Unsaturated group-containing polymerizable resin, method for producing unsaturated group-containing polymerizable resin, photosensitive resin composition, cured resin film, laminate, method for producing laminate, and method for processing laminate

Abstract

To provide an unsaturated group-containing polymerizable resin suitably applicable as a material for a photosensitive resin composition capable of forming a cured film utilizable as a positive-type resist, having superior patterning properties, exhibiting high adhesion strength without a bleaching process, and ensuring excellent peelability when irradiating the cured film with a laser.SOLUTION: An unsaturated group-containing polymerizable resin comprising a compound represented by following General Formula (1). (In Formula (1), Ars each independently represents a specific aromatic hydrocarbon group, R1s each independently represents an alkylene group having 2 to 4 carbon atoms, ls each independently represents an integer of 0 to 3, Gs each independently represents a specific group or the like, Ws each independently represents a specific group or the like, L represents a specific group, Xs each independently represents a specific group or the like, Y represents a specific tetravalent carboxylic acid residue, and n represents a natural number).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an unsaturated group-containing polymerizable resin, a method for producing the unsaturated group-containing polymerizable resin, a photosensitive resin composition using the unsaturated group-containing polymerizable resin, a cured resin film using the photosensitive resin composition, a laminate using the photosensitive resin composition, a method for producing the laminate, and a method for treating the laminate. [Background technology]

[0002] In recent years, laser mass transfer, which allows for the transfer of LED chips by laser irradiation, has been attracting attention as a transfer method for micro LEDs (μ-LEDs). To perform such laser mass transfer, the LED chip must be fixed onto a laser-decomposable adhesive layer. Examples of materials used for such adhesive layers include resins described in JP 2022-65426 A (Patent Document 1). The resin described in Patent Document 1 is a resin that can be used for negative resists. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2022-65426 Summary of the Invention [Problem to be solved by the invention]

[0004] Traditionally, the development of adhesives for laser mass transfer (LMT) has focused primarily on compositions with excellent laser processability, without considering patterning. However, laser processing without patterning results in reduced transfer accuracy, leading to problems with process margins in conventional LMT. On the other hand, when patterning is performed using conventional positive resist resins as adhesive layers, a light bleaching step is always required to achieve strong adhesive strength in the adhesive layer after pattern formation. This is because, when bonding is performed without a bleaching step, the photosensitizer required for pattern formation with conventional positive resists decomposes under light and heat, generating gas. This gas generation then creates voids between the adherend and the adhesive, significantly reducing adhesive strength. Furthermore, while reducing the amount of photosensitizer used to suppress gas generation in order to avoid the bleaching step allows for adhesion, the developer resistance is reduced, making it difficult to form the desired pattern through the photolithography process, and thus failing to achieve both patternability (developability) and adhesive strength.

[0005] Given these circumstances, it was clear that if a conventional resin composition for resists was used as an adhesive layer, it would not be possible to achieve high adhesive strength without carrying out a bleaching process while patterning, and it was difficult to improve the transfer accuracy of the LED chip and expand the process margin while using a resin composition for resists as an adhesive layer.

[0006] The present invention has been made in view of the problems associated with the prior art, and aims to provide an unsaturated group-containing polymerizable resin that can be used as a positive resist, has excellent patterning properties, is capable of forming a cured film (adhesive layer) with high adhesive strength without carrying out a bleaching step, and can be suitably used as a material for a photosensitive resin composition that enables excellent peelability when the cured film is irradiated with a laser, and a method for producing the same.

[0007] Another object of the present invention is to provide a photosensitive resin composition using such an unsaturated group-containing polymerizable resin, which can be used as a positive resist, has excellent patterning properties, and can form a cured film having high adhesive strength without performing a bleaching step, and can provide excellent peelability when the cured film is irradiated with a laser.Furthermore, another object of the present invention is to provide a cured resin film and a laminate using such a photosensitive resin composition, as well as methods for producing and treating the laminate. [Means for solving the problem]

[0008] As a result of intensive research to achieve the above object, the present inventors have found that by making the structure of a compound contained in an unsaturated group-containing polymerizable resin to be represented by the following general formula (1), when the unsaturated group-containing polymerizable resin containing the compound is used as a material for a photosensitive resin composition, the photosensitive resin composition has excellent patterning properties as a positive resist, and can form a cured film (adhesive layer) having high adhesive strength without carrying out a bleaching step, and can also have high peelability when the cured film is irradiated with a laser, thereby completing the present invention.

[0009] That is, the present invention provides the following aspects.

[0010] [1] An unsaturated group-containing polymerizable resin containing a compound represented by the following general formula (1):

[0011] [ka]

[0012] [In formula (1), each Ar independently represents an aromatic hydrocarbon group having from 6 to 14 carbon atoms, and some of the hydrogen atoms constituting the aromatic hydrocarbon group may be substituted with a substituent selected from the group consisting of an alkyl group having from 1 to 10 carbon atoms, an aryl group and an arylalkyl group having from 6 to 10 carbon atoms, a cycloalkyl group and a cycloalkylalkyl group having from 3 to 10 carbon atoms, an alkoxy group having from 1 to 5 carbon atoms, and a halogen group; Each R1 is independently an alkylene group having 2 to 4 carbon atoms, each l is independently a number between 0 and 3, G's are each independently a hydrogen atom or a substituent represented by the following general formula (2), and at least one of G's is a substituent represented by the following general formula (2), W's are each independently a hydrogen atom, a (meth)acryloyl group, a functional group represented by the following general formula (3), or a functional group represented by the following general formula (4), and at least one of W's is a (meth)acryloyl group, a functional group represented by the following general formula (3), or a functional group represented by the following general formula (4), L is a substituent represented by the following general formula (5): X's each independently represent -CO-, -SO2-, -C(CH3)2-, -C(CF3)2-, -Si(CH3)2-, -O-, -CH2-, a single bond, or a group represented by the following general formula (6): Y is a tetracarboxylic acid residue obtained by removing a carboxy group from one selected from the group consisting of a saturated linear hydrocarbon tetracarboxylic acid which may be substituted with a saturated cyclic hydrocarbon, an alicyclic tetracarboxylic acid which may be substituted with a saturated hydrocarbon, and an aromatic tetracarboxylic acid; n indicates a natural number.]

[0013] [ka]

[0014] [In formula (2), R2 is a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, Each R3 is independently a divalent saturated hydrocarbon group having 2 to 20 carbon atoms, R4 is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, Z is a hydrogen atom or a substituent represented by the following general formula (7), and at least one of Z satisfies the condition that it is a substituent represented by the following general formula (7), m is a number between 0 and 10, * indicates the binding site to the structure represented by general formula (1).

[0015] [ka]

[0016] [ka]

[0017] [In formulas (3) and (4), each R3 is independently a divalent saturated hydrocarbon group having 2 to 20 carbon atoms, R5 is a saturated or unsaturated divalent hydrocarbon group having from 2 to 20 carbon atoms, R6 is an alkylene group or alkylarylene group having from 2 to 10 carbon atoms, R7 is a hydrogen atom or a methyl group; m is a number between 0 and 10, * indicates the binding site to the structure represented by general formula (1).

[0018] [ka]

[0019] [In formula (5), V is a carboxylic acid residue obtained by removing a carboxy group from one member selected from the group consisting of saturated linear hydrocarbon dicarboxylic acids which may be substituted with a hydrocarbon group, saturated cyclic hydrocarbon dicarboxylic acids which may be substituted with a saturated hydrocarbon group, unsaturated dicarboxylic acids, aromatic dicarboxylic acids, citric acid, trimellitic acid, and hexahydrotrimellitic acid, G's are each independently a hydrogen atom or a substituent represented by the following general formula (2), and the condition that at least one of G's in formula (5) is a substituent represented by the general formula (2) is satisfied; q is 1 or 2, * indicates the binding site to the structure represented by general formula (1).

[0020] [ka]

[0021] [In formula (6), * indicates the bonding site to the structure represented by general formula (1)]

[0022] [ka]

[0023] [In formula (7), V is a carboxylic acid residue obtained by removing a carboxy group from one selected from the group consisting of saturated linear hydrocarbon dicarboxylic acids which may be substituted with a hydrocarbon group, saturated cyclic hydrocarbon dicarboxylic acids which may be substituted with a saturated hydrocarbon group, unsaturated dicarboxylic acids, aromatic dicarboxylic acids, citric acid, trimellitic acid, and hexahydrotrimellitic acid, q is 1 or 2, * indicates the binding site to the structure represented by general formula (2).

[0024] [2] The unsaturated group-containing polymerizable resin according to [1], which has a weight average molecular weight of 1,000 or more and 40,000 or less, and an acid value of 20 mgKOH / g or more and 200 mgKOH / g or less.

[0025] [3] A diol compound (a-1) represented by the following general formula (8), a tetracarboxylic dianhydride (a-2) represented by the following general formula (12), a dicarboxylic acid monoanhydride (a-3) represented by the following general formula (13), to obtain a first reactant having a carboxy group; a step of reacting the first reactant with an oxirane compound (a-4) represented by the following general formula (14) to obtain a second reactant having a hydroxyl group; a step of reacting the second reactant having a hydroxyl group with a dicarboxylic acid monoanhydride (a-5) represented by the following general formula (13) to obtain the unsaturated group-containing polymerizable resin according to [1] or [2]; Including, the molar amount of the component (a-4) used when reacting the component (a-4) with the first reactant is an amount such that the molar ratio ([component (a-4)] / [(2×[component (a-2)]))+[component (a-3)]] of the sum of twice the molar amount of the component (a-2) used in producing the first reactant and the molar amount of the component (a-3) used in producing the first reactant is 0.5 or more and 2.0 or less, and The molar amount of the component (a-5) used when reacting the second reactant with the component (a-5) is an amount such that the molar ratio ([component (a-5)] / [component (a-4)]) to the molar amount of the component (a-4) used when reacting the first reactant with the component (a-4) is 0.5 or more and 2.0 or less. A method for producing an unsaturated group-containing polymerizable resin.

[0026] [ka]

[0027] [In formula (8), each Ar independently represents an aromatic hydrocarbon group having from 6 to 14 carbon atoms, and some of the hydrogen atoms constituting the aromatic hydrocarbon group may be substituted with a substituent selected from the group consisting of an alkyl group having from 1 to 10 carbon atoms, an aryl group and an arylalkyl group having from 6 to 10 carbon atoms, a cycloalkyl group and a cycloalkylalkyl group having from 3 to 10 carbon atoms, an alkoxy group having from 1 to 5 carbon atoms, and a halogen group; Each R1 is independently an alkylene group having 2 to 4 carbon atoms, each l is independently a number between 0 and 3, W's are each independently a hydrogen atom, a (meth)acryloyl group, a functional group represented by the following general formula (9), or a functional group represented by the following general formula (10), and at least one of W's is a (meth)acryloyl group, a functional group represented by the following general formula (9), or a functional group represented by the following general formula (10), X's are each independently -CO-, -SO2-, -C(CH3)2-, -C(CF3)2-, -Si(CH3)2-, -O-, -CH2-, a single bond, or a group represented by the following general formula (11):

[0028] [ka]

[0029] [ka]

[0030] [In formulas (9) and (10), each R3 is independently a divalent saturated hydrocarbon group having 2 to 20 carbon atoms, R5 is a saturated or unsaturated divalent hydrocarbon group having from 2 to 20 carbon atoms, R6 is an alkylene group or alkylarylene group having from 2 to 10 carbon atoms, R7 is a hydrogen atom or a methyl group; m is a number between 0 and 10, * indicates the binding site to the structure represented by general formula (8).

[0031] [ka]

[0032] [In formula (11), * indicates the bonding site to the structure represented by general formula (8)]

[0033] [ka]

[0034] [In formula (12), Y represents a tetravalent carboxylic acid residue obtained by removing a carboxy group from one selected from the group consisting of saturated linear hydrocarbon tetracarboxylic acids which may be substituted with saturated cyclic hydrocarbons, alicyclic tetracarboxylic acids which may be substituted with saturated hydrocarbons, and aromatic tetracarboxylic acids. (Note that the expression "tetravalent carboxylic acid residue" refers to the structure of a moiety obtained by removing a carboxy group from one selected from the group consisting of the tetracarboxylic acids, and this structure is the same as the structure of the residue obtained by removing the acid dianhydride group from the acid dianhydride of the tetracarboxylic acid. Therefore, although the compound represented by formula (12) is an acid dianhydride, the expression "carboxylic acid residue" is used for Y in this specification.]

[0035] [ka]

[0036] [In formula (13), V is a carboxylic acid residue obtained by removing a carboxy group from one selected from the group consisting of saturated linear hydrocarbon dicarboxylic acids which may be substituted with a hydrocarbon group, saturated cyclic hydrocarbon dicarboxylic acids which may be substituted with a saturated hydrocarbon group, unsaturated dicarboxylic acids, aromatic dicarboxylic acids, citric acid, trimellitic acid, and hexahydrotrimellitic acid, q is 1 or 2.]

[0037] [ka]

[0038] [In formula (14), R2 represents a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, Each R3 is independently a divalent saturated hydrocarbon group having 2 to 20 carbon atoms, R4 is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, m is a number between 0 and 10.

[0039] [4] (A) the unsaturated group-containing polymerizable resin according to [1] or [2]; (B) a photosensitizer, and (C) a solvent, A photosensitive resin composition comprising:

[0040] [5] The photosensitive resin composition according to [4], which contains (D) an epoxy compound having two or more epoxy groups.

[0041] [6] A cured resin film obtained by curing the photosensitive resin composition according to [4] or [5].

[0042] [7] A laminate comprising an adhesive layer between a light-transmitting support and an adherend, the adhesive layer comprising a dried coating film or a cured film of the photosensitive resin composition according to [4] or [5]. (Note that, in such a laminate, the support and the adherend can be separated from the laminate by irradiating light from the support side.)

[0043] [8] A step of forming an adhesive layer on the surface of either or both of a light-transmitting support and an adherend using the photosensitive resin composition according to [4] or [5]; a step of adhering the support and the adherend via the adhesive layer formed in the step to obtain a laminate; A method for producing a laminate comprising the steps of:

[0044] [9] A step of forming an adhesive layer on the surface of one or both of a light-transmitting support and an adherend included in a laminate structure of an adherend and a holding substrate (an adherend held on a holding substrate) using the photosensitive resin composition according to [4] or [5]; a step of adhering the support and the laminated structure via the adhesive layer formed in the step to obtain a laminate in which the support, the adhesive layer, the adherend, and the holding substrate are laminated in this order; a step of exposing the adhesive layer to light from the holding substrate side; peeling the holding substrate from the laminate with light; forming a pattern in the adhesive layer by development; A method for producing a laminate comprising the steps of:

[0045]

[10] A step of preparing a laminate having an adhesive layer formed of a cured film of the photosensitive resin composition according to [4] or [5] between a light-transmitting support and an adherend; a step of irradiating the adhesive layer with light to separate the support and the adherend; Including, The support transmits light with a wavelength of 10 nm or more and 400 nm or less, and A method for treating a laminate, wherein, when separating the support and the adherend, the support and the adherend are separated by irradiating the adhesive layer with light from the support side. [Effects of the Invention]

[0046] According to the present invention, it is possible to provide an unsaturated group-containing polymerizable resin that can be used as a positive resist, has excellent patterning properties, is capable of forming a cured film having high adhesive strength without performing a bleaching step, and can provide excellent peelability when the cured film is irradiated with a laser, and that can be suitably used as a material for a photosensitive resin composition, and a method for producing the same.

[0047] Furthermore, according to the present invention, it is possible to provide a photosensitive resin composition using such an unsaturated group-containing polymerizable resin, which can be used as a positive resist, has excellent patterning properties, is capable of forming a cured film with high adhesive strength without performing a bleaching process, and enables the cured film to have excellent peelability when irradiated with a laser. Furthermore, according to the present invention, it is possible to provide a cured resin film and a laminate using such a photosensitive resin composition, as well as a method for manufacturing and processing such a laminate. Note that in the patterning process using the photosensitive resin composition as a positive resist, it is possible to form a cured film with high adhesive strength even when a bleaching process is included, so it is also possible to provide a positive resist with little process dependency using such a photosensitive resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0048] The present invention will be described in detail below based on preferred embodiments thereof.

