 230 °C for 30 minutes, use an RSA-G2 manufactured by TA Instruments to perform dynamic viscoelasticity measurement in the range of 25 °C to 300 °C under an air atmosphere with a frequency of 1 Hz and a heating rate of 4 °C / min for a cured product with a distance between the fixing jigs of 20 mm and a width of 5 mm, and take the peak temperature of tanδ obtained from the resulting storage elastic modulus and loss elastic modulus as the glass transition temperature (Tg) measured by dynamic viscoelasticity measurement (DMA) (hereinafter, also referred to as "Tg(DMA)").

[0126] When the photosensitive resin composition according to this embodiment is made into a cured product by the above method, the glass transition temperature (Tg) can also be measured by thermomechanical analysis (TMA). When determining the glass transition temperature (Tg) by thermomechanical analysis (TMA), using a TMA / SS7100 manufactured by Hitachi High-Tech Sciences, the temperature indicating the inflection point of the dimensional change amount when measuring in the range of 40 °C to 300 °C under an air atmosphere in a tensile mode with a load of 49 mN and a heating rate of 10 °C / min for a cured product with a distance between the fixing jigs of 15 mm and a width of 3 mm can be taken as the glass transition temperature (Tg) measured by dynamic viscoelasticity measurement (TMA) (hereinafter, also referred to as "Tg(TMA)").

[0127] Since the photosensitive resin composition according to this embodiment has a larger number of polymerizable unsaturated groups compared to conventional ones, its photocurability is improved, and the crosslinking density after curing can be increased without increasing the amount of the photoinitiator. That is, when irradiating with ultraviolet light or electron beam in a thick film, the cured part cures to the bottom, so there is no difference in solubility in the alkali developer between the exposed part and the unexposed part, resulting in improved pattern dimension stability, development margin, and pattern adhesion, and patterns can be formed with high resolution. And even in the case of a thin film, due to the increased sensitivity, a significant improvement in the remaining film amount of the exposed part and suppression of peeling during development can be achieved.

[0128] The photosensitive resin composition according to this embodiment is extremely useful for solder resists, plating resists, etching resists for manufacturing circuit boards, insulating films for multilayer wiring boards on which semiconductor elements are mounted, various insulating films of semiconductor devices, gate insulating films of semiconductors, photosensitive adhesives (especially adhesives that require heat adhesion performance even after pattern formation by photolithography), and the like.

Examples

[0129] Hereinafter, embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited thereto. In the present invention, when the content of each component has a zero in the first decimal place, the notation after the decimal point may be omitted.

[0130] First, the synthesis examples of the polymerizable unsaturated group-containing alkali-soluble resin represented by the general formula (1) or the general formula (4), which is the component (i), will be described. The evaluation of the resin in these synthesis examples was carried out as follows unless otherwise specified.

[0131] [Solid content concentration] The resin solutions, photosensitive resin compositions, etc. (1 g) obtained in Synthesis Examples 1 and 2 and Comparative Synthesis Example were impregnated into a glass filter [mass: W0 (g)] and weighed [W1 (g)], and the mass [W2 (g)] after heating at 130 °C for 3 hours was used to calculate from the following formula. Solid content concentration (mass%) = 100×(W2 - W0) / (W1 - W0)

[0132] [Acid value] The acid value was determined by dissolving the resin solution in tetrahydrofuran and titrating it with a 1 / 10N - KOH aqueous solution using a potentiometric titrator "COM - 1600" (manufactured by HIRANUMA), and the amount of KOH required per 1 g of solid content was defined as the acid value.

[0133] [Molecular weight] The molecular weight was measured by gel permeation chromatography (GPC) (HLC-8420GPC, manufactured by Tosoh Corporation, columns: TSKgel Super H2000 (2 columns) + TSKgel Super H3000 (1 column) + TSKgel Super H4000 (1 column) + TSKgel Super H5000 (1 column) (all manufactured by Tosoh Corporation), solvent: tetrahydrofuran, temperature: 40 °C, flow rate: 0.6 ml / min), and the value obtained as the polystyrene standard (PS-oligomer kit, manufactured by Tosoh Corporation) conversion value was taken as the weight average molecular weight (Mw).

