Negative photosensitive adhesive composition, photosensitive adhesive dry film, pattern formation method, and method for producing laminate

Abstract

The present invention employs a negative photosensitive adhesive composition comprising an epoxy resin selected from the group consisting of bisphenol epoxy resins and hydrogenated bisphenol epoxy resins, an epoxy resin having a tensile elastic modulus of 100 MPa or less when cured alone, and a compound containing an anion represented by formula (I-an). In formula (I-an), A is selected from the group consisting of boron, aluminum, gallium, phosphorus, arsenic, and bismuth. X is a halogen atom. Rb1 is an organic group. j is an integer of 1 to 3, k is an integer of 1 to 6, and l is an integer of 0 to 5. Rb1 may be connected to each other to form a divalent or higher organic group coordinating to A. l / (k + l) is at least 0 and less than 0.7. With such a negative photosensitive adhesive composition, substrates can be affixed to each other, warping of a laminate after affixing can be suppressed, and the amount of free halogen atoms can be reduced.

Description

Negative photosensitive adhesive composition, photosensitive adhesive dry film, pattern forming method, and laminate manufacturing method

[0001] The present invention relates to a negative-type photosensitive adhesive composition, a photosensitive adhesive dry film, a pattern formation method, and a laminate manufacturing method. This application claims priority to Japanese Patent Application No. 2024-106208, filed in Japan on July 1, 2024, the contents of which are incorporated herein by reference.

[0002] As electronic components become more sophisticated, semiconductor devices are becoming smaller and more sophisticated, and to address this, device integration and various packaging forms have been proposed. For example, a package (hollow package) has been proposed, which has a hollow structure in which the wiring substrate on which the electrodes are formed is kept hollow.

[0003] Photosensitive adhesives are used as one means for integrating devices and forming hollow structures. After forming a pattern by applying, exposing, and developing a photosensitive adhesive onto a substrate, the substrate on which the pattern has been formed can be bonded to another substrate that serves as a top plate by thermocompression bonding, allowing for stacking of substrates or forming a hollow structure (see, for example, Patent Document 1).

[0004] JP 2017-161837 A

[0005] However, when substrates are bonded together by thermocompression using conventional photosensitive adhesives, warping (deformation) of the laminate after bonding is a problem. Furthermore, when conventional photosensitive adhesives are used, if the laminate contains a metal such as aluminum, halogen atoms may be liberated, causing corrosion of the aluminum.

[0006] The present invention has been made in view of the above circumstances, and has an object to provide a negative photosensitive adhesive composition that can bond substrates together, suppress warping of the laminate after bonding, and reduce the amount of released halogen atoms; a photosensitive adhesive dry film using the same; pattern formation methods that use the negative photosensitive adhesive composition and the photosensitive adhesive dry film; and a method for manufacturing a laminate using the pattern formation method.

[0007] In order to solve the above problems, the present invention employs the following configuration. That is, a first aspect of the present invention is a negative-type photosensitive adhesive composition containing an epoxy group-containing compound (A) and a photoacid generator (B), in which the epoxy group-containing compound (A) contains at least one epoxy resin (A1) selected from the group consisting of bisphenol epoxy resins and hydrogenated bisphenol epoxy resins, and another epoxy resin (A2), the epoxy resin (A2) being an epoxy resin that exhibits a tensile modulus of 100 MPa or less when cured alone, and the photoacid generator (B) contains a compound (B1) comprising a cation moiety and an anion moiety, the anion moiety containing an anion represented by the following general formula (I-an):

[0008] [wherein A is a hetero element selected from the group consisting of boron, aluminum, gallium, phosphorus, arsenic and bismuth; and X is a halogen atom. ｂ１ is a monovalent organic group. j is an integer of 1 to 3. k is an integer of 1 to 6. l is an integer of 0 to 5. However, when k is an integer of 2 or more, there are multiple R ｂ１ is R ｂ１ They may be linked together to form a divalent or higher organic group that coordinates to A. l / (k+l) is 0 or more and less than 0.7.

[0009] A second aspect of the present invention is a photosensitive adhesive dry film produced using the negative photosensitive adhesive composition according to the first aspect.

[0010] A third aspect of the present invention is a pattern formation method comprising the steps of forming a photosensitive resin film on a support using the negative photosensitive adhesive composition according to the first aspect or the photosensitive adhesive dry film according to the second aspect, exposing the photosensitive resin film to light, and developing the exposed photosensitive resin film with a developer containing an organic solvent to form a negative pattern.

[0011] A fourth aspect of the present invention is a method for producing a laminate, comprising the steps of obtaining a support having a negative pattern by using the pattern formation method according to the third aspect, and bonding the support having the negative pattern to another support by thermocompression bonding to obtain a laminate.

[0012] According to the present invention, it is possible to provide a negative photosensitive adhesive composition that can bond substrates together, suppress warping of the laminate after bonding, and reduce the amount of released halogen atoms; a photosensitive adhesive dry film using the same; pattern formation methods that use the negative photosensitive adhesive composition and the photosensitive adhesive dry film; and a method for manufacturing a laminate using the pattern formation method.

[0013] In this specification and claims, "aliphatic" is a relative concept to aromatic, and is defined as meaning a group or compound that does not have aromaticity. Unless otherwise specified, "alkyl group" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups in alkoxy groups. Unless otherwise specified, "alkylene group" includes linear, branched, and cyclic divalent saturated hydrocarbon groups. A "halogenated alkyl group" is a group in which some or all of the hydrogen atoms of an alkyl group have been substituted with halogen atoms, and examples of such halogen atoms include fluorine, chlorine, bromine, and iodine atoms. A "fluorinated alkyl group" is a group in which some or all of the hydrogen atoms of an alkyl group have been substituted with fluorine atoms. A "structural unit" refers to a monomer unit that constitutes a polymeric compound (resin, polymer, copolymer). The phrase "optionally has a substituent" refers to the case in which a hydrogen atom (-H) is replaced with a monovalent group, and the case in which a methylene group (-CH ２ The term "exposure" encompasses both cases where the radical (-) is substituted with a divalent group and cases where the radical (-) is substituted with a divalent group. The term "exposure" encompasses all cases of irradiation with radiation.

[0014] In the negative photosensitive adhesive composition according to the first embodiment, the epoxy equivalent of the entire epoxy group-containing compound (hereinafter also referred to as the "blended epoxy equivalent") is calculated by the following formula.

[0015] Epoxy equivalent weight (g / eq.) of all epoxy group-containing compounds = total amount of epoxy group-containing compounds (g) / total epoxy value of each epoxy group-containing compound (eq.)

[0016] Numerator: Total amount of epoxy group-containing compounds (g) = amount of epoxy resin (A1) (g) + amount of epoxy resin (A2) (g) + ...

[0017] Denominator: Sum of epoxy values ​​of epoxy group-containing compounds (eq.) = {amount of epoxy resin (A1) (g) / epoxy equivalent of epoxy resin (A1) (g / eq.)} + {amount of epoxy resin (A2) (g) / epoxy equivalent of epoxy resin (A2) (g / eq.)} + ...

[0018] The tensile modulus of an epoxy group-containing compound when cured alone is measured as follows. A test specimen molded into a dumbbell or rectangular shape as specified in JIS K 7139 is prepared as a cured product of the epoxy group-containing compound to be measured. The test specimen is molded by the same film formation, exposure, and development steps as in the "Pattern Formation" section of the "Examples" section below, followed by a heat treatment at 100°C for 2 minutes. The molding material used to prepare the test specimen is a composition containing 100 parts by mass of an epoxy group-containing compound, 0.2 parts by mass of the photoacid generator (B) (B)-4 described below, i.e., a compound represented by chemical formula (B-4)), and 54 parts by mass of 3-methoxybutyl acetate as a solvent. Then, a test piece having an arbitrary film thickness and molded into a dumbbell shape or a rectangular shape as described in JIS K 7139 is pulled at a constant speed of 1 mm / min using a tensile tester such as EZ-LX (Shimadzu) to calculate the elastic modulus.

[0019] (Negative Photosensitive Adhesive Composition) One embodiment of the negative photosensitive adhesive composition contains an epoxy group-containing compound (A) (hereinafter also referred to as "component (A)") and a photoacid generator (B) (hereinafter also referred to as "component (B)"). The component (A) contains at least one epoxy resin (A1) selected from the group consisting of bisphenol epoxy resins and hydrogenated bisphenol epoxy resins, and another epoxy resin (A2). This epoxy resin (A2) is an epoxy resin that exhibits a tensile modulus of elasticity of 100 MPa or less when cured alone. The component (B) contains a compound (B1) composed of a cation moiety and an anion moiety. The anion moiety contains an anion represented by the general formula (I-an).

[0020] When a photosensitive resin film is formed using such a negative photosensitive adhesive composition and the photosensitive resin film is selectively exposed to light, the cationic moiety of component (B) decomposes in the exposed areas of the photosensitive resin film to generate an acid, and the epoxy groups in component (A) undergo ring-opening polymerization under the action of the acid, reducing the solubility of component (A) in a developer containing an organic solvent. Meanwhile, the solubility of component (A) in a developer containing an organic solvent remains unchanged in the unexposed areas of the photosensitive resin film, resulting in a difference in solubility in a developer containing an organic solvent between the exposed and unexposed areas of the photosensitive resin film. Therefore, when the photosensitive resin film is developed with a developer containing an organic solvent, the unexposed areas are dissolved and removed, forming a negative pattern.

[0021] <Epoxy Group-Containing Compound (A)> In the negative-type photosensitive adhesive composition of this embodiment, component (A) contains at least one epoxy resin (A1) selected from the group consisting of bisphenol epoxy resins and hydrogenated bisphenol epoxy resins, and another epoxy resin (A2). The epoxy resin (A2) is an epoxy resin that exhibits a tensile modulus of elasticity of 100 MPa or less when cured alone.

[0022] <Epoxy Resin (A1)> In the negative photosensitive adhesive composition of this embodiment, the epoxy resin (A1) (hereinafter also referred to as “component (A1)”) is at least one epoxy resin selected from the group consisting of bisphenol epoxy resins and hydrogenated bisphenol epoxy resins.

[0023] The epoxy equivalent of the component (A1) is, for example, 400 g / eq. or more, preferably 400 g / eq. or more and 3000 g / eq. or less, more preferably 450 g / eq. or more and 2500 g / eq. or less, and even more preferably 500 g / eq. or more and 2000 g / eq. or less.

[0024] The tensile modulus of elasticity of the component (A1) when cured alone is, for example, more than 100 MPa, preferably 500 MPa or more, and may be 1000 MPa or more and 10000 MPa or less, or 2000 MPa or more and 5000 MPa or less.

[0025] Regarding bisphenol-type epoxy resins: Examples of bisphenol-type epoxy resins include epoxy resins represented by the following general formula (abp1).

[0026] [In the formula, R ＥＰ is an epoxy group-containing group. ａ３１ and R ａ３２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ３１ is an integer from 1 to 50.

[0027] In the formula (abp1), R ＥＰ is an epoxy group-containing group. ＥＰ The epoxy group-containing group is not particularly limited, and examples thereof include a group consisting of only epoxy groups; a group consisting of only alicyclic epoxy groups; and a group having an epoxy group or alicyclic epoxy group and a divalent linking group. An alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure, which is a three-membered ring ether, specifically a group having an alicyclic group and an oxacyclopropane structure. The alicyclic group that forms the basic skeleton of the alicyclic epoxy group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of polycyclic alicyclic groups include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl groups. The hydrogen atoms of these alicyclic groups may be substituted with alkyl groups, alkoxy groups, hydroxyl groups, or the like. In the case of a group having an epoxy group or an alicyclic epoxy group and a divalent linking group, it is preferable that the epoxy group or the alicyclic epoxy group is bonded via the divalent linking group bonded to an oxygen atom (—O—) in the formula.