[0049] [Polymerizable resin containing unsaturated group] The unsaturated group-containing polymerizable resin of the present invention contains a compound represented by the following general formula (1).

[0050] [ka]

[0051] In formula (1), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and some of the hydrogen atoms constituting the aromatic hydrocarbon group may be substituted with a substituent selected from the group consisting of alkyl groups having 1 to 10 carbon atoms, aryl groups and arylalkyl groups having 6 to 10 carbon atoms, cycloalkyl groups and cycloalkylalkyl groups having 3 to 10 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, and halogen groups (thus, each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, which may have the aforementioned substituent). Also, in formula (1), each R is independently an alkylene group having 2 to 4 carbon atoms, and each l is independently a number from 0 to 3. Furthermore, in formula (1), each G is independently a hydrogen atom or a substituent represented by the following general formula (2), and at least one of the Gs is a substituent represented by the following general formula (2). In addition, in formula (1), each W is independently a hydrogen atom, a (meth)acryloyl group, a functional group represented by the following general formula (3), or a functional group represented by the following general formula (4), and at least one of W is a (meth)acryloyl group, a functional group represented by the following general formula (3), or a functional group represented by the following general formula (4). Furthermore, in formula (1), L is a substituent represented by the following general formula (5), and each X is independently -CO-, -SO2-, -C(CH3)2-, -C(CF3)2-, -Si(CH3)2-, -O-, -CH2-, a single bond, or a group represented by the following general formula (6). In addition, in formula (1), Y is a tetravalent carboxylic acid residue obtained by removing a carboxy group from one selected from saturated linear hydrocarbon tetracarboxylic acids which may be substituted with saturated cyclic hydrocarbons, alicyclic tetracarboxylic acids which may be substituted with saturated hydrocarbons, and aromatic tetracarboxylic acids, and n is a natural number (a numerical value indicating the number of structural moieties in parentheses in formula (1) (the number of units when one structure in parentheses is counted as one unit)).

[0052] The aromatic hydrocarbon group selected as Ar may have any of the carbon atoms within the above range, and may be either substituted or unsubstituted. When the aromatic hydrocarbon group has a substituent, the number of carbon atoms in the aromatic hydrocarbon group does not include the number of carbon atoms in the substituent within the range of 6 to 14 (preferably 6 to 10). Examples of aromatic hydrocarbon groups selected as Ar include o-, m-, and p-phenylene, toluylene, ethylphenylene, n-propylphenylene, isopropylphenylene, linear or branched butylphenylene, pentylphenylene, and divalent naphthyl. Furthermore, aromatic hydrocarbon groups substituted with 2 to 4 substituents can also be suitably used.

[0053] Furthermore, as described above, in the aromatic hydrocarbon group selected as Ar, some of the hydrogen atoms constituting the aromatic hydrocarbon group may be substituted with a substituent selected from the group consisting of alkyl groups having from 1 to 10 carbon atoms, aryl groups and arylalkyl groups having from 6 to 10 carbon atoms, cycloalkyl groups and cycloalkylalkyl groups having from 3 to 10 carbon atoms, alkoxy groups having from 1 to 5 carbon atoms, and halogen groups.

[0054] Furthermore, from the viewpoint of enhancing light absorption during laser ablation, Ar is preferably a phenylene group, which is an aryl group having 6 carbon atoms, or a naphthylene group, which is an aryl group having 10 carbon atoms.

[0055] Each R1 is independently an alkylene group having 2 to 4 carbon atoms, and preferably an alkylene group having 2 to 3 carbon atoms.

[0056] Furthermore, each 1 in the formula is independently a number of 0 to 3. From the viewpoint of enhancing solubility in a developer, the value of 1 is preferably 0 or 1, and more preferably 0.

[0057] The substituents represented by general formula (2) that can be selected as G are as follows:

[0058] [ka]

[0059] [In formula (2), R2 is a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, Each R3 is independently a divalent saturated hydrocarbon group having 2 to 20 carbon atoms, R4 is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, Z is a hydrogen atom or a substituent represented by the following general formula (7), and at least one of Z satisfies the condition that it is a substituent represented by the following general formula (7), m is a number between 0 and 10, * indicates the binding site to the structure represented by general formula (1).

[0060] Here, the divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms that can be selected as R2 may have a linear, branched, or cyclic structure. From the viewpoint of improving adhesion to the substrate, the divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms) that can be selected as R2 is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

[0061] Furthermore, the divalent saturated hydrocarbon group having from 2 to 20 carbon atoms that can be selected as R3 may have either a linear or branched structure. From the viewpoint of improving adhesion of the cured resin film to the substrate, the divalent saturated hydrocarbon group having from 2 to 20 carbon atoms that can be selected as R3 is more preferably one having from 3 to 15 carbon atoms.

[0062] Furthermore, the aliphatic hydrocarbon group having from 1 to 5 carbon atoms that can be selected as R4 may have any of a linear, branched, or cyclic structure. From the viewpoint of achieving high adhesive strength of the cured resin film, the aliphatic hydrocarbon group having from 1 to 5 carbon atoms that can be selected as R4 preferably has from 1 to 3 carbon atoms.

[0063] Furthermore, m in formula (2) is a number of 0 or more and 10 or less (more preferably 0 or more and 7 or less).

[0064] Furthermore, the substituents represented by general formula (7) that can be selected as Z in formula (2) are as follows:

[0065] [ka]

[0066] In formula (7), V is a carboxylic acid residue obtained by removing a carboxy group from one selected from the group consisting of saturated linear hydrocarbon dicarboxylic acids which may be substituted with a hydrocarbon group, saturated cyclic hydrocarbon dicarboxylic acids which may be substituted with a saturated hydrocarbon group, unsaturated dicarboxylic acids, aromatic dicarboxylic acids, citric acid, trimellitic acid, and hexahydrotrimellitic acid, and q is 1 or 2.

[0067] With respect to V in formula (7), examples of the saturated linear hydrocarbon dicarboxylic acid include 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. Examples of the saturated cyclic hydrocarbon dicarboxylic acid include hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornanedicarboxylic acid, and hexahydrotrimellitic acid. Examples of the unsaturated dicarboxylic acid or aromatic dicarboxylic acid include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methyl-endomethylenetetrahydrophthalic acid, and chlorendic acid.

[0068] Furthermore, from the viewpoint of increasing solubility in a developer, V in the formula (7) is more preferably a carboxylic acid residue obtained by removing a carboxy group from one selected from the group consisting of succinic acid, phthalic acid, tetrahydrophthalic acid, itaconic acid, hexahydrotrimellitic acid, and trimellitic acid.

[0069] In addition, q in the formula (7) is preferably 1 from the viewpoint of increasing the solubility contrast in the developer between the insolubilized portion and the soluble portion.

[0070] Furthermore, Z in formula (7) is more preferably a substituent represented by general formula (7) from the viewpoint of improving developer solubility and contrast.

[0071] In addition, in formula (1), G in the group selected as L is treated as G in formula (5), and G in formula (1) means G directly described in formula (1). Therefore, with regard to the description of G in formula (1), the provision that "each G is independently a hydrogen atom or a substituent represented by the following general formula (2), and at least one of the G (excluding G in the group selected as L) satisfies the condition that it is a substituent represented by the following general formula (2)" is a provision regarding G (excluding G in L) in formula (1). Thus, in the present invention, at least one of the G in formula (1) (excluding G in the group selected as L) is a substituent represented by the above general formula (2). This makes it possible to improve the adhesion of the cured resin film to the substrate while increasing the contrast of the developer solubility. Furthermore, it is more preferable that all of G in such formula (1) (here, excluding G in the group selected as L) be a substituent represented by general formula (2) from the viewpoints of increasing the adhesion of the cured resin film to the substrate and increasing the contrast of the solubility in a developer.

[0072] In addition, in W in formula (1), the (meth)acryloyl group means either an acryloyl group or a methacryloyl group. In addition, the substituents represented by general formula (3) and general formula (4) that can be selected as W in formula (1) are as follows:

[0073] [ka]

[0074] [ka]

[0075] In formulas (3) and (4), each R3 is independently a divalent saturated hydrocarbon group having from 2 to 20 carbon atoms, R5 is a saturated or unsaturated divalent hydrocarbon group having from 2 to 20 carbon atoms, R6 is an alkylene group or alkylarylene group having from 2 to 10 carbon atoms, R7 is a hydrogen atom or a methyl group, m is a number from 0 to 10, and * indicates a bonding site to the structure represented by general formula (1).

[0076] R3 in formula (4) has the same meaning as R3 in formula (2). R5 is a saturated or unsaturated divalent hydrocarbon group having from 2 to 20 carbon atoms (more preferably from 2 to 10 carbon atoms). Examples of divalent hydrocarbon groups that can be selected as R5 include alkylene groups, alkylarylene groups, and arylene groups, each having a carbon number within the above range. Suitable examples of divalent hydrocarbon groups that can be selected as R5 include ethylene, ethylidene, vinylene, vinylidene, propylene, trimethylene, propenylene, isopropylidene, and tetramethylene groups.

[0077] The alkylene group that can be selected as R6 may have either a linear or branched structure, and examples thereof include an ethylene group, an ethylidene group, a vinylene group, a vinylidene group, a propylene group, a trimethylene group, a propenylene group, an isopropylidene group, a tetramethylene group, etc. The alkylarylene group that can be selected as R6 may be an unsubstituted arylene group as long as it is within the above-mentioned range of carbon number, and examples thereof include o-, m-, p-phenylene, toluylene, ethylphenylene, n-propylphenylene, isopropylphenylene, linear or branched butylphenylene, pentylphenylene, etc.

[0078] Furthermore, R7 is a hydrogen atom or a methyl group, but from the viewpoint of increasing reactivity, a hydrogen atom is more preferable.

[0079] Furthermore, m in formula (4) is a number of 0 or more and 10 or less (more preferably 0 or more and 5 or less).

[0080] Furthermore, W in formula (1) is more preferably a (meth)acryloyl group (particularly preferably an acryloyl group) from the viewpoint of improving the adhesion of the cured resin film to the substrate.

[0081] Furthermore, the substituents represented by the following general formula (5) that can be selected as L in formula (1) are as follows.

[0082] [ka]

[0083] In formula (5), V is a carboxylic acid residue obtained by removing a carboxy group from one selected from the group consisting of saturated linear hydrocarbon dicarboxylic acids which may be substituted with a hydrocarbon group, saturated cyclic hydrocarbon dicarboxylic acids which may be substituted with a saturated hydrocarbon group, unsaturated dicarboxylic acids, aromatic dicarboxylic acids, citric acid, trimellitic acid, and hexahydrotrimellitic acid, each G is independently a hydrogen atom or a substituent represented by the following general formula (2), and at least one of the Gs in formula (5) is a substituent represented by the following general formula (2), q is 1 or 2, and * indicates the bonding site to the structure represented by general formula (1). The carboxylic acid residues which can be selected as V have the same meaning as those explained in formula (7) above.

[0084] In the present invention, formula (1) contains two Ls, and it is necessary to satisfy the condition that at least one of Gs (total number of 2 or more) in the two substituents represented by the above general formula (5) selected as Ls is a substituent represented by the general formula (2). Here, the group or atom that can be selected as G has the same meaning as G described in general formula (1). Furthermore, from the viewpoint of improving adhesion to the cured resin film substrate and increasing contrast in developer solubility, it is more preferable that all of Gs in formula (5) are substituents represented by general formula (2).

[0085] Furthermore, q in formula (5) is more preferably 1 from the viewpoint of increasing the adhesion of the cured resin film to the substrate and increasing the contrast of the developer solubility.

[0086] In formula (1), X's are each independently -CO-, -SO2-, -C(CH3)2-, -C(CF3)2-, -Si(CH3)2-, -O-, -CH2-, a single bond, or a group represented by the following general formula (6). Here, groups represented by the following general formula (6) that can be selected as X are as follows. Note that * in the following general formula (6) indicates the bonding site to the structure represented by general formula (1).

[0087] [ka]

[0088] Furthermore, X in formula (1) is preferably a group represented by the above general formula (6), from the viewpoint of improving the solvent resistance and adhesion to the substrate of the cured resin film.

[0089] Furthermore, in formula (1), Y is a tetravalent carboxylic acid residue obtained by removing a carboxy group from one selected from saturated linear hydrocarbon tetracarboxylic acids which may be substituted with saturated cyclic hydrocarbons, alicyclic tetracarboxylic acids which may be substituted with saturated hydrocarbons, and aromatic tetracarboxylic acids. Examples of the saturated linear hydrocarbon tetracarboxylic acids include butane tetracarboxylic acid, pentane tetracarboxylic acid, and hexane tetracarboxylic acid. Examples of the alicyclic tetracarboxylic acids include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, and norbornane tetracarboxylic acid. Examples of the aromatic tetracarboxylic acids include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and biphenyl ether tetracarboxylic acid.

[0090] It is preferable that Y contains at least one aromatic hydrocarbon group. Examples of such aromatic hydrocarbon groups include a phenyl group, a biphenyl group, a benzophenone group, a naphthalene group, and a biphenyl ether group. Among such aromatic hydrocarbon groups, a biphenyl group, a benzophenone group, or a naphthalene group is preferred.

[0091] Furthermore, from the viewpoints of improving the adhesion of the cured resin film to the substrate and increasing the contrast of the solubility in the developer, Y is preferably a tetracarboxylic acid residue obtained by removing a carboxy group from one selected from biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, diphenylethertetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid, and more preferably a tetracarboxylic acid residue obtained by removing a carboxy group from one selected from biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid.

[0092] Furthermore, n in formula (1) is a natural number and indicates the number of structural moieties (structural units) in parentheses in formula (1) contained in the molecule, and is preferably a value selected so that the average value of n for all compounds contained in the resin is 1 to 20 (more preferably 1 to 15). Furthermore, by using such a value of n, for example, when an unsaturated group-containing polymerizable resin is produced using the method for producing an unsaturated group-containing polymerizable resin of the present invention described below, the weight-average molecular weight of the resulting resin can be a value of 1,000 to 40,000.

[0093] Furthermore, a compound represented by general formula (1) contains at least one substituent represented by general formula (2) as G in general formula (1), and also contains at least one substituent represented by general formula (2) as G in L (a group represented by general formula (5)) in general formula (1). Therefore, the compound contains at least two substituents represented by general formula (2). Here, the provision regarding formula (2) that "satisfies the condition that at least one of Z is a substituent represented by general formula (7)" means that at least one of Z in such multiple substituents represented by general formula (2) satisfies the condition that it is a substituent represented by general formula (7). In this way, when multiple substituents represented by formula (2) are contained, each Z is independently a hydrogen atom or a substituent represented by the following general formula (7), and the condition that at least one of the multiple Z is a substituent represented by general formula (7) is satisfied. From the viewpoint of improving developer solubility and contrast, it is preferable that in the compound represented by general formula (1), all of the substituents represented by general formula (2) contained in the compound are substituents represented by general formula (7).

[0094] Furthermore, in formula (1), the condition that at least one of W is a (meth)acryloyl group, a functional group represented by the following general formula (3), or a functional group represented by the following general formula (4) is satisfied. Here, from the viewpoint of improving adhesion to the cured resin film substrate, it is preferable that 30 to 100% (more preferably 50 to 100%) of the Ws present in formula (1) are (meth)acryloyl groups, functional groups represented by the following general formula (3), or functional groups represented by the following general formula (4). It is more preferable that all Ws in formula (1) are (meth)acryloyl groups.

[0095] Furthermore, the unsaturated group-containing polymerizable resin of the present invention is not particularly limited as long as it contains a compound represented by formula (1), but is preferably a resin obtained by the method for producing the unsaturated group-containing polymerizable resin of the present invention described below.