[0134] Also, the abbreviations described in Synthesis Examples 1 and 2 and Comparative Synthesis Example are as follows. BPAEA: A compound obtained by reacting acrylic acid further with an epoxy compound (epoxy equivalent 232 g / eq, in the general formula (8), W is a glycidyl group (G)) obtained by reacting 4,4'-bisphenol with 4,4'-bis(hydroxyphenyl)methane so that the molar ratio is 0.8 / 0.2 when 4,4'-bisphenol is the numerator and 4,4'-bis(hydroxyphenyl)methane is the denominator in a reaction solution of 4,4'-biphenol and 4,4'-bis(chloromethyl)biphenyl (biphenyl aralkyl resin), and then reacting with epichlorohydrin (an equimolar reaction product of an epoxy group and a carboxyl group). BPDA: 3,3',4,4'-Biphenyltetracarboxylic dianhydride THPA: 1,2,3,6-Tetrahydrophthalic anhydride SA: Succinic anhydride TEAB: Tetraethylammonium bromide PGMEA: Propylene glycol monomethyl ether acetate

[0135] The following Synthesis Example 1 and Synthesis Example 2 are synthesis examples of an alkali-soluble resin having a carboxy group and a polymerizable unsaturated group in one molecule represented by the general formula (1) or the general formula (4). Further, the Comparative Synthesis Example is a polymerizable unsaturated group-containing alkali-soluble resin having a skeleton different from that of the alkali-soluble resin represented by the general formula (1) or the general formula (4), and is an epoxy acrylate acid adduct of a bisphenol A type epoxy compound.

[0136] [Synthesis Example 1] (Synthesis of the alkali-soluble resin (i)-1 represented by the general formula (1) or the general formula (4)) A 50% PGMEA solution of BPAEA (355.0 g), THPA (71.7 g), TEAB (1.3 g), and PGMEA (19.3 g) were charged into a 1000 ml four-necked flask equipped with a reflux condenser, and stirred at 120 °C to 125 °C for 6 hours to obtain the alkali-soluble resin (i)-1. The solid content concentration of the obtained resin was 56.4 wt%, the acid value (in terms of solid content) was 107.5 mgKOH / g, and the molecular weight (Mw) by GPC analysis was 7440.

[0137] [Synthesis Example 2] (Synthesis of the alkali-soluble resin (i)-2 represented by the general formula (1) or the general formula (4)) A 50% PGMEA solution of BPAEA (395.0 g), SA (52.5 g), TEAB (1.5 g), and PGMEA (0.05 g) were charged into a 1000 ml four-necked flask equipped with a reflux condenser, and stirred at 120 °C to 125 °C for 6 hours to obtain the alkali-soluble resin (i)-2. The solid content concentration of the obtained resin was 56.5 wt%, the acid value (in terms of solid content) was 118.0 mgKOH / g, and the molecular weight (Mw) by GPC analysis was 7120.

[0138] [Comparative Synthesis Example] (Synthesis of the alkali-soluble resin (i)-3) In a 1000 ml four-necked flask equipped with a reflux condenser, 50% PGMEA solution (440.0 g) of the reaction product of bisphenol A type epoxy compound (epoxy equivalent 480 g / eq) and acrylic acid, BPDA (20.5 g), THPA (24.2 g), TEAB (0.84 g), and PGMEA (6.2 g) were charged, and stirred at 120 °C to 125 °C for 6 hours to obtain an alkali-soluble resin solution (i)-3. The solid content concentration of the obtained resin was 54.6 wt%, the acid value (in terms of solid content) was 65.1 mgKOH / g, and the molecular weight (Mw) by GPC analysis was 9000.

[0139] Next, the present invention will be specifically described based on Examples 1 to 2 and Comparative Example 1 regarding the production and evaluation of the photosensitive colored resin composition and its cured product, but the present invention is not limited thereto. Here, the raw materials and abbreviations used in the production of the colored photosensitive resin compositions of Example 1 and Comparative Example 1 hereinafter are as follows.

[0140] A photosensitive colored resin composition was prepared with the blending amounts (unit: mass%) shown in Table 1. The blending components used in Table 1 are as follows.