[0028] Here, the divalent linking group is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.

[0029] Regarding the divalent hydrocarbon group which may have a substituent: The divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group in the divalent hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. More specifically, the aliphatic hydrocarbon group may be a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in its structure.

[0030] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. The linear aliphatic hydrocarbon group is preferably a linear alkylene group, and specifically, a methylene group [—CH ２ -], ethylene group [-(CH ２ ) ２ -], trimethylene group [-(CH ２ ) ３ -], tetramethylene group [-(CH ２ ) ４ -], pentamethylene group [-(CH ２ ) ５ The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms, and most preferably 2 or 3 carbon atoms. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specifically, -CH(CH ３ ) -, -CH(CH ２ CH ３ ) -, -C(CH ３ ) ２ -, -C(CH ３ ) (CH ２ CH ３ ) -, -C(CH ３ ) (CH ２ CH ２ CH ３ ) -, -C(CH ２ CH ３ ) ２ alkylmethylene groups such as -; -CH(CH ３ ) CH ２ -, -CH(CH ３ ) CH(CH３ ) -, -C(CH ３ ) ２ CH ２ -, -CH(CH ２ CH ３ ) CH ２ -, -C(CH ２ CH ３ ) ２ -CH ２ alkylethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ alkyltrimethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ CH ２ The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0031] Examples of the aliphatic hydrocarbon group containing a ring in its structure include alicyclic hydrocarbon groups (groups in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same as those described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0032] The aromatic hydrocarbon group in the divalent hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n+2) π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. Specific examples of the aromatic hydrocarbon group include groups in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic heterocycle (arylene groups or heteroarylene groups); groups in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups in which one hydrogen atom of a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) has been substituted with an alkylene group (e.g., groups in which one further hydrogen atom has been removed from the aryl group in an arylalkyl group such as a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, or 2-naphthylethyl group). The alkylene group bonded to the aryl group or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 or 2, and particularly preferably 1 carbon atom.

[0033] The divalent hydrocarbon group may have a substituent. The linear or branched aliphatic hydrocarbon group as the divalent hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and a carbonyl group.

[0034] The alicyclic hydrocarbon group in the aliphatic hydrocarbon group containing a ring in its structure as a divalent hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, and preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group. Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms. In the alicyclic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. Examples of the substituent containing a hetero atom include -O-, -C(=O)-O-, -S-, and -S(=O) ２ -, -S(=O) ２ —O— is preferred.

[0035] In the aromatic hydrocarbon group as a divalent hydrocarbon group, a hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. Examples of the alkoxy group, halogen atom, and halogenated alkyl group as the substituent include those exemplified as the substituent substituting a hydrogen atom of the alicyclic hydrocarbon group.

[0036] Regarding the divalent linking group containing a hetero atom: The hetero atom in the divalent linking group containing a hetero atom is an atom other than a carbon atom or a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

[0037] In the divalent linking group containing a hetero atom, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O)-, -O-C(=O)-O-; -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)- (H may be substituted with a substituent such as an alkyl group or an acyl group); -S-, -S(=O) ２ -, -S(=O) ２ -O-, general formula -Y ２１ -O-Y ２２ -, -Y ２１ -O-, -Y ２１ -C(=O)-O-, -C(=O)-O-Y ２１ , -[Y ２１ -C(=O)-O] ｍ” -Y ２２ - or -Y ２１ -OC(=O)-Y ２２ -, wherein Y ２１ and Y ２２ are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m" is an integer of 1 to 3. When the divalent linking group containing a hetero atom is -C(=O)-NH-, -NH-, -NH-C(=O)-O-, or -NH-C(=NH)-, the H may be substituted with a substituent such as an alkyl group or acyl. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5 carbon atoms. Formula -Y ２１ -O-Y ２２ -, -Y ２１ -O-, -Y ２１ -C(=O)-O-, -C(=O)-O-Y ２１ -, -[Y ２１ -C(=O)-O] ｍ” -Y ２２ - or -Y ２１ -OC(=O)-Y ２２ -Middle, Y２１ and Y ２２ are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same as the "divalent hydrocarbon group which may have a substituent" listed above in the description of the divalent linking group. Y ２１ As Y, a linear aliphatic hydrocarbon group is preferred, a linear alkylene group is more preferred, a linear alkylene group having 1 to 5 carbon atoms is even more preferred, and a methylene group or an ethylene group is particularly preferred. ２２ is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. ２１ -C(=O)-O] ｍ” -Y ２２ In the group represented by -, m" is an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1. That is, the group represented by the formula -[Y ２１ -C(=O)-O] ｍ” -Y ２２ The group represented by - includes the group represented by the formula -Y ２１ -C(=O)-O-Y ２２ Among them, groups represented by the formula -(CH ２ ) ａ’ -C(=O)-O-(CH ２ ) ｂ’ In the formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1.

[0038] Among them, R ＥＰ The epoxy group-containing group in is preferably a glycidyl group.

[0039] In the formula (abp1), R ａ３１ , R ａ３２The alkyl group having 1 to 5 carbon atoms is, for example, a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group, and examples of the cyclic alkyl group include a cyclobutyl group and a cyclopentyl group. Among these, R ａ３１ , R ａ３２ is preferably a hydrogen atom or a linear or branched alkyl group, more preferably a hydrogen atom or a linear alkyl group, and particularly preferably a hydrogen atom or a methyl group. ａ３１ may be the same or different. ａ３２ may be the same or different. ａ３１ and R ａ３２ When all of R are methyl groups, the epoxy resin represented by general formula (abp1) is a bisphenol A type epoxy resin. ａ３１ and R ａ３２ When all of the groups are hydrogen atoms, the epoxy resin is a bisphenol F type epoxy resin.

[0040] In the formula (abp1), na ３１ is an integer of 1 to 50, preferably an integer of 4 to 15, and more preferably an integer of 5 to 8.

[0041] Regarding hydrogenated bisphenol-type epoxy resins: Examples of hydrogenated bisphenol-type epoxy resins include epoxy resins represented by the following general formula (Aep-1).

[0042] [In the formula, Rep １ ~Rep ４ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a trifluoromethyl group. ５ represents a hydrogen atom or a glycidyl group, Rep ５ If there are multiple Rep ５ may be the same or different, and n is an integer of 1 or more.

[0043] In the formula (Aep-1), Rep １ ~Rep ４ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a trifluoromethyl group. １ ~Rep ４ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group. １ ~Rep ４ are all methyl groups, the epoxy resin represented by general formula (Aep-1) is a hydrogenated bisphenol A epoxy resin.

[0044] In the formula (Aep-1), Rep ５ represents a hydrogen atom or a glycidyl group, preferably a hydrogen atom. ５ If there are multiple Rep ５ In the formula (Aep-1), n ​​is an integer of 1 or more, preferably an integer of 1 to 20, and more preferably an integer of 3 to 10.

[0045] In the negative photosensitive adhesive composition of this embodiment, the component (A1) may be used alone or in combination of two or more. Among the above, the component (A1) is preferably an epoxy resin selected from the group consisting of bisphenol A epoxy resins, bisphenol F epoxy resins, and hydrogenated bisphenol A epoxy resins. The component (A1) is preferably a bisphenol A epoxy resin. Alternatively, the component (A1) is preferably a bisphenol F epoxy resin. Alternatively, the component (A1) is preferably a hydrogenated bisphenol A epoxy resin.

[0046] In the negative photosensitive adhesive composition of this embodiment, the content of component (A1) in component (A) is preferably 50 mass% or more, and more preferably 50 mass% or more and 90 mass% or less, relative to the total mass (100 mass%) of component (A).

[0047] <Epoxy Resin (A2)> In the negative photosensitive adhesive composition of this embodiment, the epoxy resin (A2) (hereinafter also referred to as “component (A2)”) is an epoxy resin that, when cured alone, exhibits a tensile modulus of elasticity of 100 MPa or less. However, component (A2) does not fall under the category of component (A1) above, i.e., component (A2) is different from component (A1).

[0048] The epoxy equivalent of the component (A2) is, for example, 400 g / eq. or more, preferably 400 g / eq. or more and 3000 g / eq. or less, more preferably 450 g / eq. or more and 2500 g / eq. or less, and even more preferably 500 g / eq. or more and 2000 g / eq. or less.

[0049] The tensile modulus of component (A2) when cured alone is 100 MPa or less, preferably 90 MPa or less, and may be 1 MPa to 80 MPa or less, or 2 MPa to 70 MPa or less. If the tensile modulus of component (A2) is equal to or less than the upper limit of the above range, warping of the laminate after application can be suppressed. On the other hand, if the tensile modulus is equal to or greater than the lower limit of the above preferred range, the strength of the cured product can be easily increased.

[0050] Suitable examples of the component (A2) include epoxy resins having at least one structure selected from the group consisting of a structure represented by the following general formula (A2-r-1) and a structure represented by the following general formula (A2-r-2):

[0051] [In the formula, R ａ２０ ~R ａ２３ are each independently an alkyl group or a hydrogen atom. m1 and m2 are each independently an integer of 1 to 15.

[0052] In the formula (A2-r-1), R ａ２０ ~R ａ２１ are each independently an alkyl group or a hydrogen atom. ａ２０ ~R ａ２１In formula (A2-r-1), m1 is an integer of 1 to 15, preferably an integer of 2 to 15, more preferably an integer of 3 to 13, and even more preferably an integer of 4 to 10.

[0053] In the formula (A2-r-2), R ａ２２ ~R ａ２３ are each independently an alkyl group or a hydrogen atom. ａ２２ ~R ａ２３ In formula (A2-r-2), m2 is an integer of 1 to 15, preferably an integer of 2 to 15, more preferably an integer of 3 to 13, and even more preferably an integer of 4 to 10.

[0054] When the component (A2) contains both the structure represented by general formula (A2-r-1) and the structure represented by general formula (A2-r-2) in the molecular chain, the total value of m1 and m2 is preferably an integer of 2 to 15, more preferably an integer of 3 to 13, and even more preferably an integer of 4 to 10.

[0055] Suitable examples of the component (A2) include epoxy resins having at least one structure selected from the group consisting of the structure represented by the general formula (A2-r-1) and the structure represented by the general formula (A2-r-2), as well as a linking group derived from bisphenol. The linking group derived from bisphenol here is a linking group derived from bisphenol A (—O—C ６ H ４ -C(CH ３ ) ２ -C ６ H ４ -O-), a linking group derived from bisphenol F (-O-C ６ H ４ -CH ２ -C ６ H ４ —O—) and the like.

[0056] Furthermore, examples of the component (A2) include epoxy resins having a repeating structure of structural units containing at least one structure selected from the group consisting of the structure represented by general formula (A2-r-1) and the structure represented by general formula (A2-r-2), and a linking group derived from a bisphenol.

[0057] Specific examples of suitable components (A2) are listed below. m21 is an integer of 1 to 15. mx and my each represent the number of repetitions of a structural unit. mq, mr, and mz each represent the number of repetitions of a structural unit. R Ｘ is an alkylene group, preferably an alkylene group having 1 to 15 carbon atoms.