[0096] Furthermore, such unsaturated group-containing polymerizable resins of the present invention may contain a compound represented by the general formula (1) without any particular limitation. In addition to the above compound, they may also contain a compound (i) having a structure represented by formula (1) in which each G is a hydrogen atom, a compound (ii) having a structure represented by formula (1) in which each Z is a hydrogen atom, and a compound (iii) having a structure represented by formula (1) in which each G and Z is a hydrogen atom. This is because, when a resin comprising a compound according to the present invention is produced using the method for producing an unsaturated group-containing polymerizable resin of the present invention described below, the aforementioned compounds (i) to (iii) may be formed in addition to the compound represented by formula (1) (the compound according to the present invention) depending on the degree of reaction progress, reaction conditions, etc. Thus, the unsaturated group-containing polymerizable resin of the present invention may be a mixture of the compound according to the present invention and at least one of the compounds (i) to (iii). When the unsaturated group-containing polymerizable resin of the present invention is composed of the above mixture, from the viewpoint of improving adhesion to the resin cured film substrate and increasing contrast in developer solubility, it is preferable that 20% or more of G (including G in L) in the formula of all compounds be substituents represented by the above general formula (2). Similarly, when the unsaturated group-containing polymerizable resin of the present invention is composed of the above mixture, it is preferable that 25% or more of Z (including G in L) in the formula of all compounds be substituents represented by the above general formula (7) in terms of improving solubility in an alkaline developer.

[0097] In addition, since the unsaturated group-containing polymerizable resin of the present invention can efficiently obtain the effects derived from the structure of the compound represented by the above general formula (1) (where G, Z, etc. satisfy the conditions described in the formula), it is preferable that it mainly contains the compound represented by the above general formula (1), and it is particularly preferable that it consists only of the compound represented by the above general formula (1). Here, "mainly" means that 40 mass % or more (more preferably 60 mass % or more) of all compounds contained in the resin are the compound represented by the above formula (1).

[0098] Furthermore, the unsaturated group-containing polymerizable resin (the aggregate of the aforementioned compounds) of the present invention is not particularly limited, but preferably has a weight-average molecular weight of 1,000 to 40,000 (more preferably 1,500 to 30,000, and even more preferably 2,000 to 15,000). A weight-average molecular weight of 1,000 or more is more effective in improving adhesion between the support and the adherend. Furthermore, a weight-average molecular weight of 40,000 or less is more effective in that it is easier to adjust the solution viscosity of the photosensitive resin composition to a level suitable for coating, and it does not take too long to apply the composition to the surface of the support or adherend. The weight-average molecular weight used here refers to the value determined by the method described in the "Measurement of Weight-Average Molecular Weight" section of the Examples section (polystyrene-equivalent weight-average molecular weight (Mw) measured by gel permeation chromatography (GPC) (HLC-8220GPC, manufactured by Tosoh Corporation)).

[0099] Furthermore, the unsaturated group-containing polymerizable resin of the present invention is not particularly limited, but preferably has an acid value of 20 mgKOH / g or more and 200 mgKOH / g or less (more preferably 20 mgKOH / g or more and 150 mgKOH / g or less, and even more preferably 25 mgKOH / g or more and 100 mgKOH / g or less). When the acid value is 20 mgKOH / g or more, a greater effect can be obtained in that residues are less likely to remain during alkaline development. Furthermore, when the acid value is 200 mgKOH / g or less, penetration of the alkaline developer does not become too rapid, and a greater effect can be obtained in that peeling development can be suppressed. The acid value is determined by the method described in the "Oxidation Measurement" section of the Examples section.

[0100] The method for producing the unsaturated group-containing polymerizable resin of the present invention is not particularly limited, but it is preferable to employ the method for producing the unsaturated group-containing polymerizable resin of the present invention described below.

[0101] [Method for producing unsaturated group-containing polymerizable resin] The method for producing the unsaturated group-containing polymerizable resin of the present invention comprises the steps of: a diol compound (a-1) represented by the following general formula (8); a tetracarboxylic dianhydride (a-2) represented by the following general formula (12), A dicarboxylic acid monoanhydride (a-3) represented by the following general formula (13) and in which q is 1; to obtain a first reactant having a carboxy group (hereinafter, for convenience, sometimes simply referred to as "step (A)"); a step of reacting the first reactant with an oxirane compound (a-4) represented by the following general formula (14) to obtain a second reactant having a hydroxyl group (hereinafter, for convenience, sometimes simply referred to as "step (B)"); a step of reacting the second reactant having a hydroxyl group with a dicarboxylic acid monoanhydride (a-5) represented by the following general formula (13) to obtain the unsaturated group-containing polymerizable resin of the present invention (hereinafter, for convenience, sometimes simply referred to as "step (C)"); Including, the molar amount of the component (a-4) used when reacting the component (a-4) with the first reactant is an amount such that the molar ratio ([component (a-4)] / [(2×[component (a-2)]))+[component (a-3)]] of the sum of twice the molar amount of the component (a-2) used in producing the first reactant and the molar amount of the component (a-3) used in producing the first reactant is 0.5 or more and 2.0 or less, and The molar amount of the component (a-5) used when reacting the second reactant with the component (a-5) is an amount such that the molar ratio ([component (a-5)] / [component (a-4)]) to the molar amount of the component (a-4) used when reacting the first reactant with the component (a-4) is 0.5 or more and 2.0 or less. Hereinafter, the components used in this production method will be described first, and then each step will be described.

[0102] <Ingredients used in the above method> <Diol compound (a-1): component (a-1)> The diol compound (a-1) used in the above method is a compound represented by the following general formula (8).

[0103] [ka]

[0104] In formula (8), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and some of the hydrogen atoms constituting the aromatic hydrocarbon group may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group and an arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group and a cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group. In addition, in formula (8), each R1 is independently an alkylene group having 2 to 4 carbon atoms, each 1 is independently a number of 0 to 3, each W is independently a hydrogen atom, a (meth)acryloyl group, a functional group represented by the following general formula (9), or a functional group represented by the following general formula (10), and at least one of W is a (meth)acryloyl group, a functional group represented by the following general formula (9), or a functional group represented by the following general formula (10), and each X is independently -CO-, -SO2-, -C(CH3)2-, -C(CF3)2-, -Si(CH3)2-, -O-, -CH2-, a single bond, or a group represented by the following general formula (11).

[0105] [ka]

[0106] [ka]

[0107] [In formulas (9) and (10), each R3 is independently a divalent saturated hydrocarbon group having 2 to 20 carbon atoms, R5 is a saturated or unsaturated divalent hydrocarbon group having from 2 to 20 carbon atoms, R6 is an alkylene group or alkylarylene group having from 2 to 10 carbon atoms, R7 is a hydrogen atom or a methyl group; m is a number between 0 and 10, * indicates the binding site to the structure represented by general formula (8).

[0108] [ka]

[0109] [In formula (11), * indicates the bonding site to the structure represented by general formula (8)] Ar, R, l, W, and X in formula (8) have the same meanings as those in formula (1) (the same applies to their preferred meanings). The functional group represented by general formula (9), the functional group represented by general formula (10), and the group represented by general formula (11) are each synonymous with the functional group represented by general formula (3) and (4) and the group represented by general formula (6), except that the compound to which the moiety represented by * is bonded is formula (8). Therefore, R, R, R, R, and m in formulas (9) and (10) have the same meanings as those in general formulas (3) and (4) (the preferred meanings are also synonymous). Formula (8) satisfies the condition that at least one of W is a (meth)acryloyl group, a functional group represented by general formula (9), or a functional group represented by general formula (10). Therefore, the diol compound (a-1) can be said to be a compound containing at least one polymerizable double bond.

[0110] In addition, as the diol compound (a-1) represented by such formula (8), known compounds can be appropriately used, for example, the compound disclosed in JP 2023-8789 A as "diol (d) represented by general formula (8)", the compound disclosed in JP 2022-65423 A as "diol (d) represented by general formula (8)", the compound disclosed in JP 2022-65426 A as "diol (d) represented by general formula (8)", etc. can be appropriately used. In addition, the production method of such diol compound (a-1) is not particularly limited, and methods described in known documents such as JP 2023-8789 A, JP 2022-65423 A, and JP 2022-65426 A can be appropriately adopted. For example, when the structure of X is other than the group represented by formula (11) (fluorene structure), the method may be produced by referring to the methods described in JP-A-2023-8789, JP-A-2022-65423, JP-A-2022-65426, etc., except for appropriately changing the structure of the X portion. Such diol compounds (a-1) may be used alone or in combination of two or more.

[0111] Here, as a preferred example of the method for producing diol compound (a-1), a method suitable for producing diol compound (a-1) represented by the above general formula (8) in which X is a group represented by general formula (11) will be described below. An example of such a method is a method in which an epoxy compound represented by the following general formula (20) is reacted with at least one selected from the group consisting of (meth)acrylic acid and (meth)acrylic acid derivatives represented by the following general formulas (21) and (22) to obtain diol compound (a-1) represented by the above general formula (8) in which X is a group represented by general formula (11).

[0112] [ka]

[0113] Ar, R1 and l in formula (20) have the same meanings as Ar, R1 and l in formulas (1) and (8), respectively (preferred meanings are also the same).

[0114] [ka]

[0115] [ka]

[0116] R3, R5, R6, R7 and m in formulae (21) and (22) have the same meanings as R3, R5, R6, R7 and m in formulae (3) and (4), respectively (preferred meanings are also the same).

[0117] Such a reaction is usually carried out in a solvent (using a catalyst as necessary). Examples of such a solvent include cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate; high-boiling ether 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. The reaction conditions, such as the solvent and catalyst used, are not particularly limited; however, it is preferable to use, for example, a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature as the reaction solvent.

[0118] In addition, it is preferable to use a catalyst for the reaction between an epoxy group and a carboxyl group or a hydroxyl group. Known catalysts can be used as appropriate (for example, JP-A-9-325494 discloses ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine). When carrying out such a reaction in a solvent, an antioxidant may be added to the solvent to prevent gelation due to excessive reaction. The antioxidant is not particularly limited, and known antioxidants such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-ethylphenol, 2,5-di-tert-amylhydroquinone, and 2,5-di-tert-butylhydroquinone can be used as appropriate.

[0119] <Tetracarboxylic acid dianhydride (a-2): component (a-2)> The tetracarboxylic dianhydride (a-2) used in the above method is a compound represented by the following general formula (12).

[0120] [ka]

[0121] In formula (12), Y represents a tetravalent carboxylic acid residue obtained by removing a carboxy group from one selected from the group consisting of saturated linear hydrocarbon tetracarboxylic acids which may be substituted with saturated cyclic hydrocarbons, alicyclic tetracarboxylic acids which may be substituted with saturated hydrocarbons, and aromatic tetracarboxylic acids. This Y has the same meaning as Y in formula (1). The "tetravalent carboxylic acid residue" referred to here is the same group (having the same structure) as the tetravalent acid dianhydride residue obtained by removing two acid anhydride groups from the acid dianhydride of one tetracarboxylic acid selected from the group consisting of the saturated linear hydrocarbon tetracarboxylic acids, the alicyclic tetracarboxylic acids, and the aromatic tetracarboxylic acids.

[0122] Suitable examples of such tetracarboxylic acid dianhydrides (a-2) include tetracarboxylic acid dianhydrides of saturated straight-chain hydrocarbons such as butane tetracarboxylic acid dianhydride, pentane tetracarboxylic acid dianhydride, and hexane tetracarboxylic acid dianhydride; alicyclic tetracarboxylic acid dianhydrides such as cyclobutane tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic acid dianhydride, cyclohexane tetracarboxylic acid dianhydride, cycloheptane tetracarboxylic acid dianhydride, and norbornane tetracarboxylic acid dianhydride; and aromatic tetracarboxylic acid dianhydrides such as pyromellitic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid dianhydride, and biphenyl ether tetracarboxylic acid dianhydride.

[0123] Among these, biphenyltetracarboxylic acid anhydride, benzophenonetetracarboxylic acid anhydride, diphenylethertetracarboxylic acid anhydride, naphthalene-1,4,5,8-tetracarboxylic acid anhydride, and naphthalene-2,3,6,7-tetracarboxylic acid anhydride are preferred, and biphenyltetracarboxylic acid anhydride, benzophenonetetracarboxylic acid anhydride, naphthalene-1,4,5,8-tetracarboxylic acid anhydride, and naphthalene-2,3,6,7-tetracarboxylic acid anhydride are more preferred. Such tetracarboxylic acid dianhydrides (a-2) may be used alone or in combination of two or more.

[0124] <Carboxylic acid monoanhydride (a-3): component (a-3)> The dicarboxylic acid monoanhydride (a-3) used in the above method is a compound represented by the following general formula (13).

[0125] [ka]

[0126] In formula (13), V is a carboxylic acid residue obtained by removing a carboxy group from one selected from the group consisting of saturated linear hydrocarbon dicarboxylic acids which may be substituted with a hydrocarbon group, saturated cyclic hydrocarbon dicarboxylic acids which may be substituted with a hydrocarbon group, unsaturated dicarboxylic acids, aromatic dicarboxylic acids, citric acid, trimellitic acid, and hexahydrotrimellitic acid, and q is 1 or 2. V and q in formula (13) have the same meanings as those in formulas (5) and (7) (the preferred meanings also have the same meanings). Note that, as dicarboxylic acid monoanhydride (a-3), it is preferable to use a compound in formula (13) where q is 1.

[0127] Examples of such dicarboxylic acid monoanhydrides (a-3) include succinic anhydride, acetylsuccinic anhydride, adipic anhydride, azelaic anhydride, citramalic anhydride, malonic anhydride, glutaric anhydride, citric anhydride, tartaric anhydride, oxoglutaric anhydride, pimelic anhydride, sebacic anhydride, suberic anhydride, diglycolic anhydride, hexahydrophthalic anhydride, cyclobutanedicarboxylic anhydride, cyclopentanedicarboxylic anhydride, norbornanedicarboxylic anhydride, hexahydrotrimellitic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl-endomethylenetetrahydrophthalic anhydride, and chlorendic anhydride. Among these dicarboxylic acid monoanhydrides (a-3), succinic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrotrimellitic anhydride, phthalic anhydride, trimellitic anhydride, 1,8-naphthalenedicarboxylic anhydride, and 2,3-naphthalenedicarboxylic anhydride are preferred. These dicarboxylic acid monoanhydrides (a-3) may be used alone or in combination of two or more.

[0128] <Oxirane compound (a-4): component (a-4)> The oxirane compound (a-4) used in the above method is a compound represented by the following general formula (14), which contains a polymerizable double bond and one oxirane ring.

[0129] [ka]

[0130] In formula (14), R2 is a divalent aliphatic hydrocarbon group having from 1 to 6 carbon atoms, each R3 is independently a divalent saturated hydrocarbon group having from 2 to 20 carbon atoms, R4 is a hydrogen atom or an aliphatic hydrocarbon group having from 1 to 5 carbon atoms, and m is a number from 0 to 10. R2, R3, R4, and m in formula (14) have the same meanings as those in formula (2) (and the preferred meanings thereof also have the same meanings).

[0131] Since such oxirane compounds (a-4) are oxirane compounds having a polymerizable unsaturated group, the use of such compounds makes it possible to introduce a polymerizable unsaturated group into the final resin. Examples of such oxirane compounds (a-4) include glycidyl methacrylate, 2-hydroxyethyl acrylate glycidyl ether, 3-hydroxypropyl acrylate glycidyl ether, and 4-hydroxybutyl acrylate glycidyl ether. Such oxirane compounds (a-4) may be used alone or in combination of two or more.

[0132] The dicarboxylic acid monoanhydride (a-5) used in the method is a compound represented by the general formula (13) and is the same as that described for the dicarboxylic acid monoanhydride (a-3). Such dicarboxylic acid monoanhydrides (a-5) may be used alone or in combination of two or more.

[0133] <About each process> The steps (A) to (C) in the method for producing an unsaturated group-containing polymerizable resin of the present invention will be described below.

[0134] <Process (A)> Step (A) is a step of reacting the diol compound (a-1), the tetracarboxylic dianhydride (a-2), and the dicarboxylic monoanhydride (a-3) to obtain a first reaction product having a carboxy group.

[0135] In step (A), the method for reacting the diol compound (a-1), the tetracarboxylic dianhydride (a-2), and the dicarboxylic monoanhydride (a-3) is not particularly limited as long as it is a method capable of reacting a diol, an acid dianhydride, and an acid monoanhydride, and known methods can be appropriately adopted. For example, JP-A-9-325494 describes a method for reacting an epoxy (meth)acrylate with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140° C., and such a method can be applied by appropriately setting conditions so that each component reacts.