[0141]

Table 1

[0142] (Alkali-soluble resin containing polymerizable unsaturated group) (i)-1: Alkali-soluble resin containing polymerizable unsaturated group obtained in Synthesis Example 1 (i)-2: Alkali-soluble resin containing polymerizable unsaturated group obtained in Synthesis Example 2 (i)-3: Alkali-soluble resin containing polymerizable unsaturated group obtained in Comparative Synthesis Example (Photopolymerizable compound) (ii): Dipentaerythritol hexaacrylate (Photopolymerization initiator) (iii): Omnirad184 (manufactured by IGM Resins B.V.) (Epoxy compound) (iv): EOCN-103S (Japanese Chemicals' Cresol Novolak Epoxy Resin) (Solvent) PGMEA: Propylene Glycol Monomethyl Ether Acetate

[0143] [Evaluation] [Alkaline Developability Evaluation] The photosensitive resin composition shown in Table 1 was applied onto a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after post-baking would be 10 μm, and a coated plate was prepared by pre-baking at 100°C for 5 minutes. Then, ultraviolet light with a wavelength of 365 nm was irradiated using a high-pressure mercury lamp of 500 W / cm2 through a photomask for pattern formation, and a photocuring reaction of the exposed portion was carried out. Next, this exposed coated plate was developed for an additional 20 seconds starting from the time when the pattern began to appear by shower development with a 1.0 wt% aqueous sodium carbonate solution at 23°C, and further spray water washing was performed to remove the unexposed portion of the coating film. Thereafter, a heat curing treatment was carried out at 230°C for 30 minutes using a hot air dryer to obtain cured products according to Examples 1 to 2 and Comparative Example 1.

[0144] [Alkaline Developer Solubility] It was judged from the transparency of the alkaline developer after alkaline development. 〇: The alkaline developer after alkaline development is transparent △: The alkaline developer after alkaline development is white semi-transparent ×: The alkaline developer after alkaline development is white opaque

[0145] [Via Processability] It was judged from the presence or absence of residue in the via processed portion. ○ : The via pattern diameter is 50 μm or more and there is no residue inside the via processed portion 〇△: The via pattern diameter is 50 μm or more and there is residue at the end of the via processed portion △ : The via pattern diameter is 50 μm or more and there is also residue inside the via processed portion × : The via pattern diameter is 75 μm or more and there is no residue in the via processed portion

[0146] [Dot pattern adhesion] It was judged from the remaining state of the dot pattern after alkali development. ○: Those with a dot pattern diameter of 10 μm or more and a pattern formed △: Those with a dot pattern diameter of 30 μm or more and a pattern formed ×: Those with a dot pattern diameter of 40 μm or more and a pattern formed

[0147] [Fine line pattern adhesion] It was judged from the remaining state of the fine line pattern after alkali development. ○: Those formed with a minimum L / S (line width / space width) of 10 μm / 10 μm or more △: Those formed with a minimum L / S (line width / space width) of 30 μm / 30 μm or more ×: Those formed with a minimum L / S (line width / space width) of 40 μm / 40 μm or more

[0148] [Photocurability] The photosensitive resin composition shown in Table 1 was applied onto a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after post-baking was 10 μm, and a coated plate was prepared by pre-baking at 90 °C for 3 minutes. Thereafter, ultraviolet light with a wavelength of 365 nm was irradiated using a high-pressure mercury lamp of 500 W / cm 2 through a photomask with a continuously changing ultraviolet light transmittance, and a photocuring reaction of the exposed portion was carried out. Next, this exposed coated plate was developed for an additional 10 seconds starting from the time when a pattern began to appear by shower development with a 1.0 wt% sodium carbonate aqueous solution at 23 °C, and then spray water washing was performed to remove the unexposed portion of the coating film. Thereafter, a heat curing treatment was carried out at 230 °C for 30 minutes using a hot air dryer to obtain cured products according to Examples 1 to 2 and Comparative Example 1.

[0149] [Evaluation method] The exposure amount was calculated from the position where the surface of the cured product remained at a predetermined film thickness without roughness, and the minimum exposure amount at which the cured product could be formed was taken.

[0150]

Table 2

[0151] As shown in Table 2, it was found that the polymerizable unsaturated group-containing alkali-soluble resin represented by the general formula (1) or the general formula (4) has high-precision patterning properties and photocurability.