[0058]

[0059]

[0060]

[0061] In the negative photosensitive adhesive composition of this embodiment, the component (A2) may be used alone or in combination of two or more. Among the above, the component (A2) is preferably an epoxy resin having a repeating structure of a structural unit containing at least one structure selected from the group consisting of the structure represented by the general formula (A2-r-1) and the structure represented by the general formula (A2-r-2), and a linking group derived from bisphenol. Alternatively, the component (A2) may be an epoxy resin having a repeating structure of a structural unit containing at least one structure selected from the group consisting of the structure represented by the general formula (A2-r-1) and the structure represented by the general formula (A2-r-2), and a linking group (-O-C) derived from bisphenol A. ６ H ４ -C(CH ３ ) ２ -C ６ H ４ Alternatively, the component (A2) is preferably an epoxy resin having a repeating structure of structural units containing at least one structure selected from the group consisting of the structure represented by the general formula (A2-r-1) and the structure represented by the general formula (A2-r-2), and a linking group (—O—C) derived from bisphenol F.６ H ４ -CH ２ -C ６ H ４ Preferably, the component (A2) is an epoxy resin having a repeating structure of structural units containing the following structural unit: (A2-X), (A2-Y), (A2-P), (A2-Q), (A2-R), and epoxy group-containing compounds represented by the chemical formulas (A2-Z1) to (A2-Z5). Alternatively, the component (A2) is preferably at least one selected from the group consisting of epoxy resins represented by the chemical formula (A2-X), (A2-Y), (A2-P), (A2-Q), (A2-R), and epoxy group-containing compounds represented by the chemical formulas (A2-Z1) to (A2-Z5). More preferably, the component (A2) is at least one selected from the group consisting of epoxy resins represented by the chemical formula (A2-X), (A2-Y), and (A2-R), and even more preferably, the component (A2) is at least one selected from the group consisting of epoxy resins represented by the chemical formula (A2-X) and (A2-Y).

[0062] In the negative photosensitive adhesive composition of this embodiment, the content of component (A2) in component (A) is preferably 10 mass % or more, and more preferably 20 mass % or more and 40 mass % or less, relative to the total mass (100 mass %) of component (A).

[0063] Other Epoxy Group-Containing Compounds The negative photosensitive adhesive composition of this embodiment may contain, in addition to the components (A1) and (A2), other epoxy group-containing compounds. Examples of other epoxy group-containing compounds include alicyclic epoxy resins (A3) and acrylic resins.

[0064] Alicyclic Epoxy Resin (A3): Examples of the alicyclic epoxy resin (hereinafter also referred to as "component (A3)") include compounds containing a partial structure represented by the following general formula (A3-m1).

[0065] [In the formula, n ２ is an integer from 1 to 4.

[0066] In formula (A3-m1), n ２is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2.

[0067] Examples of compounds containing a partial structure represented by general formula (A3-m1) include compounds in which a plurality of partial structures represented by general formula (A3-m1) are bonded via a divalent linking group or a single bond. Among these, compounds in which a plurality of partial structures represented by general formula (A3-m1) are bonded via a divalent linking group are preferred. The divalent linking group used here is not particularly limited, but suitable examples include divalent hydrocarbon groups which may have a substituent and divalent linking groups which contain a heteroatom. The divalent hydrocarbon groups which may have a substituent and divalent linking groups which contain a heteroatom are preferably R in formula (abp1) above. ＥＰ The divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom are the same as those explained in (epoxy group-containing group), and among these, the divalent linking group containing a hetero atom is preferred. ２１ a group represented by —C(═O)—O—, —C(═O)—O—Y ２１ A group represented by - is more preferred. ２１ As the alkyl group, a straight-chain aliphatic hydrocarbon group is preferred, a straight-chain alkylene group is more preferred, a straight-chain alkylene group having 1 to 5 carbon atoms is even more preferred, and a methylene group or ethylene group is particularly preferred.

[0068] Examples of compounds containing a partial structure represented by general formula (A3-m1) include compounds represented by the following chemical formula: In the following chemical formula, l represents an integer of 1 to 10, and m represents an integer of 1 to 30. R represents an alkylene group having 1 to 8 carbon atoms (preferably an alkylene group having 1 to 3 carbon atoms, such as a methylene group, an ethylene group, a propylene group, or an isopropylene group). n1 and n2 each represent an integer of 1 to 30.

[0069]

[0070] Further, preferred examples of the alicyclic epoxy resin include compounds represented by the following general formula (A3-m2):

[0071] [In the formula, R ＥＰis an epoxy group-containing group. ＥＰ may be the same or different from each other.

[0072] In the formula (A3-m2), R ＥＰ is an epoxy group-containing group, and R in the above formula (abp1) ＥＰ is the same as:

[0073] When the negative photosensitive adhesive composition of this embodiment contains the component (A3) in addition to the above-mentioned components (A1) and (A2), the component (A3) may be used alone or in combination of two or more. Among the above, the component (A3) is preferably a compound containing a partial structure represented by the above general formula (A3-m1).

[0074] When the negative-type photosensitive adhesive composition of this embodiment contains the component (A3), the content of the component (A3) in the component (A) is preferably 5% by mass or more, and more preferably 10% by mass or more and 20% by mass or less, relative to the total mass (100% by mass) of the component (A).

[0075] Regarding acrylic resins: Examples of acrylic resins include resins having epoxy group-containing units represented by the following general formula (a1-1) or (a1-2).

[0076] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. ４１ represents a divalent hydrocarbon group which may have a substituent. ４１ is an integer from 0 to 2. ａ４１ , R ａ４２ is an epoxy group-containing group. ４２ is 0 or 1. ４１ Is (na ４３ +1)valent aliphatic hydrocarbon group. ４３ is 1 or 2.]

[0077] In the formula (a1-1), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms represented by R is preferably linear or branched, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The halogenated alkyl group having 1 to 5 carbon atoms represented by R is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being particularly preferred. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the perspective of industrial availability, a hydrogen atom or a methyl group is most preferred.

[0078] In the formula (a1-1), Va ４１ represents a divalent hydrocarbon group which may have a substituent, and R in the formula (abp1) ＥＰ Examples of the divalent hydrocarbon group which may have a substituent include the same groups as those described in the above. ４１ The hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably a linear or branched aliphatic hydrocarbon group, still more preferably a linear aliphatic hydrocarbon group, and particularly preferably a linear alkylene group.

[0079] In formula (a1-1), na ４１ is an integer of 0 to 2, preferably 0 or 1.

[0080] In formulas (a1-1) and (a1-2), R ａ４１ , R ａ４２ is an epoxy group-containing group. ａ４１ , R ａ４２The epoxy group-containing group is not particularly limited, and examples thereof include a group consisting of only epoxy groups; a group consisting of only alicyclic epoxy groups; and a group having an epoxy group or alicyclic epoxy group and a divalent linking group. An alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure, which is a three-membered ring ether, specifically a group having an alicyclic group and an oxacyclopropane structure. The alicyclic group that forms the basic skeleton of the alicyclic epoxy group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of polycyclic alicyclic groups include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl groups. The hydrogen atoms of these alicyclic groups may be substituted with alkyl groups, alkoxy groups, hydroxyl groups, or the like. In the case of a group having an epoxy group or an alicyclic epoxy group and a divalent linking group, it is preferable that the epoxy group or the alicyclic epoxy group is bonded via the divalent linking group bonded to an oxygen atom (—O—) in the formula.

[0081] Here, the divalent linking group is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.

[0082] Regarding the divalent hydrocarbon group which may have a substituent: The divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group in the divalent hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. More specifically, the aliphatic hydrocarbon group may be a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in its structure.

[0083] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. The linear aliphatic hydrocarbon group is preferably a linear alkylene group, and specifically, a methylene group [—CH ２-], ethylene group [-(CH ２ ) ２ -], trimethylene group [-(CH ２ ) ３ -], tetramethylene group [-(CH ２ ) ４ -], pentamethylene group [-(CH ２ ) ５ The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms, and most preferably 2 or 3 carbon atoms. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specifically, -CH(CH ３ ) -, -CH(CH ２ CH ３ ) -, -C(CH ３ ) ２ -, -C(CH ３ ) (CH ２ CH ３ ) -, -C(CH ３ ) (CH ２ CH ２ CH ３ ) -, -C(CH ２ CH ３ ) ２ alkylmethylene groups such as -; -CH(CH ３ ) CH ２ -, -CH(CH ３ ) CH(CH ３ ) -, -C(CH ３ ) ２ CH ２ -, -CH(CH ２ CH ３ ) CH ２ -, -C(CH ２ CH ３ ) ２ -CH ２ alkylethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ alkyltrimethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ CH ２-, -CH ２ CH (CH ３ ) CH ２ CH ２ The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0084] Examples of the aliphatic hydrocarbon group containing a ring in its structure include alicyclic hydrocarbon groups (groups in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same as those described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0085] The aromatic hydrocarbon group in the divalent hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n+2) π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. Specific examples of the aromatic hydrocarbon group include a group (arylene group or heteroarylene group) in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic heterocycle; a group in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one hydrogen atom of a group (aryl group or heteroaryl group) in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle has been substituted with an alkylene group (e.g., a group in which another hydrogen atom has been removed from the aryl group in an arylalkyl group such as a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, or 2-naphthylethyl group). The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1. Among these, from the viewpoint of reducing autofluorescence, an aromatic hydrocarbon group not containing a fused ring is preferred as the aromatic hydrocarbon group in the divalent hydrocarbon group.

[0086] The divalent hydrocarbon group may have a substituent. The linear or branched aliphatic hydrocarbon group as the divalent hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and a carbonyl group.

[0087] The alicyclic hydrocarbon group in the aliphatic hydrocarbon group containing a ring in its structure as a divalent hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, and preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group. Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms. In the alicyclic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. Examples of the substituent containing a hetero atom include -O-, -C(=O)-O-, -S-, and -S(=O) ２ -, -S(=O) ２ —O— is preferred.

[0088] In the aromatic hydrocarbon group as a divalent hydrocarbon group, a hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. Examples of the alkoxy group, halogen atom, and halogenated alkyl group as the substituent include those exemplified as the substituent substituting a hydrogen atom of the alicyclic hydrocarbon group.

[0089] Regarding the divalent linking group containing a hetero atom: The hetero atom in the divalent linking group containing a hetero atom is an atom other than a carbon atom or a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

[0090] In the divalent linking group containing a hetero atom, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O)-, -O-C(=O)-O-; -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)- (H may be substituted with a substituent such as an alkyl group or an acyl group); -S-, -S(=O) ２ -, -S(=O) ２ -O-, general formula -Y ２１ -O-Y ２２ -, -Y ２１ -O-, -Y ２１ -C(=O)-O-, -C(=O)-O-Y ２１ , -[Y ２１ -C(=O)-O] ｍ” -Y ２２ - or -Y ２１ -OC(=O)-Y ２２ -, wherein Y ２１ and Y ２２ are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m" is an integer of 1 to 3. When the divalent linking group containing a hetero atom is -C(=O)-NH-, -NH-, -NH-C(=O)-O-, or -NH-C(=NH)-, the H may be substituted with a substituent such as an alkyl group or acyl. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5 carbon atoms. Formula -Y ２１ -O-Y ２２ -, -Y ２１ -O-, -Y ２１ -C(=O)-O-, -C(=O)-O-Y ２１ -, -[Y ２１ -C(=O)-O] ｍ” -Y ２２ - or -Y ２１ -OC(=O)-Y ２２ -Middle, Y２１ and Y ２２ are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same as the "divalent hydrocarbon group which may have a substituent" listed above in the description of the divalent linking group. Y ２１ As Y, a linear aliphatic hydrocarbon group is preferred, a linear alkylene group is more preferred, a linear alkylene group having 1 to 5 carbon atoms is even more preferred, and a methylene group or an ethylene group is particularly preferred. ２２ is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. ２１ -C(=O)-O] ｍ” -Y ２２ In the group represented by -, m" is an integer of 1 to 3, preferably 1 or 2, and more preferably 1. That is, the group represented by the formula -[Y ２１ -C(=O)-O] ｍ” -Y ２２ The group represented by - includes the group represented by the formula -Y ２１ -C(=O)-O-Y ２２ Among them, groups represented by the formula -(CH ２ ) ａ’ -C(=O)-O-(CH ２ ) ｂ’ In the formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1.