[0136] In such a reaction, it is preferable to use the diol compound (a-1), the tetracarboxylic dianhydride (a-2), and the dicarboxylic monoanhydride (a-3) in such a manner that the molar ratio ([component (a-1)]:[component (a-2)]:[component (a-3)]) of each component is 1.0:0.2-1.0:0.01-1.0 (more preferably 1.0:0.2-0.8:0.01-0.8) so that the terminal of the resulting first reactant (compound) is a carboxy group.

[0137] In addition, during such a reaction, it is preferable to conduct the reaction so that the ratio of the molar amount of the tetracarboxylic dianhydride (a-2) plus half the molar amount of the dicarboxylic monoanhydride (a-3) to the molar amount of the diol compound (a-1) [molar ratio: ([component (a-2)] + [component (a-3) / 2]) / [component (a-1)] is greater than 0.5 and less than 1.0. By setting this molar ratio to 1.0 or less, the terminal of the resulting first reaction product does not become an acid anhydride, thereby suppressing an increase in the content of unreacted acid dianhydride and improving the stability over time of each composition. Furthermore, when the molar ratio is greater than 0.5, an increase in the amount of unreacted components remaining in the diol compound (a-1) containing a polymerizable unsaturated group can be suppressed, thereby improving the stability over time of each composition.

[0138] Such reactions are typically carried out in a solvent, optionally with the use of a catalyst. Examples of such solvents include cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate; high-boiling ether or ester 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. Japanese Patent Application Laid-Open No. 9-325494 discloses examples of such catalysts, including ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine. While the reaction conditions, such as the solvent and catalyst used, are not particularly limited, it is preferable to use, for example, a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature as the reaction solvent. Furthermore, for example, when the diol compound (a-1) is produced in a solvent by referring to the methods described in JP 2023-8789 A, JP 2022-65423 A, JP 2022-65426 A, etc., the diol compound (a-1) is produced in the solvent to obtain a solution containing the diol compound (a-1). After that, the solution may be used as it is, and mixed with each component to cause a reaction.

[0139] The first reactant obtained in step (A) is a compound having a carboxy group, as represented by the following formula (15): The compound represented by the following formula (15) is a preferred embodiment of the first reactant.

[0140] [ka]

[0141] In formula (15), Ar, X, Y, W, R1, and l are each defined as those in formula (1), and L' is a group represented by the following formula (16).

[0142] [ka]

[0143] In formula (16), V and q have the same meanings as V and q in formula (7), and * indicates the bonding site to the structure represented by formula (15).

[0144] Thus, after the first reactant is obtained in step (A), step (B) is carried out in the present invention.

[0145] <Process (B)> Step (B) is a step of reacting the first reactant with the oxirane compound (a-4) to obtain a second reactant having a hydroxyl group.

[0146] The oxirane compound (a-4) is an oxirane compound (epoxy compound) having a polymerizable unsaturated group, and is a compound that can react with the carboxy group of the first reactant to introduce a polymerizable unsaturated group into the reactant.

[0147] The reaction between the first reactant and the oxirane compound (a-4) is a reaction (addition reaction) between the carboxy group of the first reactant and the epoxy group of the oxirane compound (a-4). The conditions for this reaction are not particularly limited, and general reaction conditions for the addition reaction of a carboxylic acid and an oxirane compound can be appropriately adopted. For example, a preferable example is a reaction temperature in the range of 40 to 120°C.

[0148] Furthermore, in step (B), the amount (molar amount) of component (a-4) used when reacting component (a-4) with the first reactant needs to be an amount such that the molar ratio ([component (a-4)] / [(2 × [component (a-2)]) + [component (a-3)]] of the sum of twice the molar amount of component (a-2) used in producing the first reactant and the molar amount of component (a-3) used in producing the first reactant is 0.5 or more and 2.0 or less (more preferably 0.5 or more and 1.5 or less). By setting this molar ratio to 0.5 or more, an increase in the amount of unreacted components remaining in component (a-4) can be suppressed, thereby achieving a significant effect in terms of improving stability over time. On the other hand, by setting this molar ratio to 2.0 or less, an increase in the amount of unreacted components remaining in the first reactant can be suppressed, thereby achieving a significant effect in terms of improving stability over time.

[0149] By reacting such a first reactant with the oxirane compound (a-4), the epoxy group site is cleaved to give a second reactant having a polymerizable unsaturated group and a hydroxyl group.

[0150] <Process (C)> Step (C) is a step of obtaining the unsaturated group-containing polymerizable resin of the present invention by reacting the second reactant having a hydroxyl group with a dicarboxylic acid monoanhydride (a-5) represented by the general formula (13). That is, step (C) can obtain a resin (a mixture of the compounds) composed of the compound represented by the general formula (1).

[0151] The reaction of such a second reactant with dicarboxylic acid monoanhydride (a-5) is a reaction between a hydroxyl group in the second reactant and an acid anhydride group in the dicarboxylic acid monoanhydride (a-5). The conditions for such a reaction are not particularly limited, and reaction conditions employed in known methods capable of reacting a hydroxyl group with an acid anhydride group can be appropriately employed. For example, a preferable example is a reaction temperature in the range of 40 to 120°C.

[0152] In step (C), the amount (molar amount) of component (a-5) used in reacting component (a-5) with the second reactant must be such that the molar ratio ([component (a-5)] / [component (a-4)]) of the amount of component (a-4) used in reacting component (a-4) with the first reactant is 0.5 or more and 2.0 or less (more preferably 0.5 or more and 1.5 or less). By setting the molar ratio at 0.5 or more, it is possible to suppress an increase in the amount of unreacted components remaining in component (a-5), thereby achieving a significant effect in terms of improving stability over time. On the other hand, by setting the molar ratio at 2.0 or less, it is possible to suppress an increase in the amount of unreacted components remaining in component (a-4), thereby achieving a significant effect in terms of improving stability over time. In this manner, the unsaturated group-containing polymerizable resin of the present invention can be produced.

[0153] [Photosensitive resin composition] The photosensitive resin composition of the present invention comprises: (A) the unsaturated group-containing polymerizable resin of the present invention; (B) a photosensitizer, and (C) a solvent, It includes:

[0154] The photosensitive resin composition of the present invention contains "the unsaturated group-containing polymerizable resin of the present invention" as component (A). In the photosensitive resin composition of the present invention, the content of component (A) is not particularly limited, but is preferably 30% by mass or more and 95% by mass or less (more preferably 50% by mass or more and 90% by mass or less) of the total solid content of the composition. By setting the content of component (A) at or above the lower limit, a greater effect tends to be obtained in terms of achieving a high contrast in the development solubility between exposed and unexposed areas. On the other hand, by setting the content at or below the upper limit, a greater effect tends to be obtained in terms of suppressing the development solubility of unexposed areas.

[0155] In the photosensitive resin composition of the present invention, the content of component (A) is preferably 10% by mass or more and 80% by mass or less (more preferably 20% by mass or more and 70% by mass or less) relative to the total amount of the composition. By setting the content of component (A) to the above lower limit or more, a greater effect tends to be obtained in terms of being able to increase the contrast in the development solubility between the exposed and unexposed areas, while by setting it to the above upper limit or less, a greater effect tends to be obtained in terms of being able to suppress the development solubility of the unexposed areas.

[0156] The photosensitive resin composition of the present invention also contains a "photosensitizer" as component (B). This photosensitizer as component (B) is used to increase the solubility of the exposed portion of the photosensitive resin composition in an alkaline developer by exposure. As this photosensitizer (B), any known compound that can be used in so-called positive resists can be used as appropriate, and is not particularly limited. Among these, quinone diazide compounds are preferred.

[0157] Such quinone diazide compounds are not particularly limited, and known compounds (for example, the quinone diazide compounds disclosed in JP-A-2003-29397) can be appropriately used. Examples of such quinone diazide compounds include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone Non-1,2-naphthoquinone diazide-5-sulfonic acid ester, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane-1,2-naphthoquinone diazide-4-sulfonic acid ester, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane-1,2-naphthoquinone diazide-5-sulfonic acid ester, 4,4'-[1-[4-[1-[4-hydroxid 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol-1,2-naphthoquinone diazide-4-sulfonic acid ester, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,2,4-trimethyl-7,2',4'-trihydroxyflavan-1,2-naphthoquinone diazide Suitable examples of component (B) that can be used include 1,1,1-tri(p-hydroxyphenyl)ethane-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2',4'-trihydroxyflavan-1,2-naphthoquinone diazide-5-sulfonic acid ester, 1,1,1-tri(p-hydroxyphenyl)ethane-1,2-naphthoquinone diazide-4-sulfonic acid ester, 1,1,1-tri(p-hydroxyphenyl)ethane-1,2-naphthoquinone diazide-5-sulfonic acid ester, etc. These component (B) can be used singly or in combination of two or more.

[0158] Furthermore, in the photosensitive resin composition of the present invention, the content of the component (B) is not particularly limited, but is preferably 5 to 100 parts by mass (more preferably 10 to 50 parts by mass) per 100 parts by mass of the component (A). If the amount of the component (B) is less than 5 parts by mass, the difference in solubility between the exposed area (irradiated area) and the unexposed area (unirradiated area) in the coating film formed from the photosensitive resin composition tends to be small, making patterning difficult. On the other hand, if the amount of the component (B) exceeds 100 parts by mass, the quinone diazide compound in the coating film will not be sufficiently decomposed by short-term irradiation, and as a result, sensitivity will tend to decrease.

[0159] In the photosensitive resin composition of the present invention, the content of component (B) is preferably 5 to 50 mass % (more preferably 10 to 30 mass %) of the total solid content of the composition. By setting the content of component (A) at or above the lower limit, a large difference in solubility occurs between the exposed and unexposed areas, and a greater effect tends to be obtained in terms of forming a fine pattern. On the other hand, by setting the content at or below the upper limit, a greater effect tends to be obtained in terms of developing strong adhesive strength to the adherend.

[0160] The photosensitive resin composition of the present invention also contains a "solvent" as component (C). Such a solvent is used to uniformly dissolve (disperse) each component in the composition, for example, to facilitate coating onto a substrate. Such a solvent is not particularly limited as long as it does not react with each component in the composition and can dissolve or disperse them, and known organic solvents can be used as appropriate. Examples of such organic solvents include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; and propylene glycol methyl ether. Examples of the alkyl ether include propylene glycol alkyl ether acetates such as propylene glycol teracetate and propylene glycol ethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone; and esters such as ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate.

[0161] Among these solvents, glycol ethers, alkylene glycol alkyl ether acetates, diethylene glycol dialkyl ethers, and diethylene glycols are preferred. Ethyl 3-ethoxypropionate, ethyl lactate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, methyl amyl ketone, and diethylene glycol ethyl methyl ether are particularly preferred. These solvents can be used alone or in combination of two or more.

[0162] In the photosensitive resin composition of the present invention, the content of component (C) is not particularly limited, but is preferably 5% by mass to 80% by mass (more preferably 20% by mass to 70% by mass) of the total amount of the composition. By setting the content of component (C) at or above the lower limit, the viscosity can be appropriately controlled, and the processability when applied to a substrate tends to be improved. On the other hand, by setting the content at or below the upper limit, a more uniform coating film tends to be formed more easily.

[0163] Furthermore, the photosensitive resin composition of the present invention can suitably be one that contains, in addition to the components (A), (B), and (C), an "epoxy compound having two or more epoxy groups" as component (D).

[0164] The epoxy compound having two or more epoxy groups as component (D) can be used as a crosslinking agent, and this compound enables the component (A) to form a sufficient crosslinked structure. Furthermore, the formation of such a crosslinked structure can improve the toughness of the cured film when it is formed.

[0165] Examples of such component (D) include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, bisnaphthol fluorene type epoxy compounds, diphenyl fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (e.g., NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), biphenyl type epoxy compounds (e.g., jER YX4000: manufactured by Mitsubishi Chemical Corporation, "jER" is a registered trademark of the company), naphthol aralkyl type epoxy compounds, trisphenolmethane type epoxy compounds (e.g., EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), tetrakisphenolethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polycarboxylic acids, copolymers of monomers having (meth)acrylic groups containing glycidyl (meth)acrylate as a unit, such as copolymers of methacrylic acid and glycidyl methacrylate, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (e.g., Celloxide 2021P: manufactured by Daicel Corporation, "Celloxa" Examples of epoxy compounds include butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone (e.g., Epolead GT401, manufactured by Daicel Corporation; "Epolead" is a registered trademark of the company), epoxy compounds having epoxycyclohexyl groups (e.g., HiREM-1, manufactured by Shikoku Chemicals Corporation), multifunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series, manufactured by DIC Corporation), 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150, manufactured by Daicel Corporation), epoxidized polybutadiene (e.g., NISSO-PB JP-100, manufactured by Nippon Soda Co., Ltd.; "NISSO-PB" is a registered trademark of the company), and epoxy compounds having a silicone skeleton. These compounds may be used alone or in combination.

[0166] Among these, component (D) is preferably a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol fluorene epoxy compound, a bisnaphthol fluorene epoxy compound, a phenol novolac epoxy compound, a cresol novolac epoxy compound, or a biphenyl epoxy compound, and more preferably a biphenyl epoxy compound. Use of a biphenyl epoxy compound makes it possible to achieve both the required mechanical strength and chemical resistance of the cured product and the patternability of the composition upon photocuring, and also allows for greater freedom in designing the composition.

[0167] The epoxy equivalent of the epoxy compound of component (D) is preferably 100 g / eq or more and 300 g / eq or less, more preferably 100 g / eq or more and 250 g / eq or less. The number average molecular weight (Mn) of the epoxy compound of component (D) is preferably 100 or more and 5000 or less. When the epoxy equivalent is 100 g / eq or more and the number average molecular weight (Mn) of the epoxy compound is 100 or more, a cured film having good solvent resistance can be obtained. When the epoxy equivalent is 300 g / eq or less and the number average molecular weight (Mn) is 5000 or less, sufficient alkali resistance can be maintained even when alkaline chemicals are used in a subsequent process.

[0168] The epoxy equivalent of the epoxy compound of component (D) can be determined by titration with a 1 / 10N perchloric acid solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) The number average molecular weight (Mn) of the epoxy compound can be determined, for example, by the aforementioned gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation).

[0169] The content of the epoxy compound of the component (D) is not particularly limited, but is preferably 1 to 50 parts by mass per 100 parts by weight of the component (A).

[0170] Furthermore, the photosensitive resin composition of the present invention may suitably contain, in addition to the components (A), (B), and (C), a "crosslinking agent" consisting of a compound other than an epoxy compound having two or more epoxy groups (component (D)) as component (E). Such component (E) may be used in combination with component (D). Among the crosslinking agents used as component (E), a "phenol compound" is more preferred from the viewpoint of adjusting the solubility of exposed and unexposed areas in the development step. That is, it is preferable that component (E) be a phenol compound (a crosslinking agent consisting of a phenol compound).

[0171] The "phenol compound" suitably used as component (E) can be any known phenol compound that can be used as a crosslinking agent in the field of photosensitive resin compositions, and is not particularly limited. Examples include TekP-4HBPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TML-BPAF (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TML-BPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), DML-POP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), DML-PC (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TMOM-BP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), HMOM-TPPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TMOM-BPS (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), and the like. Examples of such hydroxyphenyl ethers include bisphenol A (manufactured by Tokyo Chemical Industry Co., Ltd.), bisphenol B (manufactured by Tokyo Chemical Industry Co., Ltd.), bisphenol M (manufactured by Tokyo Chemical Industry Co., Ltd.), bisphenol A (manufactured by Tokyo Chemical Industry Co., Ltd.), and bis(4-hydroxyphenyl)sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0172] In addition to the components (A) to (E), the photosensitive resin composition of the present invention can also appropriately use other components that can be used in so-called positive resists. Such other components are not particularly limited, and known additives such as sensitizers, surfactants, adhesion promoters, antistatic agents, storage stabilizers, antifoaming agents, pigments, and dyes can be appropriately used. Furthermore, known components (e.g., components described in JP-A-2003-29397 (sensitizers, surfactants, etc.)) can also be appropriately used as each of these components. Furthermore, the photosensitive resin composition of the present invention can be easily prepared by uniformly mixing the aforementioned components.