[0152] [Heat Resistance Evaluation] The photosensitive resin composition shown in Table 1 was applied onto a glass substrate with a 125 mm × 125 mm aluminum sheet with a release agent attached using a spin coater so that the film thickness after post-baking became 30 μm, and pre-baked at 90°C for 3 minutes to prepare a coated plate. Then, ultraviolet rays with a wavelength of 365 nm were irradiated using a high-pressure mercury lamp of 500 W / cm 2 to carry out the photocuring reaction of the exposed portion. Next, the exposed coated plate was developed with a 0.8 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) by shower development at 23°C until the unexposed portion was dissolved, and further spray rinsed to remove the unexposed portion of the coating film. Thereafter, heat curing treatment was performed at 230°C for 30 minutes using a hot air dryer to obtain cured products according to Examples 1 to 2 and Comparative Example 1. Further, the aluminum sheet with a release agent was immersed in hot water and dissolved to isolate the cured product.

[0153] [Evaluation Method] The glass transition temperature (Tg) and coefficient of thermal expansion (CTE) of the isolated cured product were measured by thermomechanical analysis (TMA) and dynamic viscoelasticity measurement (DMA). When determining the glass transition temperature (Tg) by thermomechanical analysis (TMA), using TMA / SS7100 manufactured by Hitachi High-Tech Sciences, for a cured product with a distance between the fixed jigs of 15 mm and a width of 3 mm, the temperature at the inflection point of the dimensional change amount when measured in the range of 40 °C to 300 °C in a tensile mode with a load of 49 mN and a heating rate of 10 °C / min under an air atmosphere was defined as Tg(TMA). When determining the glass transition temperature (Tg) by dynamic viscoelasticity measurement (DMA), using RSA-G2 manufactured by TA Instruments, for a cured product with a distance between the fixed jigs of 20 mm and a width of 5 mm, dynamic viscoelasticity measurement was performed in the range of 25 °C to 300 °C under an air atmosphere at a frequency of 1 Hz and a heating rate of 4 °C / min, and the peak temperature of tanδ obtained from the resulting storage modulus and loss modulus was defined as Tg(DMA).

[0154] [Coefficient of Thermal Expansion] The glass transition temperature (Tg) measured by thermomechanical analysis (TMA) was calculated as follows. α1: The dimensional change amount in the loading direction of the cured product in the range of Tg - 20 °C to Tg - 10 °C was divided by the length of the test piece at 25 °C to calculate the dimensional change rate, and the dimensional change rate per 1 °C further divided by 10 was defined as α1. α2: The dimensional change amount in the loading direction of the cured product in the range of Tg + 10 °C to Tg + 20 °C was divided by the length of the test piece at 25 °C to calculate the dimensional change rate, and the dimensional change rate per 1 °C further divided by 10 was defined as α2.

[0155]

Table 3

[0156] As shown in Table 3, it was found that the polymerizable unsaturated group-containing alkali-soluble resin represented by the general formula (1) or the general formula (4) exhibits a high glass transition temperature and has high heat resistance.

Industrial Applicability

[0157] The photosensitive resin composition containing the alkali-soluble resin of the present invention is applicable as a solder resist, plating resist, etching resist for circuit board fabrication, resist for insulating films such as semiconductor devices, and a composition for photosensitive optical waveguides. Its cured product is a protective film, color filter, light-shielding film, etc., which are components of liquid crystal display devices, organic EL display devices, μLED display devices, image sensors, etc., various cured products formed by photolithography, and is further applicable as a wiring insulator for semiconductors, an insulator for build-up substrates, a partition wall, an optical component, an optical fiber, and an optical waveguide.

Claims

1. An alkali-soluble resin represented by the following general formula (1) and having a carboxy group and a polymerizable unsaturated group in one molecule: (In formula (3), L represents a divalent or trivalent residue derived from a dicarboxylic acid, a tricarboxylic acid, or an acid anhydride thereof, and p is a number of 1 or 2. * indicates the bonding site with the oxygen atom in formula (2).) 【Chemical 1】 (In formula (1), X １ and X ２ each independently represent different tetravalent aromatic ring-containing groups, and Y １ independently represents a divalent aromatic ring-containing group. Some of the hydrogen atoms of X １ , X ２ and Y １ may be substituted with a linear or branched hydrocarbon group having 1 to 20 carbon atoms. V １ each independently is a linear or branched hydrocarbon group having 1 to 5 carbon atoms or a substituent Z represented by the following general formula (2). However, at least two of V １ are the substituent Z. Q １ each independently is a hydrogen atom or a linear or branched hydrocarbon group having 1 to 20 carbon atoms. k is a number from 1 to 20, and l is a number from 0 to 20. The structural unit containing X １ and the structural unit containing X ２ may be arranged randomly or in blocks, and k and l represent the number of introductions of their respective structural units.) 【Chemical 2】 (In formula (2), R １ represents a hydrogen atom or a methyl group. J represents a substituent represented by the following general formula (3). * represents the bonding site with the oxygen atom in formula (1).) 【Chemical Formula 3】