[0091] Among them, R ａ４１ , R ａ４２ The epoxy group-containing group in is preferably a glycidyl group.

[0092] In formula (a1-2), Wa ４１ In (na４３ The (+1)-valent aliphatic hydrocarbon group means a hydrocarbon group that is not aromatic and may be saturated or unsaturated, but is usually preferably saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, aliphatic hydrocarbon groups containing a ring in their structure, and groups that combine linear or branched aliphatic hydrocarbon groups with aliphatic hydrocarbon groups containing a ring in their structure.

[0093] Furthermore, the acrylic resin in component (A) may contain structural units derived from other polymerizable compounds in order to appropriately control the physical and chemical properties. Examples of such polymerizable compounds include known radically polymerizable compounds and anionically polymerizable compounds. Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxyl group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; hydroxypropyl acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl ... (meth)acrylic acid aryl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and amide bond-containing polymerizable compounds such as acrylamide and methacrylamide.

[0094] In the negative photosensitive adhesive composition of this embodiment, the combined epoxy equivalent of the entire component (A) is preferably 600 g / eq. or more, more preferably 600 g / eq. or more and 4000 g / eq. or less, even more preferably 600 g / eq. or more and 3000 g / eq. or less, and particularly preferably 600 g / eq. or more and 2000 g / eq. When the combined epoxy equivalent of the entire component (A) is at least the lower limit of the above-mentioned preferred range, a pattern with high rectangularity is more likely to be formed.

[0095] In the negative-type photosensitive adhesive composition of this embodiment, component (A) comprises component (A1) and component (A2), and the content of component (A1) in component (A) is preferably 50 mass% or more, more preferably 50 mass% or more and 90 mass% or less, and even more preferably more than 50 mass% and 85 mass% or less, relative to the total mass (100 mass%) of component (A). The content of component (A2) in component (A) is preferably 50 mass% or less, more preferably 10 mass% or more and 50 mass% or less, and even more preferably 15 mass% or more and less than 50 mass%, relative to the total mass (100 mass%) of component (A). When the contents of component (A1) and component (A2) are within the above-mentioned preferred ranges, the effects of the present invention are easily achieved, and in particular, warping of the laminate after application is easily suppressed.

[0096] In the negative photosensitive adhesive composition of this embodiment, the component (A) preferably contains the epoxy resin (A1), the alicyclic epoxy resin (A3), and an epoxy resin (A2") other than these that exhibits a tensile modulus of elasticity of 100 MPa or less when cured alone. In addition, the epoxy resin (A1) is preferably an epoxy resin selected from the group consisting of bisphenol A epoxy resins, bisphenol F epoxy resins, and hydrogenated bisphenol A epoxy resins. In addition, the alicyclic epoxy resin (A3) is preferably a compound containing a partial structure represented by general formula (A3-m1) above. In addition, the epoxy resin (A2") is preferably an epoxy resin having a repeating structure of structural units containing at least one structure selected from the group consisting of the structure represented by general formula (A2-r-1) and the structure represented by general formula (A2-r-2), and a linking group derived from a bisphenol.

[0097] It is preferred that the content of the epoxy resin (A1) in the component (A) is 50% by mass or more and 80% by mass or less, relative to the total mass (100% by mass) of the component (A); the content of the alicyclic epoxy resin (A3) in the component (A) is 10% by mass or more and 20% by mass or less, relative to the total mass (100% by mass) of the component (A); and the content of the epoxy resin (A2") in the component (A) is 10% by mass or more and 40% by mass or less, relative to the total mass (100% by mass) of the component (A). When the contents of the components (A1), (A2), and (A3) are within the above-mentioned preferred ranges, warping of the laminate after bonding is easily suppressed, and the sensitivity of pattern formation and rectangularity of the pattern are easily improved.

[0098] In the negative photosensitive adhesive composition of this embodiment, the content of component (A) is preferably 50% by mass or more, may be 60% by mass or more, or may be 60 to 99.9% by mass, relative to the total mass (100% by mass) of the negative photosensitive adhesive composition. Furthermore, in the case of a negative photosensitive adhesive composition that is substantially free of a solvent (component (S)) (i.e., an embodiment in which the solids concentration is 100% by mass), the content of component (A) is preferably 90% by mass or more, may be 95% by mass or more, or may be 95 to 99.9% by mass, relative to the total mass (100% by mass) of the solids. The solids in the negative photosensitive adhesive composition refer to all components remaining after excluding the solvent (component (S)) from all components contained in the negative photosensitive adhesive composition.

[0099] <Photoacid Generator (B)> The photoacid generator (B) (component (B)) contained in the negative photosensitive adhesive composition of this embodiment contains a compound (B1) (hereinafter also referred to as "component (B1)") consisting of a cation moiety and an anion moiety, in which the anion moiety contains an anion represented by the following general formula (I-an): Component (B1) is a compound that generates cations upon irradiation with radiation, and the cations can serve as a polymerization initiator.

[0100] [wherein A is a hetero element selected from the group consisting of boron, aluminum, gallium, phosphorus, arsenic and bismuth; and X is a halogen atom. ｂ１ is a monovalent organic group. j is an integer of 1 to 3. k is an integer of 1 to 6. l is an integer of 0 to 5. However, when k is an integer of 2 or more, there are multiple R ｂ１ is R ｂ１ They may be linked together to form a divalent or higher organic group that coordinates to A. l / (k+l) is 0 or more and less than 0.7.

[0101] In the formula (I-an), A is a hetero element selected from the group consisting of boron, aluminum, gallium, phosphorus, arsenic, and bismuth. These hetero elements are composed of metals in Groups 13 and 15 of the long-form periodic table. Of these hetero atoms, the hetero element selected as A is preferably selected from the group consisting of boron, gallium, and phosphorus. One or more of these hetero elements may be selected.

[0102] In the formula (I-an), X is a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, with a fluorine atom being preferred.

[0103] In the formula (I-an), R ｂ１ In the formula (I-an), when k is an integer of 2 or more, a plurality of R ｂ１ is R ｂ１ They may be linked together to form a divalent or higher organic group that coordinates to A. The "organic group" here refers to a group that contains carbon atoms and may also contain atoms other than carbon atoms (for example, hydrogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, halogen atoms, etc.). R ｂ１ is preferably a hydrocarbon group containing a halogen atom, and particularly preferably a monovalent hydrocarbon group containing a fluorine atom. The hydrocarbon group containing a halogen atom may be linear, branched, or cyclic, and preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 8 carbon atoms. ｂ１ may be free of halogen atoms.

[0104] R ｂ１ Specific examples of the monovalent organic group include a fluorinated alkyl group, a fluorinated aryl group, a pentafluorophenyl group, a 3,5-ditrifluoromethylphenyl group, an alkoxylate, and a nonafluoro-tert-butyl alkoxylate ((CF ３ ) ３ C—O—) and the like. ｂ１Specific examples of the divalent organic group include catechol, a compound having a 2,2-prime dihydroxyphenyl group, succinic acid, and oxalic acid.

[0105] In the formula (I-an), j is an integer of 1 to 3. k is an integer of 1 to 6. l is an integer of 0 to 5. l / (k+l) is 0 or more and less than 0.7. The upper limit of l / (k+l) is preferably less than 0.6, more preferably 0.5 or less. The value of l / (k+l) is an index regarding whether the halogen atom (X) is directly bonded to the hetero element (A). The lower the value of l / (k+l), the better. Therefore, the value of l / (k+l) may be 0.

[0106] Examples of the component (B1) include a compound represented by the following general formula (B1-1) (hereinafter referred to as "component (B11)"), a compound represented by the following general formula (B1-2) (hereinafter referred to as "component (B12)"), and a compound represented by the following general formula (B1-3) (hereinafter referred to as "component (B13)"):

[0107] <Component (B11)> The component (B11) is a compound represented by the following general formula (B1-1).

[0108] [In the formula, R ｂ０１ ~R ｂ０４ are each independently an aryl group which may have a substituent, or a fluorine atom, provided that the number of fluorine atoms (l) and the number of aryl groups which may have a substituent (k) satisfy the relationship l / (k+l) is 0 or more and less than 0.7. q is an integer of 1 or more, and Q ｑ＋ is a q-valent organic cation.

[0109] Anion part In the formula (B1-1), R ｂ０１ ~R ｂ０４ R each independently represents an aryl group which may have a substituent, or a fluorine atom. ｂ０１ ~R ｂ０４The aryl group in R preferably has 5 to 30 carbon atoms, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples include naphthyl, phenyl, and anthracenyl groups, with the phenyl group being preferred because of its easy availability. ｂ０１ ~R ｂ０４ The aryl group in formula (B1-1) may have a substituent. The substituent is not particularly limited, but is preferably a halogen atom, a hydroxyl group, an alkyl group (preferably a linear or branched alkyl group, preferably having 1 to 5 carbon atoms), or a halogenated alkyl group, more preferably a halogen atom or a halogenated alkyl group having 1 to 5 carbon atoms, and particularly preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. When the aryl group has a fluorine atom, the polarity of the anion moiety is increased, which is preferable. Among these, R in formula (B1-1) is ｂ０１ ~R ｂ０４ As each of the groups, a fluorinated phenyl group is preferred, and a perfluorophenyl group is particularly preferred.

[0110] A preferred example of the anion moiety of the compound represented by formula (B1-1) is tetrakis(pentafluorophenyl)borate ([B(C ６ F ５ ) ４ ] － tetrakis[(trifluoromethyl)phenyl]borate ([B(C ６ H ４ CF ３ ) ４ ] － ); difluorobis(pentafluorophenyl)borate ([(C ６ F ５ ) ２ BF ２ ] － tetrakis(difluorophenyl)borate ([B(C ６ H ３ F ２ ) ４ ] － Among them, tetrakis(pentafluorophenyl)borate ([B(C ６ F ５ ) ４ ]－ Among the above anions, the anion (([B(C ６ F ５ ) ４ ] － ), ([B(C ６ H ４ CF ３ ) ４ ] － ), ([B(C ６ H ３ F ２ ) ４ ] － ), ([B(C ６ F ５ ) ４ ] － In the above anions, the relationship between the number of fluorine atoms (l) and the number of fluorinated alkyl groups (k) which may have a substituent, l / (k+l), is 0. Among the above anions, the anion (([(C ６ F ５ ) ２ BF ２ ] － In the anion (([(C ６ F ５ ) BF ３ ] － )), l / (k+l) is 0.75.

[0111] <Component (B12)> The component (B12) is a compound represented by the following general formula (B1-2).

[0112] [In the formula, R ｂ０５ is a fluorine atom or a fluorinated alkyl group which may have a substituent. ｂ０５ may be the same or different, provided that the number of fluorine atoms (l) and the number of fluorinated alkyl groups (k) which may have a substituent satisfy the relationship l / (k+l) of 0 or more and less than 0.7. q is an integer of 1 or more, and Q ｑ＋ is a q-valent organic cation.