[0173] [Cured resin film] The cured resin film of the present invention is obtained by curing the photosensitive resin composition of the present invention. The method for producing such a cured resin film is not particularly limited, and for example, a method may be employed in which the photosensitive resin composition of the present invention is applied to a substrate or the like, the solvent is removed to form a dry coating film, and then the dry coating film is cured.

[0174] When such a method is adopted, the step of forming a dry coating film is preferably a step of applying a photosensitive resin composition to a desired thickness and prebaking to remove the solvent to form a dry coating film. The method of applying the photosensitive resin composition is not particularly limited, and known methods can be appropriately used. For example, a solution immersion method; a spray method; or a method using known coating equipment such as a roller coater, land coater, slit coater, or spinner; etc., can be appropriately adopted. The prebaking method is also not particularly limited, and known methods can be appropriately adopted. For example, heating using an oven or hot plate, vacuum drying, or a heating method combining these can be adopted. The heating temperature and heating time in the prebaking are not particularly limited and can be appropriately designed depending on the solvent used. The prebaking conditions may be, for example, heating at a temperature of 80 to 120°C for 1 to 10 minutes.

[0175] The method for curing the dried coating film is not particularly limited, but is preferably a method in which the dried coating film is cured by completing polymerization or curing (both of which are sometimes collectively referred to as curing) by heating (post-baking). The heating temperature (curing temperature) during such curing is preferably 120°C or higher and 250°C or lower. The method for such post-baking is also not particularly limited, and any known method can be used as appropriate. For example, a method of heating using an oven, a hot plate, or the like, similar to pre-baking, may be used.

[0176] Furthermore, when producing a cured resin film in this manner, patterning may be performed by carrying out an exposure step and a development step before carrying out the post-baking, and then post-baking may be carried out to produce a cured resin film. Note that such exposure step and development step are not particularly limited, and known methods may be appropriately adopted, and the steps described below may also be adopted.

[0177] [Laminate] The laminate of the present invention comprises an adhesive layer formed between a light-transmitting support and an adherend, the adhesive layer comprising a dried coating film or a cured film of the photosensitive resin composition of the present invention.

[0178] <Support> The support may be any support capable of laminating (forming) an adhesive layer on its surface and capable of transmitting light, and the type of support is not particularly limited. Among such supports, those having laser transparency are preferred, more preferably those capable of transmitting light (laser) with a wavelength of 10 nm to 400 nm, and even more preferably those capable of transmitting light (laser) with a wavelength of 100 nm to 400 nm. Supports having such laser transparency are not particularly limited, and examples thereof include glass substrates, acrylic substrates, sapphire substrates, and quartz glass substrates. However, from the viewpoint of laser transparency, glass substrates and acrylic substrates having a composition that provides sufficient transmittance for the wavelength of light used are preferred. From the viewpoint of economy, glass substrates are preferred as such supports.

[0179] Such a support preferably has a transmittance of 70% or more for light with a wavelength of 200 nm or more and 800 nm or less across the entire wavelength range. This is because a support with such transmittance can sufficiently transmit a long-wavelength laser (e.g., 355 nm) irradiated from the support side to reach the adhesive layer. The transmittance of such a support can be measured using a UV-Vis-Infrared Spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation) as a numerical value with the transmittance of air as a baseline.

[0180] <Adherend> The adherend is not particularly limited, but suitable examples include semiconductor wafers, semiconductor chips, light-emitting elements (such as LEDs), optical glass wafers, metal foils, polishing pads, resin coatings, and wiring layers. Note that the adhesive layer described below has excellent patterning properties, can achieve high adhesion without a bleaching step, and exhibits excellent peelability when irradiated with a laser after curing, so it is preferable to use an LED chip as the adherend for laser transfer.

[0181] <Adhesive layer> The adhesive layer provided in the laminate of the present invention is a layer consisting of a dried coating film or a cured film thereof of the photosensitive resin composition of the present invention. The cured film of such a photosensitive resin composition is capable of sufficiently absorbing a long-wavelength laser (e.g., 355 nm) and can be sufficiently ablated by irradiation with such a laser, and therefore can be said to be a layer that can easily peel off an adherend by laser irradiation. Therefore, the properties of the adhesive layer enable the laminate of the present invention to have excellent laser processability. From the viewpoint of adhesive strength, the adhesive layer is more preferably a cured film (resin cured film) of the photosensitive resin composition of the present invention.

[0182] The thickness of such an adhesive layer can be arbitrarily designed depending on the application and is not particularly limited, but is preferably 0.1 μm to 50 μm, and more preferably 0.5 μm to 30 μm. When the thickness of the adhesive layer is 0.1 μm or more, the adhesive layer can have sufficient holding power to adhere to the adherend. When the thickness is 50 μm or less, the adhesive layer can be efficiently produced as a cured film (by making the thickness of the dried coating film below the above upper limit, efficient curing can be achieved during thermal curing).

[0183] The support, adherend, and adhesive layer have been described above. The laminate of the present invention comprises an adhesive layer consisting of a dried coating film of the photosensitive resin composition of the present invention or a cured film thereof between the light-transmitting support and adherend, and the manufacturing method thereof can suitably be the manufacturing method of the laminate of the present invention described below.

[0184] [Method of manufacturing laminate] The method for producing a laminate of the present invention includes the steps of forming an adhesive layer on the surface of either or both of a light-transmitting support and an adherend using the photosensitive resin composition of the present invention; a step of adhering the support and the adherend via the adhesive layer formed in the step to obtain a laminate; The method includes:

[0185] In the method for producing a laminate of the present invention, first, an adhesive layer is formed on the surface of either or both of a light-transmitting support and an adherend using the photosensitive resin composition of the present invention.

[0186] In the adhesive layer forming step, the photosensitive resin composition is first applied (coated) to the surface of either or both of a light-transmitting support and an adherend. The method for applying (coating) the photosensitive resin composition is not particularly limited, and examples thereof include known methods such as a solution immersion method, a spin coating method, an inkjet method, a spray method, and methods using a roller coater, a land coater, a slit coater, and a spinner.

[0187] Furthermore, when forming an adhesive layer using the photosensitive resin composition, it is preferable to apply the photosensitive resin composition to the surface of one or both of a light-transmitting support and an adherend, and then pre-bake to dry the solvent, thereby forming an adhesive layer consisting of a dried coating film. The pre-bake method and conditions can be the same as those described in the method for producing a cured resin film of the present invention.

[0188] In addition, in the present invention, an adhesive is applied (coated) to the surface of one or both of a light-transmitting support and an adherend, and then the support and the adherend are bonded together via the formed adhesive layer to obtain a laminate. That is, in the present invention, an adhesive layer is formed using the photosensitive resin composition of the present invention, and then the support and the adherend are bonded together via the formed adhesive layer to obtain a laminate.

[0189] In this way, when bonding the support and the adherend, the support and the adherend may be bonded using a laminated structure (a laminated structure of an adherend and a holding substrate) in which the adherend is held (laminated) on a so-called holding substrate (the holding substrate referred to here may be any substrate capable of holding the adherend, and may be any known substrate used as a substrate for holding an adherend, and is not particularly limited, but is preferably a light-transmitting substrate (e.g., a glass substrate, an acrylic substrate, a sapphire substrate, a quartz substrate, etc.)). In this case, an adhesive layer is formed on the surface of one or both of the support and the adherend (the adherend provided in the laminated structure), and then the support and the laminated structure are bonded via the formed adhesive layer (note that, during bonding, the support and the adherend need to be bonded so that the holding substrate is positioned on the outermost layer side). As a result, the support and the adherend are bonded. After bonding the support and the adherend (the laminate structure), the resulting laminate (a laminate formed by laminating the support, adhesive layer, adherend, and holding substrate in this order) of the support and the adherend (the laminate structure) may be subjected to an exposure step (exposure step) in which the adhesive layer is irradiated with light from the adherend side (holding substrate side). After the exposure step, a step of irradiating the laminate with light may be performed to peel the holding substrate that held the adherend from the laminate (in other words, a step of peeling the holding substrate from the adherend included in the laminate). (Hereinafter, for convenience, the step of irradiating the laminate with light (or a laser) to peel the holding substrate from the adherend will be simply referred to as the "photo-separating step.") The light or laser irradiated to peel the holding substrate is preferably ultraviolet light, more preferably ultraviolet laser light (ultraviolet laser) having a wavelength in the range of 10 to 400 nm (more preferably 100 to 400 nm). In addition, when irradiating with light in the step of separating with light, it is preferable to irradiate with light from the holding substrate side in accordance with the interface between the holding substrate and the adherend. Note that the order of the exposure step and the step of separating with light may be reversed.Furthermore, a development step may be carried out after the exposure step and the light-based separation step (the step of peeling the support substrate from the adherend). By carrying out the exposure step and the development step in this way, it is possible to pattern the adhesive layer in the resulting laminate. Furthermore, by patterning the adhesive layer in this way, the adhesive layer can be formed only in the area where the adherend is adhered (the adhesive layer can be left), and poor peeling or misalignment of the adherend can be suppressed in the step of separating the support and the adherend (described below).

[0190] Furthermore, when patterning the adhesive layer, the light used in the exposure step is not particularly limited, and examples thereof include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays, but radiation with a wavelength in the range of 250 to 450 nm can be preferably used.

[0191] In the development step, development is preferably carried out using an alkaline developer. Examples of such alkaline developers include aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, and tetramethylammonium hydroxide. A desired pattern can be formed by alkaline development using such an alkaline developer. The developer used in such alkaline development may be appropriately selected depending on the characteristics of the resin constituting the dried coating film. A surfactant may be added to such an alkaline developer, if necessary. Such alkaline development is preferably carried out at a temperature of 20 to 35°C. Known development methods, such as shower development, spray development, dip (immersion) development, and puddle (puddle) development, can be appropriately employed for alkaline development. Commercially available developing machines, ultrasonic cleaners, and the like may also be used for alkaline development. After such alkaline development, it is preferable to rinse with water.

[0192] Thus, in the present invention, when adhering the support and the adherend, an adhesion step may be carried out using a laminated structure of the adherend and a holding substrate (a laminate consisting of the adherend and a substrate that holds the adherend), and then an exposure step and a development step may be carried out to pattern the adhesive layer in the laminate. When patterning the adhesive layer in this manner, the method for producing a laminate of the present invention preferably includes the steps of: forming an adhesive layer using the photosensitive resin composition of the present invention on the surface of one or both of a light-transmitting support and an adherend (adherend held by a holding substrate) comprising a laminate structure of an adherend and a holding substrate; adhering the support and the laminate structure via the adhesive layer formed in the step to obtain a laminate (laminate) in which the support, adhesive layer, adherend, and holding substrate are stacked in this order; exposing the adhesive layer by irradiating it with light from the holding substrate side (the exposure step); peeling the holding substrate from the laminate with light (the light-separating step); and forming a pattern in the adhesive layer by development (the development step).

[0193] In the above, we have described a suitable process that can be adopted when performing the adhesion process using the adherend (the laminated structure) held on the holding substrate when adhering the support and the adherend via the adhesive layer. However, the adherend that is adhered to the support via the adhesive layer is not limited to one held on a holding substrate as described above, and may be one that does not have a holding substrate (the adherend itself).

[0194] In addition, in the present invention, after applying (coating) the adhesive to the surface of either or both of a light-transmitting support and an adherend, an exposure step and a development step may be carried out to pattern the adhesive layer before bonding the support and the adherend. By patterning the adhesive layer in this manner, the adhesive layer can be formed only in the area where the adherend is to be bonded, thereby suppressing poor peeling or misalignment of the adherend during the step of separating the support and the adherend (described below). The step of bonding the support and the adherend via the adhesive layer after patterning the adhesive layer is particularly suitable, for example, when the adherend is not held on a support substrate (e.g., when it is the adherend itself). Thus, in the present invention, a laminate may be obtained by forming an adhesive layer using the photosensitive resin composition of the present invention as described above, followed by an exposure step and a development step, and then bonding the support and the adherend via the patterned adhesive layer.

[0195] In the present invention, the method for adhering the support and the adherend is not particularly limited. For example, when an adhesive layer is formed on the surface of the support, the adherend (which may have an adhesive layer formed on the surface of the support that comes into contact with the adhesive layer) is contacted with the surface of the formed adhesive layer and pressed to adhere the support and the adherend via the adhesive layer. Alternatively, when an adhesive layer is formed on the surface of the adherend, the support (which may have an adhesive layer formed on the surface of the adherend that comes into contact with the adhesive layer) is contacted with the surface of the formed adhesive layer and pressed to adhere the support and the adherend via the adhesive layer. In such a method, the temperature conditions for contacting the support and the adherend and applying pressure are not particularly limited, but are preferably room temperature or higher and 200 ° C or lower, and more preferably 30 ° C or higher and 150 ° C or lower. The pressure conditions when the support and the adherend are brought into contact and pressed are not particularly limited, but are preferably 0.01 MPa or more and 20 MPa or less, and more preferably 0.03 MPa or more and 15 MPa or less.

[0196] Furthermore, when the adhesive layer is a cured film, it is preferable to heat (post-bake) the adhesive layer at a temperature of 120°C or higher and 250°C or lower to thermally cure it after bonding the support and the adherend via the adhesive layer as described above. By bonding the support and the adherend under the above conditions and forming the adhesive layer as a cured film, the adherend is more firmly fixed to the surface of the support via the adhesive layer. Note that such a laminate before post-baking may be subjected to an exposure step and a development step to perform patterning, and then post-baking may be performed.

[0197] In this way, a laminate can be obtained which comprises a support, an adherend, and an adhesive layer between the support and the adherend, the adhesive layer being a dried coating film of the photosensitive resin composition of the present invention or a cured film thereof.

[0198] [Laminate processing method] The method for treating a laminate of the present invention includes the steps of: preparing a laminate having an adhesive layer formed of a cured film of the photosensitive resin composition of the present invention between a light-transmitting support and an adherend; a step of irradiating the adhesive layer with light to separate the support and the adherend; Including, The support transmits light with a wavelength of 10 nm or more and 400 nm or less, and In this method, when separating the support and the adherend, the support and the adherend are separated by irradiating the adhesive layer with light from the support side. Each step will be described below.

[0199] <Step of Preparing Laminate> The process for preparing such a laminate is not particularly limited, but it is preferable to prepare the laminate by employing the laminate manufacturing method of the present invention described above. In such a laminate, the support must be a support that transmits light with a wavelength of 10 nm or more and 400 nm or less. By using such a support, it becomes possible to efficiently irradiate the adhesive layer with light from the support side. As such a support, any of the supports described in the laminate of the present invention above that satisfy the condition of "transmitting light with a wavelength of 10 nm or more and 400 nm or less" can be appropriately used. Suitable conditions for the support are the same as those for the support described in the laminate of the present invention described above.

[0200] <Step of Separating the Support and the Adherend> The step of separating the support and the adherend is a step of separating the support and the adherend by irradiating the adhesive layer with light.

[0201] The light (irradiation light) irradiated onto the adhesive layer may be any light capable of separating the support and the adherend, but is preferably ultraviolet light. The wavelength of such irradiation light (preferably ultraviolet light) is more preferably 10 nm or more and 400 nm or less, even more preferably 100 nm or more and 400 nm or less, and particularly preferably 150 nm or more and 380 nm or less. By using irradiation light (preferably ultraviolet light) with a wavelength of 10 nm or more, the light can be absorbed by the polymer, which is a component of the adhesive layer, thereby altering or decomposing the adhesive layer and reducing its mechanical strength and adhesive force, thereby making it easier to separate the support and the adherend. When the wavelength of the irradiation light (preferably ultraviolet light) is 400 nm or less, the light can be efficiently absorbed by the adhesive layer in the processed area, which tends to significantly reduce the generation of cured film residue at the peeled area. Furthermore, when the wavelength of the ultraviolet light is 350 nm or more, inexpensive glass and acrylic substrates (particularly preferably glass substrates) can be used, thereby reducing running costs.