2. The alkali-soluble resin according to Claim 1. Said V １ For the hydrocarbon group and substituent Z that can be taken, the number of moles of the hydrocarbon group is Mc １ , the number of moles of the substituent Z is Mz １ When it is so, Mc １ / Mz １ The value of is 0.05 to 2.0,

3. An alkali-soluble resin represented by the following general formula (4) and having a carboxy group and a polymerizable unsaturated group in one molecule: (In formula (3), L represents a divalent or trivalent residue derived from a dicarboxylic acid, a tricarboxylic acid, or an acid anhydride thereof, and p is a number of 1 or 2. * indicates the bonding site with the oxygen atom in formula (2).)

4. 【Chemical Formula 4】 (In formula (4), X ３ is a tetravalent substituent represented by the following general formula (5) independently derived from a biphenol compound, and X ４ is a tetravalent substituent represented by the following general formula (6) independently derived from a bisphenol compound. Y ２ is a divalent substituent represented by the following general formula (7) independently. In the following general formulas (5), (6), and the following general formula (7), a part of the hydrogen atoms may be substituted with a linear or branched hydrocarbon group having 1 to 20 carbon atoms. In the following general formula (6), V ２ is independently a linear or branched hydrocarbon group having 1 to 5 carbon atoms or a substituent Z represented by formula (2). However, at least two of V ２ are the substituent Z. m is a number from 1 to 20, and n is a number from 0 to 20. Q ２ is independently a hydrogen atom or a linear or branched hydrocarbon group having 1 to 20 carbon atoms. Also, X ３ The structural unit containing and X ４ The structural unit containing may be arranged randomly or in blocks, and m and n indicate the number of introductions of the respective structural units.) 【Chemical Formula 5】 (In formula (5), * indicates the bonding site with the oxygen atom in formula (4), and ** indicates the bonding site with Y ２ or Q ２ .) 【Chemical Formula 6】 (In formula (6), M is a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a halogen atom, an aromatic hydrocarbon group, -O-, -C(=O)-, -S- and -SO ２ is a divalent substituent selected from the group consisting of -. In formula (6), * indicates the bonding site with the oxygen atom in formula (4), and ** indicates Y ２ or Q ２ indicates the bonding site with. ) 【Chemical Formula 7】 (In formula (7), * represents the bonding site with X in formula (4) ３ or X ４ .) [Chemical 8] (In formula (2), R １ represents a hydrogen atom or a methyl group. J represents a substituent represented by the following general formula (3). * indicates the bonding site with the oxygen atom in formula (4).) 【Chemical Formula 9】 The alkali-soluble resin according to Claim 3.

5. The above-mentioned V ２ For the hydrocarbon group and the substituent Z that can be taken, the number of moles of the hydrocarbon group is Mc ２ Let it be, and the number of moles of the substituent Z is Mz ２ When it is, Mc ２ / Mz ２ The value of is 0.05 to 2.0 (i) The alkali-soluble resin according to any one of Claims 1 to 4; (ii) A photopolymerizable compound having at least one polymerizable unsaturated group; (iii) A photopolymerization initiator; A photosensitive resin composition containing the same.

6. The content of the (iii) photopolymerization initiator is 0.1 part by mass to 10.0 parts by mass with respect to a total of 100 parts by mass of the (i) alkali-soluble resin and the (ii) photopolymerizable compound. The photosensitive resin composition according to Claim 5.

7. The photosensitive resin composition according to Claim 5, containing (iv) an epoxy compound.

8. The content of the (iv) epoxy compound is 10 parts by mass to 40 parts by mass with respect to a total of 100 parts by mass of the (i) alkali-soluble resin and the (ii) photopolymerizable compound. The photosensitive resin composition according to Claim 7.

9. The photosensitive resin composition according to Claim 5, containing (v) a dispersoid.

10. A cured product obtained by curing the photosensitive resin composition according to Claim 5. ​ ​

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