[0113] Anion part In the formula (B1-2), R ｂ０５ is a fluorine atom or a fluorinated alkyl group which may have a substituent. ｂ０５ may be the same or different. ｂ０５ The fluorinated alkyl group in the formula (I) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms. Specific examples include alkyl groups having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms. Among these, R ｂ０５ As the alkyl group, a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms is preferred, a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms is more preferred, and a fluorine atom, a trifluoromethyl group or a pentafluoroethyl group is even more preferred.

[0114] Preferable specific examples of the anion moiety of the compound represented by formula (B1-2) include (CF ３ CF ２ ) ２ PF ４ － , (CF ３ CF ２ ) ３ PF ３ － , ((CF ３ ) ２ CF) ２ PF ４ － , ((CF ３ ) ２ CF) ３ PF ３ － , (CF ３ CF ２ CF ２ ) ２ PF ４ － , (CF ３ CF ２ CF ２ ) ３ PF ３ － , ((CF ３ ) ２ CFCF ２ ) ２ PF ４－ , ((CF ３ ) ２ CFCF ２ ) ３ PF ３ － , (CF ３ CF ２ CF ２ CF ２ ) ２ PF ４ － and (CF ３ CF ２ CF ２ CF ２ ) ３ PF ３ － Among them, anions represented by ((CF ３ ) ２ CF) ３ PF ３ － Among the above anions, R ｂ０５ In the anion having two fluorine atoms, the relationship between the number of fluorine atoms (l) and the number of fluorinated alkyl groups (k) which may have a substituent, l / (k+l), is 0.667. ｂ０５ In an anion having "three", l / (k+l) is 0.5.

[0115] <Component (B13)> The component (B13) is a compound represented by the following general formula (B1-3).

[0116] [In the formula, R ｂ０６ ~R ｂ０９ are each independently an aryl group which may have a substituent, or a fluorine atom, provided that the number of fluorine atoms (l) and the number of aryl groups which may have a substituent (k) satisfy the relationship l / (k+l) is 0 or more and less than 0.7. q is an integer of 1 or more, and Q ｑ＋ is a q-valent organic cation.

[0117] Anion part In the formula (B1-3), R ｂ０６ ~Rｂ０９ R each independently represents an aryl group which may have a substituent, or a fluorine atom. ｂ０６ ~R ｂ０９ The aryl group in the formula (B1-1) is explained in detail in the above formula (B1-2). ｂ０１ ~R ｂ０４ Among them, R in formula (B1-3) ｂ０６ ~R ｂ０９ As each of the groups, a fluorinated phenyl group is preferred, and a perfluorophenyl group is particularly preferred.

[0118] A preferred example of the anion moiety of the compound represented by formula (B1-3) is tetrakis(pentafluorophenyl)gallate ([Ga(C ６ F ５ ) ４ ] － tetrakis[(trifluoromethyl)phenyl]gallate ([Ga(C ６ H ４ CF ３ ) ４ ] － ); difluorobis(pentafluorophenyl)gallate ([(C ６ F ５ ) ２ GaF ２ ] － tetrakis(difluorophenyl)gallate ([Ga(C ６ H ３ F ２ ) ４ ] － Among them, tetrakis(pentafluorophenyl)gallate ([Ga(C ６ F ５ ) ４ ] － Among the above anions, the anion ([Ga(C ６ F ５ ) ４ ] － ), ([Ga(C ６ H ４ CF ３ ) ４ ] － ), ([Ga(C ６ H３ F ２ ) ４ ] － ), ([Ga(C ６ F ５ ) ４ ] － In the above anions, the relationship between the number of fluorine atoms (l) and the number of fluorinated alkyl groups (k) which may have a substituent, l / (k+l), is 0. Among the above anions, the anion (([(C ６ F ５ ) ２ GaF ２ ] － In the anion (([(C ６ F ５ ) GaF ３ ] － )), l / (k+l) is 0.75.

[0119] Cation moiety In the formulas (B1-1), (B1-2) and (B1-3), Q ｑ＋ Suitable examples of the cation include sulfonium cations and iodonium cations, and the organic cations represented by the following general formulae (ca-1) to (ca-5) are particularly preferred.

[0120] [In the formula, R ２０１ ~R ２０７ , and R ２１１ ~R ２１２ R each independently represents an aryl group, a heteroaryl group, an alkyl group, or an alkenyl group, which may have a substituent. ２０１ ~R ２０３ , R ２０６ ~R ２０７ , R ２１１ ~R ２１２ may be bonded to each other to form a ring together with the sulfur atom in the formula. ２０８ ~R ２０９ R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ２１０represents an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted —SO ２ -containing cyclic group. ２０１ represents —C(═O)— or —C(═O)—O—. ２０１ each independently represents an arylene group, an alkylene group, or an alkenylene group; x is 1 or 2. ２０１ represents a (x+1)-valent linking group.

[0121] R ２０１ ~R ２０７ , and R ２１１ ~R ２１２ The aryl group in R is an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. ２０１ ~R ２０７ , and R ２１１ ~R ２１２ Examples of the heteroaryl group in the formula (I) include those in which some of the carbon atoms constituting the aryl group have been substituted with heteroatoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of this heteroaryl group include a group in which one hydrogen atom has been removed from 9H-thioxanthene; and examples of the substituted heteroaryl group include a group in which one hydrogen atom has been removed from 9H-thioxanthen-9-one. R ２０１ ~R ２０７ , and R ２１１ ~R ２１２ The alkyl group in R is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. ２０１ ~R ２０７ , and R ２１１ ~R ２１２ The alkenyl group in R preferably has 2 to 10 carbon atoms. ２０１ ~R ２０７ , and R ２１０ ~R ２１２Examples of the substituent that may be possessed by the group include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an oxo group (═O), an aryl group, and groups represented by the following formulas (car-r-1) to (car-r-10):

[0122] [In the formula, R' ２０１ are each independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted chain alkyl group, or an optionally substituted chain alkenyl group.

[0123] In the above formulae (car-r-1) to (car-r-10), R' ２０１ are each independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted chain alkyl group, or an optionally substituted chain alkenyl group.

[0124] Optionally substituted cyclic group: The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0125] R' ２０１ The aromatic hydrocarbon group in R' is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in the substituent. ２０１Specific examples of the aromatic ring possessed by the aromatic hydrocarbon group in R' include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms, or rings in which some of the hydrogen atoms constituting these aromatic rings or aromatic heterocycles are substituted with oxo groups or the like. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. ２０１ Specific examples of the aromatic hydrocarbon group in the formula (I) include a group in which one hydrogen atom has been removed from the aromatic ring (an aryl group: for example, a phenyl group, a naphthyl group, or an anthracenyl group), a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group), a group in which one hydrogen atom has been removed from a ring in which some of the hydrogen atoms constituting the aromatic ring have been substituted with an oxo group or the like (for example, anthraquinone), and a group in which one hydrogen atom has been removed from an aromatic heterocycle (for example, 9H-thioxanthene or 9H-thioxanthen-9-one). The alkylene group (the alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 or 2, and particularly preferably 1.

[0126] R' ２０１Examples of the cyclic aliphatic hydrocarbon group in the formula (I) include aliphatic hydrocarbon groups containing a ring within their structure. Examples of aliphatic hydrocarbon groups containing a ring within their structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed within a linear or branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be either a polycyclic group or a monocyclic group. Preferred monocyclic alicyclic hydrocarbon groups are groups in which one or more hydrogen atoms have been removed from a monocycloalkane. Preferred monocycloalkanes have 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. Preferred polycyclic alicyclic hydrocarbon groups are groups in which one or more hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among these, the polycycloalkane is more preferably a polycycloalkane having a polycyclic skeleton of a bridged ring system, such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane; or a polycycloalkane having a polycyclic skeleton of a fused ring system, such as a cyclic group having a steroid skeleton.

[0127] Among them, R' ２０１ The cyclic aliphatic hydrocarbon group in is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, particularly preferably an adamantyl group or a norbornyl group, and most preferably an adamantyl group.

[0128] The linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred, and specifically, a methylene group [—CH ２ -], ethylene group [-(CH ２ ) ２-], trimethylene group [-(CH ２ ) ３ -], tetramethylene group [-(CH ２ ) ４ -], pentamethylene group [-(CH ２ ) ５ As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, —CH(CH ３ ) -, -CH(CH ２ CH ３ ) -, -C(CH ３ ) ２ -, -C(CH ３ ) (CH ２ CH ３ ) -, -C(CH ３ ) (CH ２ CH ２ CH ３ ) -, -C(CH ２ CH ３ ) ２ alkylmethylene groups such as -; -CH(CH ３ ) CH ２ -, -CH(CH ３ ) CH(CH ３ ) -, -C(CH ３ ) ２ CH ２ -, -CH(CH ２ CH ３ ) CH ２ -, -C(CH ２ CH ３ ) ２ -CH ２ alkylethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ alkyltrimethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ CH ２The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0129] A chain alkyl group which may have a substituent: R' ２０１ The chain alkyl group may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, heneicosyl, and docosyl groups. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0130] A chain alkenyl group which may have a substituent: R' ２０１ The chain alkenyl group may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 3. Examples of linear alkenyl groups include vinyl, propenyl (allyl), and butynyl groups. Examples of branched alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl groups. Of the above chain alkenyl groups, linear alkenyl groups are preferred, vinyl and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0131] R' ２０１ Examples of the substituent in the cyclic group, chain alkyl group or alkenyl group include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, an oxo group, the above-mentioned R' ２０１ Examples of the groups include a cyclic group, an alkylcarbonyl group, and a thienylcarbonyl group.

[0132] Among them, R' ２０１ is preferably a cyclic group which may have a substituent, or a chain alkyl group which may have a substituent.

[0133] R ２０１ ~R ２０３ , R ２０６ ~R ２０７ , R ２１１ ~R ２１２ When they are bonded to each other to form a ring together with the sulfur atom in the formula, they are not substituted with heteroatoms such as sulfur atoms, oxygen atoms, and nitrogen atoms, or with carbonyl groups, -SO-, -SO ２ -, -SO ３ -, -COO-, -CONH- or -N(R Ｎ )-(the R Ｎ is an alkyl group having 1 to 5 carbon atoms.) The ring formed is preferably a 3- to 10-membered ring, including the sulfur atom, and particularly preferably a 5- to 7-membered ring, inclusive of the sulfur atom. Specific examples of the ring formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthrene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0134] In the formula (ca-3), R ２０８ ~R ２０９ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when they are alkyl groups, they may be bonded to each other to form a ring.

[0135] In the formula (ca-3), R ２１０represents an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted —SO ２ -containing cyclic group. ２１０ The aryl group in R is an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. ２１０ The alkyl group in R is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. ２１０ The alkenyl group in the formula (I) preferably has 2 to 10 carbon atoms.

[0136] In the formulas (ca-4) and (ca-5), Y ２０１ each independently represents an arylene group, an alkylene group, or an alkenylene group. ２０１ The arylene group in ２０１ Examples of the aromatic hydrocarbon group in the above formula include groups in which one hydrogen atom has been removed from the aryl groups exemplified in the formula Y. ２０１ The alkylene group and alkenylene group in R' ２０１ Examples of the chain alkyl group and the chain alkenyl group include groups in which one hydrogen atom has been removed from the groups exemplified above as the chain alkyl group and the chain alkenyl group.