[0202] Examples of the light source for the irradiation light include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and far-ultraviolet laser light sources. Laser light sources capable of emitting laser light are preferred as such light sources. Examples of such lasers include solid-state lasers, liquid lasers, and gas lasers. Examples of such solid-state lasers include semiconductor-pumped lasers. Examples of the liquid lasers include dye lasers. Examples of the gas lasers include excimer lasers. Among these lasers, semiconductor-pumped lasers are preferred.

[0203] Examples of the semiconductor pumped laser include Nd:YAG laser, Nd:YLF laser, Nd:glass laser, Nd:YVO4 laser, Yb:YAG laser, Yb-doped fiber laser, Er:YAG laser, Tm:YAG laser, etc. Examples of excimer lasers include KrF laser, XeCl laser, ArF laser, F2 laser, etc. Of these, the Nd:YAG laser is preferred as the semiconductor pumped laser.

[0204] The output and cumulative light amount of the light (irradiated light) irradiated onto the adhesive layer vary depending on the type of light source, etc., but when the irradiated light is a laser, the output is preferably 0.1 mW or more and 200 W or less, and the cumulative light amount is preferably 1 mJ / cm. 2 More than 50J / cm 2 It is preferable that the cumulative light amount is 0.1 mJ / cm or less. 2 If the integrated light intensity is 50 J / cm or more, scorching and peeling residues that occur during ablation tend to be less likely to occur. 2 When the ablation speed is equal to or less than this, processing can be performed while appropriately controlling the ablation speed, and the processability tends to be further improved.

[0205] Furthermore, when irradiating the adhesive layer with light (preferably laser), it is necessary to irradiate the adhesive layer with light from the support side. In this case, it is preferable to irradiate the entire surface of the adhesive layer with light (preferably laser) from the support side. The laser irradiation method is not particularly limited except for irradiating the adhesive layer with light from the support side, and known methods can be used. The present invention may also include a step of processing the laminate before separating the support from the adherend. When the step of processing the laminate is included, such processing steps (processing methods) are not particularly limited, but examples include thinning of the adherend, such as dicing and backside grinding, photofabrication, stacking of semiconductor chips, mounting of various elements, and resin encapsulation. In this way, the support and the adherend can be separated. Such a processing method can be applied, for example, to laser mass transfer, which transfers an LED chip by laser irradiation. [Example]

[0206] The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples.

[0207] [Unsaturated group-containing polymeric resin] <Abbreviations for components used in each example> The abbreviations used in the following synthesis examples and examples respectively represent the following compounds. BPFE: bisphenol fluorene type epoxy compound (a compound represented by the above formula (20), in which Ar is a phenylene group and l is 0, epoxy equivalent: 250 g / eq) AA: Acrylic acid TPP: Triphenylphosphine BHT: 2,6-di-tert-butyl-p-cresol PGMEA: Propylene glycol monomethyl ether acetate FHPA: the compound prepared in Synthesis Example 1 below [a compound represented by the above formula (8), in which X is a group represented by the above formula (11), l is 0, and W is an acryloyl group (hereinafter sometimes referred to as "compound (a-1)-1")] BPEF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (hereinafter sometimes referred to as "compound (a-1)-2") BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride (hereinafter sometimes referred to as "compound (a-2)-1") THPA: 1,2,3,6-tetrahydrophthalic anhydride (hereinafter sometimes referred to as "compound (a-3)-1" or "compound (a-5)-1") 4HBAGE: 4-hydroxybutyl acrylate glycidyl ether (hereinafter sometimes referred to as "compound (a-4)-1") GMA: glycidyl methacrylate (hereinafter sometimes referred to as "compound (a-4)-2") 2EHG: 2-ethylhexyl glycidyl ether (hereinafter sometimes referred to as "compound (a-4)-3") 1,2-Epoxydodecane: 1,2-epoxydodecane (hereinafter sometimes referred to as "compound (a-4)-4") THPA: 1,2,3,6-tetrahydrophthalic anhydride (hereinafter sometimes referred to as "compound (a-5)-1") PA: phthalic anhydride (hereinafter sometimes referred to as "compound (a-5)-2") SA: succinic anhydride (hereinafter sometimes referred to as "compound (a-5)-3").

[0208] (Synthesis Example 1: Synthesis of a solution containing FHPA (resin solution)) A 300 mL four-neck flask equipped with a reflux condenser was charged with BPFE (50.00 g, 0.10 mol), AA (14.41 g, 0.20 mol), TPP (0.26 g, used as a catalyst), BHT (0.02 g, used as an antioxidant), and PGMEA (15.00 g, used as a solvent). The mixture was then stirred at a temperature of 100 to 105 ° C for 12 hours to react the hydroxyl groups of BPFE with the carboxyl groups in AA to form FHPA (reaction product) in the mixture. Then, PGMEA (49.60 g) was further charged into the four-neck flask, and the solids concentration was adjusted to 50% by mass to obtain a resin solution containing FHPA (compound (a-1)-1). In addition, in all of Examples 1 to 7 and Comparative Examples 1 to 4 shown below, a resin solution (solid content concentration of FHPA: 50 mass %, molar amount of FHPA: 0.10 mol) obtained by the same method as that described in Synthesis Example 1 was used. Furthermore, the "solid content concentration" referred to here is a value measured by the same method as that used to measure the solid content concentration of the resin solutions obtained in Examples 1 to 7 and Comparative Examples 1 to 5 described below.

[0209] <Methods for evaluating the properties of resins obtained in Examples 1 to 7 and Comparative Examples 1 to 5> Below, we will explain examples and comparative examples related to unsaturated group-containing polymerizable resins. Unless otherwise specified, the properties of the resins and resin solutions obtained in each example and comparative example were evaluated according to the methods described below. When the same model of measuring equipment was used for the various measuring equipment described below, the name of the equipment manufacturer will be omitted from the second position. Furthermore, when the first decimal place of the content of each component is 0, the decimal point may be omitted.

[0210] [Measurement of solid concentration] The solids concentration of the resin solutions obtained in Examples 1 to 7 and Comparative Examples 1 to 5 was measured as follows. First, 1 g of the obtained resin solution was impregnated into a glass filter (mass: W0 (g)), and the mass of the glass filter carrying the obtained resin solution (W1 (g)) was weighed. Next, the glass filter carrying the resin solution was heated at 160°C for 2 hours, and the mass of the heated glass filter (W2 (g)) was weighed. Then, the solids concentration was calculated using the calculated mass values ​​(W0, W1, and W2) according to the following formula: [Solid content concentration (mass%)]=[(W2-W0) / (W1-W0)]×100.

[0211] [Acid value measurement] The resin solutions obtained in Examples 1 to 7 and Comparative Examples 1 to 5 were each dissolved in dioxane, and titrated with a 1 / 10N KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to determine the acid values ​​of the resins obtained in Examples 1 to 7 and Comparative Examples 1 to 5.

[0212] [Measurement of weight-average molecular weight] The weight-average molecular weights (Mw) of the resins obtained in Examples 1 to 7 and Comparative Examples 1 to 5 were measured using the resin solutions obtained in Examples 1 to 7 and Comparative Examples 1 to 5, respectively, using gel permeation chromatography (GPC) "HLC-8220GPC" (Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2 columns), TSKgelSuper H-3000 (1 column), TSKgelSuper H-4000 (1 column), and TSKgelSuper H-5000 (1 column) (Tosoh Corporation), temperature: 40°C, flow rate: 0.6 ml / min), and the values ​​were calculated in terms of standard polystyrene (Tosoh Corporation, PS-Oligomer Kit). Hereinafter, the measured weight-average molecular weights (Mw) will sometimes be referred to simply as "Mw by GPC analysis."

[0213] Example 1 Using a method similar to that used in Synthesis Example 1, a resin solution containing FHPA (129.30 g, solids concentration of FHPA: 50 mass%, molar amount of FHPA 0.10 mol) was prepared in a 300 mL four-neck flask equipped with a reflux condenser. The resulting resin solution containing FHPA (0.10 mol) was used as is. BPDA (14.78 g, 0.05 mol), THPA (7.64 g, 0.05 mol), and PGMEA (22.00 g, used as a solvent) were added, and the mixture was stirred for 8 hours at a temperature of 115 to 120 ° C. to obtain a solution containing the first reactant. Next, 4HBAGE (28.66 g, 0.14 mol) and TPP (0.38 g, used as a catalyst) were added to the solution containing the first reactant, and the mixture was stirred for 8 hours at 100 to 105 ° C. to obtain a solution containing the second reactant. Then, THPA (16.33 g, 0.11 mol) was added to the solution containing the second reactant, and the mixture was stirred at 100 to 105°C for 8 hours to obtain a resin solution containing unsaturated group-containing polymerizable resin (A)-1. The solids concentration of the obtained resin solution was 60.5 mass%, the acid value (solids equivalent) was 46 mg KOH / g, and the Mw by GPC analysis was 6600. The types of components used in the production of the resin and the measurement results are shown in Table 1.

[0214] Example 2 Using a method similar to that used in Synthesis Example 1, a resin solution containing FHPA (129.30 g, solids concentration of FHPA: 50 mass%, molar amount of FHPA 0.10 mol) was prepared in a 300 mL four-neck flask equipped with a reflux condenser. The resulting resin solution containing FHPA (0.10 mol) was used as is. BPDA (14.78 g, 0.05 mol), THPA (7.64 g, 0.05 mol), and PGMEA (22.00 g) were added, and the mixture was stirred at 115 to 120 ° C. for 8 hours to obtain a solution containing the first reactant. Next, 4HBAGE (28.66 g, 0.14 mol) and TPP (0.38 g) were added to the solution containing the first reactant, and the mixture was stirred at 100 to 105 ° C. for 8 hours to obtain a solution containing the second reactant. Subsequently, PA (15.90 g, 0.11 mol) was added to the solution containing the second reactant, and the mixture was stirred at 100 to 105°C for 8 hours to obtain a resin solution containing unsaturated group-containing polymerizable resin (A)-2. The solids concentration of the obtained resin solution was 60.4 mass%, the acid value (solids equivalent) was 47 mg KOH / g, and the Mw by GPC analysis was 6100. The types of components used in the production of the resin and the measurement results are shown in Table 1.

[0215] Example 3 Using a method similar to that used in Synthesis Example 1, a resin solution containing FHPA (129.30 g, solids concentration of FHPA: 50 mass%, molar amount of FHPA 0.10 mol) was prepared in a 300 mL four-neck flask equipped with a reflux condenser. The resulting resin solution containing FHPA (0.10 mol) was used as is. BPDA (14.78 g, 0.05 mol), THPA (7.64 g, 0.05 mol), and PGMEA (22.00 g) were added, and the mixture was stirred at 115 to 120 ° C. for 8 hours to obtain a solution containing the first reactant. Next, 4HBAGE (28.66 g, 0.14 mol) and TPP (0.38 g) were added to the solution containing the first reactant, and the mixture was stirred at 100 to 105 ° C. for 8 hours to obtain a solution containing the second reactant. Then, SA (10.74 g, 0.11 mol) was added to the solution containing the second reactant, and the mixture was stirred at 100 to 105°C for 8 hours to obtain a resin solution containing unsaturated group-containing polymerizable resin (A)-3. The solids concentration of the obtained resin solution was 59.4 mass%, the acid value (solids equivalent) was 48 mg KOH / g, and the Mw by GPC analysis was 6000. The types of components used in the production of the resin and the measurement results are shown in Table 1.

[0216] Example 4 Using a method similar to that used in Synthesis Example 1, a 300 mL four-neck flask equipped with a reflux condenser was used to prepare a resin solution containing FHPA (129.30 g, solids concentration of FHPA: 50 mass%, molar amount of FHPA 0.10 mol). The resulting resin solution containing FHPA (0.10 mol) was added with BPDA (14.78 g, 0.05 mol), THPA (7.64 g, 0.05 mol), and PGMEA (22.00 g), and stirred at 115 to 120 ° C. for 8 hours to obtain a solution containing the first reactant. Next, GMA (20.34 g, 0.14 mol) and TPP (0.38 g) were added to the solution containing the first reactant, and the mixture was stirred at 100 to 105 ° C. for 8 hours to obtain a solution containing the second reactant. Then, THPA (16.33 g, 0.11 mol) was added to the solution containing the second reactant, and the mixture was stirred at 100 to 105°C for 8 hours to obtain a resin solution containing unsaturated group-containing polymerizable resin (A)-4. The solids concentration of the obtained resin solution was 58.9 mass%, the acid value (solids equivalent) was 50 mgKOH / g, and the Mw by GPC analysis was 6000. The types of components used in the production of the resin and the measurement results are shown in Table 1.

[0217] Example 5 Using a method similar to that used in Synthesis Example 1, a resin solution containing FHPA (129.30 g, solids concentration of FHPA: 50 mass%, molar amount of FHPA 0.10 mol) was prepared in a 300 mL four-neck flask equipped with a reflux condenser. The resulting resin solution containing FHPA (0.10 mol) was used as is. BPDA (14.78 g, 0.05 mol), THPA (7.64 g, 0.05 mol), and PGMEA (22.00 g) were added and stirred at 115 to 120 ° C. for 8 hours to obtain a solution containing the first reactant. Next, 4HBAGE (15.08 g, 0.08 mol) and TPP (0.20 g) were added to the solution containing the first reactant, and the mixture was stirred at 100 to 105 ° C. for 8 hours to obtain a solution containing the second reactant. Then, THPA (8.60 g, 0.06 mol) was added to the solution containing the second reactant, and the mixture was stirred at 100 to 105°C for 8 hours to obtain a resin solution containing unsaturated group-containing polymerizable resin (A)-5. The solids concentration of the obtained resin solution was 56.2 mass%, the acid value (solids equivalent) was 40 mg KOH / g, and the Mw by GPC analysis was 6000. The types of components used in the production of the resin and the measurement results are shown in Table 1.

[0218] Example 6 Using a method similar to that used in Synthesis Example 1, a resin solution containing FHPA (129.30 g, solids concentration of FHPA: 50 mass%, molar amount of FHPA 0.10 mol) was prepared in a 300 mL four-neck flask equipped with a reflux condenser. The resulting resin solution containing FHPA (0.10 mol) was used as is. BPDA (14.78 g, 0.05 mol), THPA (7.64 g, 0.05 mol), and PGMEA (22.00 g) were added and stirred at 115 to 120 ° C. for 8 hours to obtain a solution containing the first reactant. Next, 4HBAGE (28.66 g, 0.14 mol) and TPP (0.38 g) were added to the solution containing the first reactant, and the mixture was stirred at 100 to 105 ° C. for 8 hours to obtain a solution containing the second reactant. Then, THPA (20.69 g, 0.13 mol) was added to the solution containing the second reactant and stirred at 100 to 105°C for 8 hours to obtain a resin solution containing unsaturated group-containing polymerizable resin (A)-6. The solids concentration of the obtained resin solution was 61.2 mass%, the acid value (solids equivalent) was 57 mgKOH / g, and the Mw by GPC analysis was 6000.

[0219] Example 7 Using a method similar to that used in Synthesis Example 1, a resin solution containing FHPA (129.30 g, solids concentration of FHPA: 50 mass%, molar amount of FHPA 0.10 mol) was prepared in a 300 mL four-neck flask equipped with a reflux condenser. The resulting resin solution containing FHPA (0.10 mol) was used as is. BPDA (14.78 g, 0.05 mol), THPA (7.64 g, 0.05 mol), and PGMEA (22.00 g) were added and stirred at 115 to 120 ° C. for 8 hours to obtain a solution containing the first reactant. Next, 4HBAGE (28.66 g, 0.14 mol) and TPP (0.38 g) were added to the solution containing the first reactant, and the mixture was stirred at 100 to 105 ° C. for 8 hours to obtain a solution containing the second reactant. Then, THPA (10.89 g, 0.07 mol) was added to the solution containing the second reactant, and the mixture was stirred at 100 to 105°C for 8 hours to obtain a resin solution containing unsaturated group-containing polymerizable resin (A)-7. The solids concentration of the obtained resin solution was 59.5 mass%, the acid value (solids equivalent) was 33 mg KOH / g, and the Mw by GPC analysis was 6000. The types of components used in the production of the resin and the measurement results are shown in Table 1.