[0137] In the formulas (ca-4) and (ca-5), x is 1 or 2. ２０１ is a (x+1)-valent linking group, i.e., a divalent or trivalent linking group. ２０１ The divalent linking group in W is preferably a divalent hydrocarbon group which may have a substituent. ２０１ The divalent linking group in may be linear, branched, or cyclic, and is preferably cyclic. Among them, a group in which two carbonyl groups are combined at both ends of an arylene group, or a group consisting of only an arylene group is preferred. Examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is particularly preferred. ２０１ The trivalent linking group in ２０１Examples of the divalent linking group include a group in which one hydrogen atom has been removed from the divalent linking group shown in the formula: and a group in which the divalent linking group is further bonded to the divalent linking group shown in the formula: ２０１ The trivalent linking group in the formula (I) is preferably a group in which two carbonyl groups are bonded to an arylene group.

[0138] Specific examples of suitable cations represented by the formula (ca-1) include cations represented by the following formulas (ca-1-1) to (ca-1-24).

[0139]

[0140] [In the formula, R” ２０１ is a hydrogen atom or a substituent. The substituent includes the above-mentioned R ２０１ ~R ２０７ and R ２１０ ~R ２１２ The substituents are the same as those exemplified as the substituents that may be possessed by

[0141] As the cation represented by the formula (ca-1), cations represented by the following general formulae (ca-1-25) to (ca-1-35) are also preferred.

[0142]

[0143] [In the formula, R' ２１１ is an alkyl group. ｈａｌ is a hydrogen atom or a halogen atom.

[0144] As the cation represented by the formula (ca-1), cations represented by the following chemical formulas (ca-1-36) to (ca-1-48) are also preferred.

[0145]

[0146] As the cation represented by the formula (ca-1), cations having a benzoylphenyl group represented by the following chemical formulas (ca-1-49) to (ca-1-56) are also preferred.

[0147]

[0148] Specific examples of suitable cations represented by the formula (ca-2) include diphenyliodonium cation and bis(4-tert-butylphenyl)iodonium cation.

[0149] Specific examples of suitable cations represented by the formula (ca-3) include cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0150]

[0151] Specific examples of suitable cations represented by the formula (ca-4) include cations represented by the following formulas (ca-4-1) to (ca-4-2).

[0152]

[0153] As the cation represented by the formula (ca-5), cations represented by the following general formulas (ca-5-1) to (ca-5-3) are also preferred.

[0154] [In the formula, R' ２１２ is an alkyl group or a hydrogen atom. ２１１ is an alkyl group.

[0155] Among the above, the cation part [(Q ｑ＋ ) １／ｑ is preferably a cation represented by the general formula (ca-1), more preferably a cation represented by each of formulas (ca-1-1) to (ca-1-56), still more preferably a cation represented by each of formulas (ca-1-25) to (ca-1-56), and particularly preferably a cation represented by each of formulas (ca-1-27) to (ca-1-29), (ca-1-35), (ca-1-47), and (ca-1-55).

[0156] Furthermore, the component (B1) is preferably a compound having a molar absorption coefficient of 150 L / mol cm or more at a wavelength of 365 nm. The molar absorption coefficient of the component (B1) at a wavelength of 365 nm is more preferably 150 L / mol cm or more and 30,000 L / mol cm or less, even more preferably 300 L / mol cm or more and 20,000 L / mol cm or less, and particularly preferably 500 L / mol cm or more and 10,000 L / mol cm or less. When the molar absorption coefficient of the component (B1) is equal to or greater than the lower limit of the preferred range, sensitivity during pattern formation is likely to be improved. On the other hand, when the molar absorption coefficient is equal to or less than the upper limit of the preferred range, a pattern with a good shape and high rectangularity is likely to be formed.

[0157] [Method for Measuring the Molar Absorption Coefficient of Component (B1)] The molar absorption coefficient of component (B1) is a value calculated using the Beer-Lambert law by measuring the absorbance of component (B1) at a wavelength of 365 nm using a spectrophotometer. Specifically, component (B1) is dissolved in acetonitrile, the solution is placed in a cell with an optical path length of 10 mm, and the UV spectrum is measured using a spectrophotometer (UV-3600, manufactured by Shimadzu Corporation) to obtain the absorbance at a wavelength of 365 nm. The molar absorption coefficient ε (L / mol cm) is then calculated using the Beer-Lambert law from the obtained absorbance and the solution concentration.

[0158] Specific examples of suitable components (B1) are listed below.

[0159]

[0160] In the negative-type photosensitive adhesive composition of this embodiment, the component (B1) may be used alone or in combination of two or more types. In the negative-type photosensitive adhesive composition, the content of the component (B1) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the component (A). When the content of the component (B1) is within the above-mentioned preferred range, sufficient sensitivity is likely to be obtained during pattern formation. Furthermore, the lithography properties of the pattern are further improved. Additionally, the strength of the film formed is further increased.

[0161] The negative photosensitive adhesive composition of this embodiment is also used in the (Laminate Manufacturing Method) described below. This (Laminate Manufacturing Method) can be used to manufacture microchannel devices and BioMEMS devices such as μ-TAS. For example, a pattern (channel) is formed on a silicon wafer using the negative photosensitive adhesive composition. The pattern and a glass substrate are then bonded together by thermocompression bonding. In this way, by applying the negative photosensitive adhesive composition of this embodiment, a desired channel structure is formed by patterning, and then a glass substrate is directly bonded to the pattern, thereby making it possible to produce a microchannel device (silicon wafer / pattern (channel) / glass substrate).

[0162] In the use of microfluidic devices and BioMEMS devices such as μ-TAS, cells flowing through the channels are often fluorescently stained and observed. When the negative photosensitive adhesive composition of this embodiment is used in the manufacture of such devices, it is preferable to use a photoacid generator that can reduce autofluorescence, from the viewpoint of the autofluorescence of the pattern. As such a photoacid generator, it is more preferable to use a photoacid generator selected from the group consisting of the component (B12) and the component (B13), and among these, it is preferable to use a photoacid generator selected from the group consisting of the cation moiety [(Q ｑ＋ ) １／ｑ ] is a cation represented by the general formula (ca-1); and a component (B12) in which the cationic moiety [(Q ｑ＋ ) １／ｑ It is particularly preferable to use a photoacid generator selected from the group consisting of components (B13) in which

[0045] is a cation represented by general formula (ca-1).

[0163] In the negative photosensitive adhesive composition of this embodiment, in addition to the component (B1) described above, a photoacid generator other than the component (B1) may be used in combination.

[0164] <Other Components> The negative photosensitive adhesive composition of this embodiment may contain other components as needed in addition to the above-mentioned components (A) and (B). If desired, the negative photosensitive adhesive composition of this embodiment may appropriately contain miscible additives such as a silane coupling agent, a sensitizer component, a metal oxide, a solvent, an additional resin for improving film performance, a dissolution inhibitor, a basic compound, a plasticizer, a stabilizer, a colorant, or an antihalation agent.

[0165] <Silane Coupling Agent> The negative photosensitive adhesive composition of this embodiment may further contain an adhesive aid to improve adhesion to the support or substrate. A silane coupling agent is preferred as this adhesive aid. That is, the negative photosensitive adhesive composition of this embodiment may further contain a silane coupling agent. Examples of silane coupling agents include silane coupling agents having reactive substituents such as carboxy groups, methacryloyl groups, and isocyanate groups. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. One type of silane coupling agent may be used alone, or two or more types may be used in combination. When a silane coupling agent is included, the content is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and even more preferably 1 to 3 parts by mass, per 100 parts by mass of component (A). When the content of the silane coupling agent is within the above-mentioned preferred range, the strength of the cured film is further increased, and in addition, the adhesion between the support or substrate and the cured film is further strengthened.

[0166] <Sensitizer Component> The negative photosensitive adhesive composition of this embodiment may further contain a sensitizer component. The sensitizer component is not particularly limited as long as it is capable of absorbing energy from exposure and transmitting that energy to another substance. Specific examples of the sensitizer component include benzophenone-based photosensitizers such as benzophenone and p,p'-tetramethyldiaminobenzophenone; carbazole-based photosensitizers; acetophenone-based photosensitizers; naphthalene-based photosensitizers such as 1,5-dihydroxynaphthalene; phenol-based photosensitizers; anthracene-based photosensitizers such as 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, and 9-ethoxyanthracene; and known photosensitizers such as biacetyl, eosin, rose bengal, pyrene, phenothiazine, and anthrone. Among these, compounds having an aromatic ring without a fused ring are preferred as the sensitizer component from the viewpoint of reducing autofluorescence. The sensitizer component may be used alone or in combination of two or more. When the sensitizer component is included, the content thereof is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass, per 100 parts by mass of component (A). When the content of the sensitizer component is within the above-mentioned preferred range, sensitivity and resolution can be further improved.

[0167] <Metal Oxide> The negative photosensitive adhesive composition of this embodiment may further contain a metal oxide (hereinafter also referred to as "component (M)"), since this facilitates the production of a cured film with enhanced strength. Furthermore, the inclusion of component (M) also enables the formation of a highly shaped, high-resolution pattern. Examples of component (M) include oxides of metals such as silicon (metallic silicon), titanium, zirconium, and hafnium. Among these, silicon oxide is preferred, and silica is particularly preferred. Furthermore, component (M) is preferably in the form of particles. Such a particulate (M) component preferably comprises particles having a volume average particle diameter of 5 to 40 nm, more preferably particles having a volume average particle diameter of 5 to 30 nm, and even more preferably particles having a volume average particle diameter of 10 to 20 nm. When the volume average particle diameter of component (M) is equal to or greater than the lower limit of the preferred range, the strength of the cured film is likely to be enhanced. On the other hand, when the content is equal to or less than the upper limit of the preferred range, residues are less likely to be generated during pattern formation, making it easier to form higher-resolution patterns. In addition, the transparency of the resin film is improved. The particle size of the (M) component can be appropriately selected depending on the exposure light source. It is generally believed that particles having a particle size of 1 / 10 or less of the wavelength of light are virtually immune to the effects of light scattering. For this reason, when forming a microstructure by photolithography using i-line (365 nm), for example, it is preferable to use a particle group (particularly preferably a silica particle group) having a primary particle size (volume average) of 10 to 20 nm as the (M) component. One type of (M) component may be used alone, or two or more types may be used in combination. When the (M) component is included, its content is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of the (A) component. When the (M) component is included, its content is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of the (A) component. When the (M) component is included, its content is equal to or greater than the lower limit of the preferred range, it further enhances the strength of the cured film. On the other hand, when it is equal to or less than the upper limit of the above-mentioned preferred range, the transparency of the resin film is further improved.

[0168] The negative photosensitive adhesive composition of this embodiment may further contain a solvent (hereinafter sometimes referred to as "component (S)"). Examples of component (S) include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds having an ester bond such as 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate; monoalkyl ethers or monoalkyl ethers of the polyhydric alcohols or the compounds having an ester bond such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether; Examples of the solvent include derivatives of polyhydric alcohols such as compounds having an ether bond, such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), cyclic ethers such as dioxane, and esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate, aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene, and dimethyl sulfoxide (DMSO). The component (S) may be used alone or as a mixed solvent of two or more.

[0169] When the (S) component is contained, its amount is not particularly limited and is set appropriately according to the coating film thickness at a concentration that allows the negative photosensitive adhesive composition to be applied to a substrate or the like without dripping. For example, the (S) component can be used so that the solids concentration of the negative photosensitive adhesive composition is 50% by mass or more, or the (S) component can be used so that the solids concentration is 60% by mass or more. Also, an embodiment that does not substantially contain the (S) component (i.e., an embodiment in which the solids concentration is 100% by mass) can be employed.