[0220] (Comparative Example 1) Using a method similar to that used in Synthesis Example 1, a resin solution containing FHPA (129.30 g, FHPA solids concentration: 50% by mass, FHPA molar content: 0.10 mol) was prepared and used as is in a 300 mL four-neck flask equipped with a reflux condenser. THPA (7.64 g, 0.05 mol) was added to the resulting resin solution containing FHPA (0.10 mol) and stirred at 115 to 120 °C for 8 hours to obtain a resin solution containing a comparative unsaturated group-containing polymerizable resin (A')-8. The solids concentration of the resulting resin solution was 57.4% by mass, the acid value (solids equivalent) was 97 mg KOH / g, and the Mw by GPC analysis was 3500. The types of components used in the production of the resin and the measurement results are shown in Table 1.

[0221] (Comparative Example 2) Using a method similar to that used in Synthesis Example 1, a resin solution containing FHPA (129.30 g, FHPA solids concentration: 50 mass%, FHPA molar content 0.10 mol) was prepared in a 300 mL four-neck flask equipped with a reflux condenser. BPDA (14.78 g, 0.05 mol) and PGMEA (15.00 g) were added to the resulting resin solution containing FHPA (0.10 mol), and the mixture was stirred at 115 to 120 ° C. for 8 hours to obtain a solution containing the first comparative reactant. 4HBAGE (19.11 g, 0.10 mol) and TPP (0.25 g) were then added to the solution containing the first comparative reactant, and the mixture was stirred at 100 to 105 ° C. for 8 hours to obtain a solution containing the second comparative reactant. Then, THPA (10.89 g, 0.07 mol) was added to the solution containing the second comparative reactant, and the mixture was stirred at 100 to 105°C for 8 hours to obtain a resin solution containing comparative unsaturated group-containing polymerizable resin (A')-9. The solids concentration of the resulting resin solution was 58.0 mass%, the acid value (solids equivalent) was 37 mg KOH / g, and the Mw by GPC analysis was 6000. The types of components used in the production of the resin and the measurement results are shown in Table 1.

[0222] (Comparative Example 3) Using a method similar to that used in Synthesis Example 1, a 300 mL four-neck flask equipped with a reflux condenser was used to prepare a resin solution containing FHPA (129.30 g, solids concentration of FHPA: 50 mass%, molar amount of FHPA 0.10 mol). The resulting resin solution containing FHPA (0.10 mol) was added with BPDA (14.78 g, 0.05 mol), THPA (7.64 g, 0.05 mol), and PGMEA (22.00 g), and stirred at 115 to 120 ° C. for 8 hours to obtain a solution containing the first reactant. Next, 2EHG (26.67 g, 0.14 mol), and TPP (0.38 g) were added to the solution containing the first reactant, and the mixture was stirred at 100 to 105 ° C. for 8 hours to obtain a solution containing a comparative reactant. Then, THPA (16.33 g, 0.11 mol) was added to the solution containing the comparative reactant, and the mixture was stirred at 100 to 105°C for 8 hours to obtain a resin solution containing a comparative unsaturated group-containing polymerizable resin (A')-10. The solids concentration of the resulting resin solution was 60.1 mass%, the acid value (solids equivalent) was 47 mg KOH / g, and the Mw by GPC analysis was 6000. The types of components used in the production of the resin and the measurement results are shown in Table 1.

[0223] Comparative Example 4 Using a method similar to that used in Synthesis Example 1, a resin solution containing FHPA (129.30 g, solids concentration of FHPA: 50 mass%, molar amount of FHPA 0.10 mol) was prepared in a 300 mL four-neck flask equipped with a reflux condenser. The resulting resin solution containing FHPA (0.10 mol) was used as is. BPDA (14.78 g, 0.05 mol), THPA (7.64 g, 0.05 mol), and PGMEA (22.00 g) were added and stirred at 115 to 120 ° C. for 8 hours to obtain a solution containing the first reactant. Next, 1,2-epoxydodecane (26.38 g, 0.14 mol) and TPP (0.38 g) were added to the solution containing the first reactant, and the mixture was stirred at 100 to 105 ° C. for 8 hours to obtain a solution containing a comparative reactant. Then, THPA (16.33 g, 0.11 mol) was added to the solution containing the comparative reactant, and the mixture was stirred at 100 to 105°C for 8 hours to obtain a resin solution containing a comparative unsaturated group-containing polymerizable resin (A')-11. The solids concentration of the resulting resin solution was 60.1 mass%, the acid value (solids equivalent) was 47 mg KOH / g, and the Mw by GPC analysis was 6000. The types of components used in the production of the resin and the measurement results are shown in Table 1.

[0224] (Comparative Example 5) To BPEF (55.00 g, 0.13 mol), BPDA (18.45 g, 0.06 mol), THPA (9.54 g, 0.06 mol), and PGMEA (83.00 g) were added and stirred at 115-120 °C for 8 hours to obtain a solution containing the first comparative reactant. Next, to the solution containing the first comparative reactant, 4HBAGE (35.79 g, 0.18 mol) and TPP (0.45 g) were added and stirred at 100-105 °C for 8 hours to obtain a solution containing the second comparative reactant. Then, THPA (20.39 g, 0.13 mol) was added to the solution containing the second comparative reactant and stirred at 100-105 °C for 8 hours to obtain a resin solution containing the comparative unsaturated group-containing polymerizable resin (A')-12. The solids concentration of the obtained resin solution was 62.7% by mass, the acid value (solids equivalent) was 55 mgKOH / g, and the Mw according to GPC analysis was 3000. The types of components used in the production of the resin and the measurement results are shown in Table 1.

[0225] [Table 1]

[0226] [Photosensitive resin composition] <Abbreviations of components used in Examples 8 to 21 and Comparative Examples 6 to 10> First, the abbreviations of the components used in each example will be explained. Note that, in the following, each component will be represented by its abbreviation where appropriate.

[0227] [Solution of component (A): resin solution] The abbreviations for the solutions of component (A) used in the examples are shown in Table 2 below. Here, "component (A)" refers to an unsaturated group-containing polymerizable resin.

[0228] [Table 2]

[0229] [Component (B): Photosensitizer] (B1): Ester of 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol and 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid (trade name: TPPA-300A, manufactured by Toyo Gosei Co., Ltd.).

[0230] [Component (C): Solvent] (C1): Propylene glycol monomethyl ether acetate (abbreviation: PGMEA)

[0231] [Component (D): Epoxy compound] (D1): Tetramethylbiphenol-type solid epoxy resin (product name: jER YX4000HK, manufactured by Mitsubishi Chemical Corporation) (D2): Bisphenol A liquid epoxy resin (trade name: jER 828, manufactured by Mitsubishi Chemical Corporation).

[0232] [Component (E): Crosslinking agent] (E1): 4,4'-[1-[4-[1-[4-hydroxy-3,5-bis(methoxymethyl)-1-methylethyl]phenyl]ethylidene]-bis[2,6-bis(methoxymethyl)phenol] (trade name: HMOM-TPPA, Honshu Chemical Industry Co., Ltd.) (E2): 4,4'-isopropylidenebis[2,6-bis(hydroxymethyl)phenol] (trade name: TML-BPA-MF, Honshu Chemical Industry Co., Ltd.) (E3): 3,3',5,5'-tetrakis(methoxymethyl)biphenyl-4,4'-diol (trade name: TMOM-BP, Honshu Chemical Industry Co., Ltd.).

[0233] <Synthesis of Photosensitive Resin Composition> (Examples 8 to 21 and Comparative Examples 6 to 10) Photosensitive resin compositions of Examples 8 to 21 and Comparative Examples 6 to 10 were produced using the blending ratios (unit: mass %) shown in Table 3. In Table 3, "component (A)" refers to the unsaturated group-containing polymerizable resin, the value for "solution of component (A)" in the blending ratio refers to the content (mass %) as a resin solution, "concentration of component (A) in the solid content" refers to the content (mass %) of the unsaturated group-containing polymerizable resin as component (A) in the solid content of the photosensitive resin composition, and "concentration of component (B) in the solid content" refers to the content (mass %) of the photosensitizer as component (B) in the solid content of the photosensitive resin composition.

[0234] [Table 3]

[0235] <Method for evaluating photosensitive resin composition> The following describes the methods for evaluating the properties of the photosensitive resin compositions obtained in Examples 8 to 21 and Comparative Examples 6 to 10. The properties of the photosensitive resin compositions were evaluated using, as samples, coating films obtained by applying each photosensitive resin composition to a substrate and drying it, or cured films obtained by curing such coating films.

[0236] [Preparation of substrate with cured film (measurement sample (I)) for measuring laser processability, etc.] Using the photosensitive resin compositions obtained in Examples 8 to 21 and Comparative Examples 6 to 10, measurement samples (I) each consisting of a substrate with a cured film were produced as follows: First, the photosensitive resin composition was irradiated with a low-pressure mercury lamp at a wavelength of 254 nm and an illuminance of 1000 mJ / cm. 2 The surface was cleaned by irradiating ultraviolet light of 1000 kJ / cm 2 at 100°C. The surface was then cleaned by applying the photosensitive resin composition onto a synthetic quartz glass substrate (hereinafter referred to as "quartz glass substrate") having a surface of 125 mm long and 125 mm wide using a spin coater so that the film thickness after heat curing would be 2.0 μm. The composition was then prebaked at 90°C for 3 minutes using a hot plate to form a coating film (dried coating film). The quartz glass substrate after the coating film formation was then subjected to a heat treatment (post-baking) using a hot air dryer at a temperature of 230°C for 30 minutes to cure the coating film, thereby obtaining a substrate with a cured film (measurement sample (I)). The quartz glass substrate used had a transmittance of 90% or more for light with wavelengths of 350 nm to 450 nm across the entire wavelength range.

[0237] [Evaluation of laser processability (peelability)] The laser processability was evaluated using each of the above-mentioned measurement samples (I) as follows. First, the measurement samples (I) were prepared, and a flash lamp-pumped Nd:YAG Q-SW laser oscillator "Callisto" (manufactured by V-Technology Co., Ltd.) was used to irradiate the measurement samples (I) with a laser (laser wavelength: 355 nm) from the cured film side. In this way, 50 to 650 mJ / cm 2The cured film in the measurement sample (I) was laser-processed by irradiating the cured film with a laser at a laser energy (energy density). The state of the laser-irradiated area (laser-processed area) of the cured film was then observed using an optical microscope, and the laser processability was evaluated using the following evaluation criteria. The following evaluation criteria are ranked in descending order of A, B, and C, with those rated B or higher (A and B) being considered to have high laser processability, and therefore those rated B or higher were evaluated as passing. The evaluation results are shown in Tables 4 and 5.

[0238] <Laser processability evaluation criteria> A: 200mJ / cm 2 The cured film will thin out below the following B: 200 mJ / cm 2 Super 500mJ / cm 2 The cured film will thin out below the following C: 500mJ / cm 2 The hardened film does not thin even with ultra-high temperature.

[0239] [Evaluation of solvent resistance] The solvent resistance of each of the measurement samples (I) was evaluated as follows. First, the measurement samples (I) were prepared, and the thickness of the cured film (thickness of the cured film before the immersion treatment described below) was measured. Next, the measurement samples (I) were immersed in each of the following chemical solutions (a) to (c) at a temperature of 25°C (immersion treatment in chemical solution). <Types of chemical solutions (a) to (c)> (a) PGMEA (b) Acetone (c) N-methyl-pyrrolidone (NMP) Next, the thickness of the cured film after immersion in the chemical solution was measured. The film thickness change rate was then calculated from the film thicknesses of the cured film before and after immersion using the following formula: In the formula, T1 represents the film thickness of the cured film before immersion in the chemical solution, and T2 represents the film thickness of the cured film after immersion in the chemical solution. [Film thickness change rate (%)] = {(T1-T2) / T1} x 100

[0240] In this way, the film thickness change rate of the cured film of the photosensitive resin composition obtained in each Example was determined for each of the chemical solutions (a) to (c), and the solvent resistance was evaluated according to the following evaluation criteria. The evaluation criteria, listed in descending order of evaluation, were S, A, B, and C, and a rating of B or higher (S, A, and B) was evaluated as having high solvent resistance, so that a rating of B or higher was evaluated as passing. The evaluation results are shown in Tables 4 and 5.

[0241] <Evaluation Criteria for Solvent Resistance> S: The film thickness change rate is less than 3% for all of the chemical solutions (a) to (c). A: The film thickness change rate is 3% or more and less than 5% for all of the chemical solutions (a) to (c). B: The film thickness change rate is 5% or more and less than 10% for all of the chemical solutions (a) to (c). C: The film thickness change rate is 10% or more for all of the chemical solutions (a) to (c).

[0242] [Preparation of substrate with cured film (measurement sample (II)) for evaluation of developability, etc.] Using the photosensitive resin compositions obtained in Examples 8 to 21 and Comparative Examples 6 to 10, measurement samples (II) consisting of substrates with cured films were produced as follows. That is, first, the photosensitive resin composition was applied to a glass substrate (Corning Incorporated: #1737) using a spin coater so that the film thickness after heat curing would be 2.0 μm, and then the substrate was prebaked at 90°C for 3 minutes using a hot plate to form a coating film (dried coating film). Next, a photomask of 10 to 50 μm (5 μm intervals) was placed on the surface of the coating film, and an i-line illuminance of 30 mW / cm was applied to the surface covered with the photomask. 2 200mJ / cm 2The coating film was then irradiated (exposed) with ultraviolet light of 1000 kJ / cm². The exposed coating film was then immersed in a 0.2% by mass aqueous solution of tetramethylammonium hydroxide at a temperature of 23°C, and developed by immersing for an additional 10 seconds (development time + 10 seconds) from the development time (break time = BT) at which a pattern began to appear. The exposed portion of the coating film was then removed by rinsing with water, forming a pattern on the film on the glass substrate. The film with the pattern formed on the glass substrate was then cured (post-baked) by heating at 230°C for 30 minutes using a hot air dryer, to obtain a substrate with a cured film (measurement sample (II)) for development evaluation.

[0243] [Evaluation of developer solubility] During the manufacturing process of the measurement sample (II), the state of dissolution of the exposed portion during the development process was visually observed and evaluated according to the following evaluation criteria. The evaluation criteria were listed in descending order of evaluation as A, B, and C, and a grade of B or higher (A and B) was evaluated as being capable of forming a pattern and usable as a positive resist, so a grade of B or higher was evaluated as passing. The evaluation results are shown in Tables 4 and 5.

[0244] <Evaluation Criteria for Developer Solubility> A: The exposed area dissolves in the developer to form a pattern. B: The exposed area does not dissolve in the developer, and the film peels off to form a pattern. C: The exposed area does not dissolve in the developer, does not peel off, and no pattern can be formed.

[0245] [Evaluation of remaining film rate] During the production of the measurement sample (II), the film thickness of the coating film was measured before and after development, the film thickness change rate was calculated using the following formula, and the remaining film rate was evaluated according to the following evaluation criteria: In the formula, T3 represents the film thickness of the coating film before development (initial film thickness), and T4 represents the film thickness of the coating film after development. [Residual film rate (%)]=(T4 / T3)×100

[0246] In this way, the film retention rate of the coating film of the photosensitive resin composition obtained in each Example was determined, and the film retention rate was evaluated according to the following evaluation criteria. The evaluation criteria, listed in descending order of evaluation, are S, A, B, and C, and a rating of B or higher (S, A, and B) indicates high resistance to the developer in the unexposed area and high pattern formability (processability), so a rating of B or higher was evaluated as passing. The evaluation results are shown in Tables 4 and 5.

[0247] <Evaluation criteria for film remaining rate> S: Remaining film rate is 95% or more A: The remaining film rate is 90% or more but less than 95% B: Residual film rate is less than 90% C: Unable to develop (pattern cannot be formed)

[0248] [Evaluation of developability] Using each measurement sample (II), the mask patterns formed on the measurement sample (II) (patterns formed after post-baking of 10 to 50 μm (in 5 μm increments)) were observed under an optical microscope, and the developability was evaluated according to the following evaluation criteria. The evaluation criteria, listed in descending order of evaluation, are S, A, B, and C, and a rating of B or higher (S, A, and B) indicates that a sufficiently fine pattern can be formed and the developability is high, so that a rating of B or higher was evaluated as passing. The evaluation results are shown in Tables 4 and 5.

[0249] <Evaluation Criteria for Developability> S: A pattern with four sides less than 20 μm can be confirmed on the measurement sample (II). A: A pattern with four sides of 20 μm or more and less than 30 μm can be confirmed on the measurement sample (II). B: A pattern with four sides of 30 μm or more and less than 40 μm can be confirmed on the measurement sample (II). C: No pattern with four sides less than 40 μm can be confirmed on the measurement sample (II).

[0250] [Preparation of laminate for evaluation of adhesive strength (measurement sample (III))] Using the photosensitive resin compositions obtained in Examples 8 to 21 and Comparative Examples 6 to 10, measurement samples (II) consisting of substrates with cured films were produced as follows. Specifically, the photosensitive resin composition was first applied to a glass substrate (Corning Incorporated: #1737) using a spin coater so that the film thickness after heat curing would be 2.0 μm, and the substrate was prebaked at 90°C for 3 minutes on a hot plate to form a coating (dried coating). Next, a glass substrate (Corning Incorporated: #1737) cut to a size of 2 mm long and 2 mm wide was placed on the coating, and the substrate was heated on a hot plate at 100°C for 5 minutes to temporarily bond the coating, thereby obtaining a first laminate. Thereafter, the first laminate was subjected to a heat treatment (post-baking) using a hot air dryer at 230°C for 30 minutes to harden the coating film in the laminate, thereby obtaining a laminate (measurement sample (III)) in which a glass substrate (2 mm long, 2 mm wide) was adhered to the surface of the cured film.

[0251] [Evaluation of adhesive strength (shear strength)] Using the measurement sample (III), a die shear test (die shear test) was performed on a glass substrate (2 mm long, 2 mm wide) on top of the cured film using a die shear tester (manufactured by Arctec). The load value when the glass substrate (2 mm long, 2 mm wide) peeled from the cured film was determined as the adhesive strength, and the adhesive strength was evaluated according to the following evaluation criteria. The evaluation criteria, listed in descending order of evaluation, were S, A, B, and C. A rating of B or higher (S, A, and B) indicates sufficiently high adhesive strength, and the photosensitive resin composition can be evaluated as having high adhesiveness, so a rating of B or higher was evaluated as passing. The evaluation results are shown in Tables 4 and 5.

[0252] <Adhesive strength evaluation criteria> S: Adhesive strength is 15 MPa or more A: The adhesive strength is 10 MPa or more and less than 15 MPa. B: Adhesion strength is 5 MPa or more and less than 10 MPa C: Adhesion strength is less than 5 MPa

[0253] [Table 4]

[0254] [Table 5]

[0255] As is clear from the results shown in Tables 4 and 5, when the photosensitive resin compositions obtained in Examples 8 to 21 (corresponding to the photosensitive resin compositions of the present invention) were used, the developer solubility, film retention rate, and developability were all at high levels, indicating that they can be suitably used as positive resists. Furthermore, when the photosensitive resin compositions obtained in Examples 8 to 21 (corresponding to the photosensitive resin compositions of the present invention) were used, the laser processability, solvent resistance, and adhesive strength of the cured films were all at high levels. These results confirmed that the photosensitive resin compositions obtained in Examples 8 to 21 (corresponding to the photosensitive resin compositions of the present invention) can be used as positive resists, have excellent patterning properties, and can form cured films with high adhesive strength by heat treatment without performing a bleaching step. Furthermore, from the above results, it was confirmed that the photosensitive resin compositions obtained in Examples 8 to 21 (corresponding to the photosensitive resin compositions of the present invention) have excellent laser processability, as the laser-irradiated area is reduced when the cured film (resin cured film) is irradiated with a laser. This also shows that the cured film has high peelability when irradiated with a laser from the substrate side after forming a cured film (a layer with high adhesive strength: adhesive layer) on a substrate. Therefore, it is understood that the photosensitive resin compositions obtained in Examples 8 to 21 (corresponding to the photosensitive resin compositions of the present invention) are particularly useful as adhesives for laser mass transfer in micro LEDs.

[0256] Furthermore, a comparison of Examples 8 to 21 with Comparative Examples 6 to 10 revealed that by using the photosensitive resin compositions obtained in Examples 8 to 21, which contain unsaturated group-containing polymerizable resins containing components (a-1) to (a-5) other than the comparative components and in which the molar ratio of the amount (molar amount) of component (a-4) containing at least one unsaturated group to the sum of twice the amount (molar amount) of component (a-2) and the amount of component (a-3) used ([component (a-4)] / [(2 × [component (a-2)]) + [component (a-3)]) and the molar ratio of the amount (molar amount) of component (a-5) to the amount (molar amount) of component (a-4) used ([component (a-5)] / [component (a-4)]) are both 0.5 or more and 2.0 or less, both adhesive strength between the cured resin film and the adherend and developability can be achieved.

[0257] Furthermore, a comparison of Examples 15, 17, and 18 revealed that photosensitive resin compositions containing an epoxy compound having two or more epoxy groups as component (D) exhibited superior adhesiveness, and the inventors speculate that this is because the inclusion of component (D) improved the toughness of the cured film of the photosensitive resin composition. [Industrial Applicability]

[0258] As described above, according to the present invention, it is possible to provide an unsaturated group-containing polymerizable resin that can be used as a positive resist, has excellent patterning properties, is capable of forming a cured film having high adhesive strength without performing a bleaching step, and can provide excellent peelability when the cured film is irradiated with a laser, and that can be suitably used as a material for a photosensitive resin composition, and a method for producing the same.

[0259] Furthermore, according to the present invention, it is possible to provide a photosensitive resin composition using such an unsaturated group-containing polymerizable resin, which can be used as a positive resist, has excellent patterning properties, can form a cured film having high adhesive strength without performing a bleaching step, and can provide excellent peelability when the cured film is irradiated with a laser. Furthermore, according to the present invention, it is possible to provide a cured resin film and a laminate using such a photosensitive resin composition, and a method for manufacturing and processing the laminate.

[0260] Therefore, the unsaturated group-containing polymerizable resin of the present invention is useful as a resin material for positive resists used in various applications (for example, laser mass transfer applications for micro LEDs, etc.).

Claims

1. An unsaturated group-containing polymerizable resin comprising a compound represented by the following general formula (1): 【Chemical 1】 [In formula (1), each Ar independently represents an aromatic hydrocarbon group having from 6 to 14 carbon atoms, and some of the hydrogen atoms constituting the aromatic hydrocarbon group may be substituted with a substituent selected from the group consisting of an alkyl group having from 1 to 10 carbon atoms, an aryl group and an arylalkyl group having from 6 to 10 carbon atoms, a cycloalkyl group and a cycloalkylalkyl group having from 3 to 10 carbon atoms, an alkoxy group having from 1 to 5 carbon atoms, and a halogen group; R １ are each independently an alkylene group having 2 to 4 carbon atoms, each l is independently a number from 0 to 3, G's are each independently a hydrogen atom or a substituent represented by the following general formula (2), and at least one of G's is a substituent represented by the following general formula (2), W's are each independently a hydrogen atom, a (meth)acryloyl group, a functional group represented by the following general formula (3), or a functional group represented by the following general formula (4), and at least one of W's is a (meth)acryloyl group, a functional group represented by the following general formula (3), or a functional group represented by the following general formula (4), L is a substituent represented by the following general formula (5): Each X is independently —CO— or —SO ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ -, -Si(CH ３ ) ２ -, -O-, -CH ２ -, a single bond, or a group represented by the following general formula (6): Y is a tetravalent carboxylic acid residue obtained by removing a carboxy group from one selected from the group consisting of a saturated linear hydrocarbon tetracarboxylic acid which may be substituted with a saturated cyclic hydrocarbon, an alicyclic tetracarboxylic acid which may be substituted with a saturated hydrocarbon, and an aromatic tetracarboxylic acid; n represents a natural number. 【Chemistry 2】 [In formula (2), R ２ is a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, R ３ are each independently a divalent saturated hydrocarbon group having from 2 to 20 carbon atoms, R ４ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, Z is a hydrogen atom or a substituent represented by the following general formula (7), and at least one of Z satisfies the condition that it is a substituent represented by the following general formula (7), m is a number between 0 and 10, * indicates the binding site to the structure represented by general formula (1). 【Chemistry 3】 【Chemistry 4】 [In formulas (3) and (4), R ３ are each independently a divalent saturated hydrocarbon group having from 2 to 20 carbon atoms, R ５ is a saturated or unsaturated divalent hydrocarbon group having from 2 to 20 carbon atoms, R ６ is an alkylene group or alkylarylene group having from 2 to 10 carbon atoms, R ７ is a hydrogen atom or a methyl group, m is a number between 0 and 10, * indicates the binding site to the structure represented by general formula (1). 【Chemistry 5】 [In formula (5), V is a carboxylic acid residue obtained by removing a carboxy group from one selected from the group consisting of saturated linear hydrocarbon dicarboxylic acids which may be substituted with a hydrocarbon group, saturated cyclic hydrocarbon dicarboxylic acids which may be substituted with a saturated hydrocarbon group, unsaturated dicarboxylic acids, aromatic dicarboxylic acids, citric acid, trimellitic acid, and hexahydrotrimellitic acid, G's are each independently a hydrogen atom or a substituent represented by the following general formula (2), and the condition that at least one of G's in formula (5) is a substituent represented by the general formula (2) is satisfied: q is 1 or 2; * indicates the binding site to the structure represented by general formula (1). 【Chemistry 6】 [In formula (6), * indicates the bonding site to the structure represented by general formula (1)] 【Chemistry 7】 [In formula (7), V is a carboxylic acid residue obtained by removing a carboxy group from one selected from the group consisting of saturated linear hydrocarbon dicarboxylic acids which may be substituted with a hydrocarbon group, saturated cyclic hydrocarbon dicarboxylic acids which may be substituted with a saturated hydrocarbon group, unsaturated dicarboxylic acids, aromatic dicarboxylic acids, citric acid, trimellitic acid, and hexahydrotrimellitic acid, q is 1 or 2; * indicates the binding site to the structure represented by general formula (2).

2. 2. The unsaturated group-containing polymerizable resin according to claim 1, which has a weight average molecular weight of 1,000 to 40,000 and an acid value of 20 to 200 mgKOH / g.

3. a diol compound (a-1) represented by the following general formula (8); a tetracarboxylic dianhydride (a-2) represented by the following general formula (12), a dicarboxylic acid monoanhydride (a-3) represented by the following general formula (13), to obtain a first reactant having a carboxy group; a step of reacting the first reactant with an oxirane compound (a-4) represented by the following general formula (14) to obtain a second reactant having a hydroxyl group; a step of reacting the second reactant having a hydroxyl group with a dicarboxylic acid monoanhydride (a-5) represented by the following general formula (13) to obtain the unsaturated group-containing polymerizable resin according to claim 1 or 2; Including, the molar amount of the component (a-4) used when reacting the first reactant with the component (a-4) is an amount such that the molar ratio ([component (a-4)] / [(2×[component (a-2)]))+[component (a-3)]] to the sum of twice the molar amount of the component (a-2) used in producing the first reactant and the molar amount of the component (a-3) used in producing the first reactant is 0.5 or more and 2.0 or less, and the molar amount of the component (a-5) used when reacting the second reactant with the component (a-5) is an amount such that the molar ratio ([component (a-5)] / [component (a-4)]) to the molar amount of the component (a-4) used when reacting the first reactant with the component (a-4) is 0.5 or more and 2.0 or less; A method for producing an unsaturated group-containing polymerizable resin. 【Chemistry 8】 [In formula (8), each Ar is independently an aromatic hydrocarbon group having from 6 to 14 carbon atoms, and some of the hydrogen atoms constituting the aromatic hydrocarbon group may be substituted with a substituent selected from the group consisting of an alkyl group having from 1 to 10 carbon atoms, an aryl group and an arylalkyl group having from 6 to 10 carbon atoms, a cycloalkyl group and a cycloalkylalkyl group having from 3 to 10 carbon atoms, an alkoxy group having from 1 to 5 carbon atoms, and a halogen group; R １ are each independently an alkylene group having 2 to 4 carbon atoms, each l is independently a number from 0 to 3, W's are each independently a hydrogen atom, a (meth)acryloyl group, a functional group represented by the following general formula (9), or a functional group represented by the following general formula (10), and at least one of W's is a (meth)acryloyl group, a functional group represented by the following general formula (9), or a functional group represented by the following general formula (10), Each X is independently —CO— or —SO ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ -, -Si(CH ３ ) ２ -, -O-, -CH ２ -, a single bond, or a group represented by the following general formula (11): 【Chemistry 9】 【Chemistry 10】 [In formulas (9) and (10), R ３ are each independently a divalent saturated hydrocarbon group having from 2 to 20 carbon atoms, R ５ is a saturated or unsaturated divalent hydrocarbon group having from 2 to 20 carbon atoms, R ６ is an alkylene group or alkylarylene group having from 2 to 10 carbon atoms, R ７ is a hydrogen atom or a methyl group, m is a number between 0 and 10, * indicates the binding site to the structure represented by general formula (8). 【Chemistry 11】 [In formula (11), * indicates the bonding site to the structure represented by general formula (8)] 【Chemistry 12】 [In formula (12), Y represents a tetravalent carboxylic acid residue obtained by removing a carboxy group from one selected from the group consisting of saturated linear hydrocarbon tetracarboxylic acids which may be substituted with saturated cyclic hydrocarbons, alicyclic tetracarboxylic acids which may be substituted with saturated hydrocarbons, and aromatic tetracarboxylic acids.] 【Chemistry 13】 [In formula (13), V is a carboxylic acid residue obtained by removing a carboxy group from one selected from the group consisting of saturated linear hydrocarbon dicarboxylic acids which may be substituted with a hydrocarbon group, saturated cyclic hydrocarbon dicarboxylic acids which may be substituted with a saturated hydrocarbon group, unsaturated dicarboxylic acids, aromatic dicarboxylic acids, citric acid, trimellitic acid, and hexahydrotrimellitic acid, q is 1 or 2. 【Chemistry 14】 [In formula (14), R ２ is a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, R ３ are each independently a divalent saturated hydrocarbon group having from 2 to 20 carbon atoms, R ４ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, m is a number between 0 and 10.

4. (A) the unsaturated group-containing polymerizable resin according to claim 1 or 2; (B) a photosensitizer, and (C) a solvent, A photosensitive resin composition comprising:

5. The photosensitive resin composition according to claim 4, further comprising (D) an epoxy compound having two or more epoxy groups.

6. A cured resin film obtained by curing the photosensitive resin composition according to claim 4.

7. A laminate comprising an adhesive layer formed between a light-transmitting support and an adherend, the adhesive layer comprising a dried coating film or a cured film of the photosensitive resin composition according to claim 4.

8. forming an adhesive layer on the surface of one or both of a light-transmitting support and an adherend using the photosensitive resin composition according to claim 4; a step of adhering the support and the adherend via the adhesive layer formed in the step to obtain a laminate; A method for producing a laminate comprising the steps of:

9. forming an adhesive layer on one or both surfaces of a light-transmitting support and an adherend included in a laminate structure of an adherend and a holding substrate using the photosensitive resin composition according to claim 4; a step of adhering the support and the laminated structure via the adhesive layer formed in the step above to obtain a laminate in which the support, the adhesive layer, the adherend, and the holding substrate are laminated in this order; a step of exposing the adhesive layer to light from the holding substrate side; peeling the holding substrate from the laminate with light; forming a pattern in the adhesive layer by development; A method for producing a laminate comprising the steps of:

10. a step of preparing a laminate having an adhesive layer formed of a cured film of the photosensitive resin composition according to claim 4 between a light-transmitting support and an adherend; a step of irradiating the adhesive layer with light to separate the support and the adherend; Including, The support transmits light with a wavelength of 10 nm or more and 400 nm or less, and A method for treating a laminate, wherein, when separating the support and the adherend, the support and the adherend are separated by irradiating the adhesive layer with light from the support side.

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