[0170] As described above, the negative photosensitive adhesive composition of this embodiment contains an epoxy group-containing compound (A) and a photoacid generator (B). This negative photosensitive adhesive composition contains at least one epoxy resin (A1) selected from the group consisting of bisphenol epoxy resins and hydrogenated bisphenol epoxy resins; an epoxy resin (A2) that exhibits a tensile modulus of 100 MPa or less when cured alone; and a compound (B1) containing an anion represented by the general formula (I-an). For example, this negative photosensitive adhesive composition is suitable for forming an adhesive layer in a laminate including a support, another support, and an adhesive layer interposed between the two supports to bond the two supports. By using the epoxy resin (A2) in combination with the epoxy resin (A1), the elastic modulus of the cured film at room temperature (80°C or less) is reduced. This minimizes the difference in thermal expansion between the two supports during and after thermocompression bonding, thereby reducing warpage of the laminate after bonding. Furthermore, a compound (B1) with a specific anionic structure is used as the photoacid generator (B). This makes it possible to reduce the amount of released halogen atoms.

[0171] In the negative photosensitive adhesive composition of this embodiment, the epoxy equivalent (g / eq.) of the epoxy group-containing compound (A) as a whole is preferably 600 or more, and when this negative photosensitive adhesive composition is used, the rectangularity of the formed pattern is improved. The negative photosensitive adhesive composition of this embodiment can be applied to structures that have a light-emitting or light-receiving function, such as various measuring instruments such as microchannel devices, image sensors, microscopes, and absorptiometers, and displays.

[0172] (Photosensitive adhesive dry film) One embodiment of the photosensitive adhesive dry film comprises a negative photosensitive adhesive composition layer (photosensitive resin film) and a cover film laminated in this order on a substrate film. The negative photosensitive adhesive composition layer (photosensitive resin film) here is formed using the negative photosensitive adhesive composition of the above-described embodiment.

[0173] Known substrate films can be used, such as thermoplastic resin films. Examples of such thermoplastic resins include polyesters such as polyethylene terephthalate. The thickness of the substrate film is preferably 2 to 150 μm. The thickness of the negative photosensitive adhesive composition layer (photosensitive resin film) is preferably 100 μm or less, and more preferably 5 to 50 μm.

[0174] Known cover films can be used, such as thermoplastic resin films. Examples of such thermoplastic resins include polyethylene film and polypropylene film. The cover film is preferably a film whose adhesive strength to the negative photosensitive adhesive composition layer is smaller than the adhesive strength between the base film and the negative photosensitive adhesive composition layer. The thickness of the cover film is preferably 2 to 150 μm, more preferably 2 to 100 μm, and even more preferably 5 to 50 μm. The base film and cover film may be made of the same film material or different film materials.

[0175] The photosensitive adhesive dry film of this embodiment can be produced, for example, by applying the negative photosensitive adhesive composition of the above-described embodiment to a substrate film, drying it to form a negative photosensitive adhesive composition layer (photosensitive resin film), and then laminating a cover film on the negative photosensitive adhesive composition layer (photosensitive resin film). The negative photosensitive adhesive composition can be applied to the substrate film using an appropriate method such as a blade coater, lip coater, comma coater, or film coater. The negative photosensitive adhesive composition layer (photosensitive resin film) included in the photosensitive adhesive dry film of this embodiment is typically composed of a B-stage (semi-cured) material. The photosensitive adhesive dry film of this embodiment is provided, for example, as a roll wound around a core.

[0176] (Pattern Forming Method) One embodiment of the pattern forming method is a pattern forming method comprising a step of forming a photosensitive resin film on a support using the negative photosensitive adhesive composition of the above-described embodiment or the photosensitive adhesive dry film of the above-described embodiment (hereinafter referred to as the "film forming step"), a step of exposing the photosensitive resin film (hereinafter referred to as the "exposure step"), and a step of developing the exposed photosensitive resin film with a developer containing an organic solvent to form a negative pattern (hereinafter referred to as the "development step"). The pattern forming method of this embodiment can be carried out, for example, as follows.

[0177] [Film Formation Step] First, the negative photosensitive adhesive composition of the above-described embodiment is applied to a support by a known method such as spin coating, roll coating, or screen printing, and then baked (post-applied bake (PAB)) for 2 to 60 minutes at a temperature of, for example, 50 to 150°C to form a photosensitive resin film. Alternatively, a photosensitive adhesive dry film of the above-described embodiment is used to form a photosensitive resin film on a support.

[0178] The support is not particularly limited, and conventionally known supports can be used. Examples include substrates for electronic components, substrates on which a predetermined wiring pattern is formed, and resins suitable for forming microchannels. More specifically, silicon, silicon nitride, titanium, tantalum, lithium tantalate (LiTaO ３ ), niobium, lithium niobate (LiNbO ３ Examples of the substrate include metal substrates such as palladium, titanium tungsten, copper, chromium, iron, and aluminum, as well as glass substrates. Examples of materials that can be used for the wiring pattern include copper, aluminum, nickel, and gold. Examples of resins that can be used include acrylic resin, polypropylene, polycarbonate resin, cycloolefin resin, polystyrene resin, polyester resin, urethane resin, vinyl chloride resin, silicone resin, and fluorine-based resin.

[0179] The thickness of the photosensitive resin film formed from the negative photosensitive adhesive composition or the photosensitive adhesive dry film is not particularly limited, but is preferably about 10 to 100 μm. The negative photosensitive adhesive composition or the photosensitive adhesive dry film of the above-mentioned embodiment can obtain good properties even when formed into a thick film.

[0180] [Exposure Step] Next, the formed photosensitive resin film is subjected to selective exposure using a known exposure device, for example, through a mask (mask pattern) on which a predetermined pattern has been formed, or by drawing using direct irradiation with an electron beam without using a mask pattern, and then, if necessary, baked (post-exposure bake (PEB)) at a temperature of 80 to 150°C for 40 to 1200 seconds, preferably 40 to 1000 seconds, and more preferably 60 to 900 seconds.

[0181] The wavelength used for exposure is not particularly limited, and radiation such as ultraviolet light having a wavelength of 300 to 500 nm, i-rays (wavelength 365 nm), or visible light is selectively irradiated (exposed). Examples of radiation sources that can be used include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and argon gas lasers. Here, radiation refers to ultraviolet light, visible light, far ultraviolet light, X-rays, electron beams, and the like. The radiation dose varies depending on the type and amount of each component in the composition, the thickness of the coating film, and the like, but for example, when an ultra-high-pressure mercury lamp is used, it is 100 to 2000 mJ / cm. ２ is.

[0182] The exposure method for the photosensitive resin film may be a normal exposure (dry exposure) carried out in air or an inert gas such as nitrogen, or may be liquid immersion exposure (liquid immersion lithography).

[0183] The photosensitive resin film after the exposure step has high transparency, and for example, the haze value when irradiated with i-line (wavelength 365 nm) is preferably 3% or less, more preferably 1.0 to 2.5%. Thus, the photosensitive resin film formed using the negative photosensitive adhesive composition of the above-described embodiment or the photosensitive adhesive dry film of the above-described embodiment has high transparency. Therefore, during exposure in pattern formation, light transmittance is increased, making it easier to obtain a negative pattern with good lithography properties. The haze value of the photosensitive resin film after such an exposure step is measured using a method in accordance with JIS K 7136 (2000).

[0184] [Development Step] Next, the photosensitive resin film after exposure is developed with a developer containing an organic solvent (organic developer). After development, a rinse treatment is preferably performed. If necessary, a bake treatment (post-bake) may be performed.

[0185] The organic solvent contained in the organic developer may be any solvent capable of dissolving the component (A) (the component (A) before exposure), and may be appropriately selected from known organic solvents. Specific examples include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents.

[0186] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, methyl amyl ketone (2-heptanone), etc. Among these, methyl amyl ketone (2-heptanone) is preferred as the ketone solvent.

[0187] Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Pyrene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, milk Examples of the alkyl esters include ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, and propyl-3-methoxypropionate.Among these, butyl acetate or PGMEA is preferred as the ester solvent.

[0188] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0189] Known additives can be blended into the organic developer as needed. Examples of such additives include surfactants. The surfactant is not particularly limited, but examples include ionic and nonionic fluorine-based and / or silicon-based surfactants. Nonionic surfactants are preferred, and nonionic fluorine-based surfactants or nonionic silicon-based surfactants are more preferred. When a surfactant is blended, the blending amount is typically 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, based on the total amount of the organic developer.

[0190] The development process can be carried out by a known development method, for example, a method of immersing the support in a developer for a certain period of time (dip method), a method of piling up the developer on the surface of the support by surface tension and leaving it standing for a certain period of time (puddle method), a method of spraying the developer onto the surface of the support (spray method), a method of continuously applying the developer while scanning a developer application nozzle at a constant speed onto a support rotating at a constant speed (dynamic dispense method), etc.

[0191] The rinse treatment (cleaning treatment) using a rinse solution can be carried out by a known rinse method. Examples of the rinse treatment method include a method in which the rinse solution is continuously applied onto a support rotating at a constant speed (spin coating method), a method in which the support is immersed in the rinse solution for a certain period of time (dip method), and a method in which the rinse solution is sprayed onto the surface of the support (spray method). For the rinse treatment, it is preferable to use a rinse solution containing an organic solvent.

[0192] A negative pattern can be formed by the above-described film forming step, exposure step, and development step.

[0193] In the pattern formation method of the above-described embodiment, the negative photosensitive adhesive composition of the above-described embodiment or the photosensitive adhesive dry film of the above-described embodiment is used, and therefore, a pattern with good adhesion to the support, high sensitivity, and good shape with high rectangularity can be easily formed.

[0194] (Laminate) One embodiment of the laminate is a laminate obtained by laminating a support and a cured product of a photosensitive resin film formed using the negative photosensitive adhesive composition of the above-mentioned embodiment or the photosensitive adhesive dry film of the above-mentioned embodiment. The cured product of the photosensitive resin film is typically obtained by obtaining a support having a pattern by the pattern formation method of the above-mentioned embodiment, and then curing the pattern (photosensitive resin film).

[0195] (Method for manufacturing a laminate) One embodiment of the method for manufacturing a laminate is a manufacturing method including a step of obtaining a support having a negative pattern by using the pattern formation method of the above-mentioned embodiment, and a step of bonding the support having the negative pattern to another support by thermocompression bonding to obtain a laminate.

[0196] After the step of obtaining a support having a pattern by the pattern forming method of the above-described embodiment, it is preferable to harden the photosensitive resin film. The hardening treatment can be carried out under conditions such as a temperature of 100 to 250°C, for 0.5 to 2 hours, in a nitrogen atmosphere.

[0197] According to the laminate manufacturing method of the above-described embodiment, since the negative photosensitive adhesive composition of the above-described embodiment or the photosensitive adhesive dry film of the above-described embodiment is used, a support can be bonded to another support without the need for etching or resist stripping. Furthermore, according to the manufacturing method of the above-described embodiment, warping of the laminate after bonding can be suppressed. Furthermore, according to the manufacturing method of the above-described embodiment, the amount of halogen atoms released can be reduced, thereby suppressing aluminum corrosion even when the laminate contains a metal such as aluminum. The laminate manufactured by the manufacturing method of such an embodiment is suitable for semiconductor devices or can also be applied to microchannel devices. Furthermore, the laminate can also be applied to various measuring instruments such as image sensors, microscopes, and absorptiometers, as well as displays and other structures that have the function of emitting or receiving light.

[0198] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0199] <Preparation of Negative-Type Photosensitive Adhesive Compositions> (Examples 1 to 16, Comparative Examples 1 to 3) Each of the components shown in Tables 1 and 2 was mixed and dissolved in 3-methoxybutyl acetate, and the resulting solution was filtered using a PTFE filter (pore size 1 μm, manufactured by PALL Corporation) to prepare a negative-type photosensitive adhesive composition (solution with a solids concentration of 65% by mass) for each example.

[0200]

[0201]

[0202] In Tables 1 and 2, the abbreviations have the following meanings: The numbers in brackets [ ] are the amounts of each component blended (parts by mass; solid content equivalent).

[0203] (A1)-1: Epoxy resin represented by the following chemical formula (A1-X); tensile modulus of elasticity: about 2 GPa, epoxy equivalent: 500 g / eq. (A1)-2: Epoxy resin represented by the following chemical formula (A1-X); tensile modulus of elasticity: about 2 GPa, epoxy equivalent: 650 g / eq. (A1)-3: Epoxy resin represented by the following chemical formula (A1-X); tensile modulus of elasticity: about 2 GPa, epoxy equivalent: 1000 g / eq. (A1)-4: Epoxy resin represented by the following chemical formula (A1-X); tensile modulus of elasticity: about 2 GPa, epoxy equivalent: 2000 g / eq.

[0204]

[0205] (A1)-5: Epoxy resin represented by the following chemical formula (A1-Y); tensile modulus of elasticity: about 1.8 GPa, epoxy equivalent: 1000 g / eq.

[0206]

[0207] (A1)-6: Epoxy resin represented by the following chemical formula (A1-Z); tensile modulus of elasticity: about 1.7 GPa, epoxy equivalent: 1000 g / eq.

[0208]

[0209] (A2)-1: Epoxy resin represented by the following chemical formula (A2-X); tensile modulus of elasticity: 2.5 MPa, epoxy equivalent: 450 g / eq.

[0210]

[0211] (A2)-2: Epoxy resin represented by the following chemical formula (A2-Y); tensile modulus of elasticity: 63 MPa, epoxy equivalent: 500 g / eq. (A2)-3: Epoxy resin represented by the following chemical formula (A2-Y); tensile modulus of elasticity: 7 MPa, epoxy equivalent: 1100 g / eq.

[0212]

[0213] (A3)-1: Epoxy resin represented by the following chemical formula (A3-1); epoxy equivalent 100 g / eq. (A3)-2: Epoxy resin represented by the following chemical formula (A3-2); epoxy equivalent 130 g / eq. (A3)-3: Epoxy resin represented by the following chemical formula (A3-3); epoxy equivalent 200 g / eq.

[0214]

[0215] (B)-1: A photoacid generator comprising a compound represented by the following chemical formula (B-1); having a molar absorption coefficient at a wavelength of 365 nm of 9600 L / mol cm. (B)-2: A photoacid generator comprising a compound represented by the following chemical formula (B-2); having a molar absorption coefficient at a wavelength of 365 nm of 600 L / mol cm. (B)-3: A photoacid generator comprising a compound represented by the following chemical formula (B-3); having a molar absorption coefficient at a wavelength of 365 nm of 600 L / mol cm. (B)-4: A photoacid generator comprising a compound represented by the following chemical formula (B-4); having a molar absorption coefficient at a wavelength of 365 nm of 600 L / mol cm. (B)-5: A photoacid generator comprising a compound represented by the following chemical formula (B-5); having a molar absorption coefficient at a wavelength of 365 nm of 80 L / mol cm. (B)-6: A photoacid generator comprising a compound represented by the following chemical formula (B-6); having a molar absorption coefficient at a wavelength of 365 nm of 80 L / mol cm

[0216]

[0217] Method for calculating the combined epoxy equivalent of the entire component (A): For example, the combined epoxy equivalent of the entire component (A) in the negative photosensitive adhesive composition of Example 8 was calculated as follows. Composition of component (A) (A1)-6 Epoxy equivalent 1000 g / eq. 60 parts by mass (A2)-3 Epoxy equivalent 1100 g / eq. 30 parts by mass (A3)-3 Epoxy equivalent 200 g / eq. 10 parts by mass The epoxy value of each epoxy resin was calculated based on 100 g of the entire component (A). (A1)-6 60 g ÷ 1000 g / eq. = 0.060 eq. (A2)-3 30 g ÷ 1100 g / eq. = 0.0273 parts by mass (A3)-3 10 g ÷ 200 g / eq. = 0.050 parts by mass Total epoxy value 0.060 + 0.0273 + 0.050 = 0.1373 eq. Blended epoxy equivalent 100 g ÷ 0.1373 eq. = 728 g / eq.

[0218] <Pattern Formation> Film Formation Step: Each of the negative photosensitive adhesive compositions of the examples was spin-coated onto an 8-inch silicon (Si) substrate, and the resulting substrate was pre-baked (PAB) on a hot plate at 100°C for 10 minutes, followed by drying to form a photosensitive resin film with a thickness of 50 µm.

[0219] Exposure process: Next, the photosensitive resin film was exposed to ghi broadband light using a SUSS-MA8 aligner. A line and space pattern with a line width of 100 μm and a pitch width of 200 μm (hereinafter referred to as a "1:1 LS pattern") was used as the target. After that, post-exposure baking was performed on a hot plate at 100°C for 2 minutes.

[0220] Development Step: Next, development was carried out for 300 seconds using propylene glycol monomethyl ether acetate (PGMEA) to form a 1:1 LS pattern as a negative pattern.

[0221] <Production of Laminate> Thermocompression Bonding Step Next, the support having the 1:1 LS pattern and a glass substrate were bonded by thermocompression bonding under vacuum conditions of 1000 kgf (9800 N) - 200°C - 5 minutes to obtain a laminate.

[0222] <Evaluation> The following evaluations were carried out in forming patterns and producing laminates using the negative photosensitive adhesive compositions of each example.

[0223] [Evaluation of warpage of laminate] After bonding in the thermocompression bonding step, the warpage of the obtained laminate was measured and evaluated according to the following criteria. The results are shown in Table 3. A: Warpage of the laminate is less than 130 μm B: Warpage of the laminate is 130 μm or more and less than 150 μm C: Warpage of the laminate is 150 μm or more

[0224] [Evaluation of free fluorine generation] The negative patterns formed in the above <Pattern formation> using the negative photosensitive adhesive composition of each example were heat-treated under vacuum at 1000 kgf (9800 N) at 200°C for 5 minutes to obtain cured products. 4 g of the cured product of the negative photosensitive adhesive composition of each example was immersed in 40 mL of water and treated at 120°C for 20 hours (continuous immersion). Thereafter, the extract was sampled and quantitatively analyzed for free fluorine ions by ion chromatography, and evaluated according to the following criteria. The results are shown in Table 3. A: No free fluorine ions were detected. C: Free fluorine ions were detected.

[0225] [Evaluation of sensitivity of pattern formation] When forming a negative pattern in the above <Pattern formation>, the minimum required exposure dose was measured for each negative photosensitive adhesive composition example, and the results were evaluated according to the following criteria. The results are shown in Table 3. A: Exposure dose of 50 mJ / cm ２ B: The exposure dose was 100 mJ / cm ２ C: The exposure dose was 200 mJ / cm ２ A pattern was formed with

[0226] [Evaluation of rectangularity of pattern] The negative patterns formed in the above <Pattern formation> were observed with an SEM, and the rectangularity of the patterns was evaluated according to the following criteria. The results are shown in Table 3. A: Pattern shape is rectangular B: Pattern shape is not rectangular

[0227]

[0228]

[0229] The results shown in Tables 3 and 4 confirm that when the negative photosensitive adhesive compositions of Examples 1 to 16 were used, it was possible to bond a Si substrate and a glass substrate together, suppress warping of the laminate after bonding, and prevent liberation of fluorine atoms.

[0230] On the other hand, when the negative photosensitive adhesive compositions of Comparative Examples 1 and 2 were used, significant warping occurred in the laminate after application, and when the negative photosensitive adhesive composition of Comparative Example 3 was used, liberation of fluorine atoms was observed.

[0231] Comparing Examples 1 to 3, which differ in the amount of the component (A3), it was confirmed that the sensitivity during pattern formation was improved by using the component (A3) in addition to the components (A1) and (A2).

[0232] A comparison of Examples 13, 14, and 16, which have different cationic structures of photoacid generators, confirmed that the sensitivity when forming a pattern was improved when the negative photosensitive adhesive compositions of Examples 13 and 14 were used compared to when the negative photosensitive adhesive composition of Example 16 was used.

[0233] It was confirmed that when the negative photosensitive adhesive compositions of Examples 1 to 16 were used, a pattern with high rectangularity was more easily formed when the combined epoxy equivalent of the entire component (A) was 600 g / eq. or more.

[0234] Although the preferred embodiments of the present invention have been described above, the present invention is not limited to these embodiments. Addition, omission, substitution, and other modifications of the configuration are possible within the scope of the spirit of the present invention. The present invention is not limited by the above description, but is limited only by the scope of the appended claims.

Claims

1. A negative-type photosensitive adhesive composition comprising an epoxy group-containing compound (A) and a photoacid generator (B), wherein the epoxy group-containing compound (A) comprises at least one epoxy resin (A1) selected from the group consisting of bisphenol-type epoxy resins and hydrogenated bisphenol-type epoxy resins, and another epoxy resin (A2), wherein the other epoxy resin (A2) is an epoxy resin that exhibits a tensile modulus of elasticity of 100 MPa or less when cured alone, and the photoacid generator (B) comprises a compound (B1) comprising a cation moiety and an anion moiety, and the anion moiety comprises an anion represented by the following general formula (I-an): [wherein A is a hetero element selected from the group consisting of boron, aluminum, gallium, phosphorus, arsenic and bismuth; and X is a halogen atom. ｂ１ is a monovalent organic group. j is an integer of 1 to 3. k is an integer of 1 to 6. l is an integer of 0 to 5. However, when k is an integer of 2 or more, there are multiple R ｂ１ is R ｂ１ They may be linked together to form a divalent or higher organic group that coordinates to A. l / (k+l) is 0 or more and less than 0.

7.

2. The negative photosensitive adhesive composition according to claim 1, wherein the compound (B1) has a molar absorption coefficient of 150 L / mol·cm or more at a wavelength of 365 nm.

3. The negative photosensitive adhesive composition according to claim 1, wherein the epoxy group-containing compound (A) comprises the epoxy resin (A1), an alicyclic epoxy resin (A3), and an epoxy resin (A2″) other than these that exhibits a tensile modulus of elasticity of 100 MPa or less when cured alone.

4. The negative photosensitive adhesive composition according to claim 3, wherein the content of the epoxy resin (A1) is 50% by mass or more and 80% by mass or less, relative to the total mass (100% by mass) of the epoxy group-containing compound (A); the content of the alicyclic epoxy resin (A3) is 10% by mass or more and 20% by mass or less, relative to the total mass (100% by mass) of the epoxy group-containing compound (A); and the content of the epoxy resin (A2") is 10% by mass or more and 40% by mass or less, relative to the total mass (100% by mass) of the epoxy group-containing compound (A).

5. The negative photosensitive adhesive composition according to claim 1, wherein the epoxy group-containing compound (A) as a whole has an epoxy equivalent of 600 g / eq. or more.

6. The negative photosensitive adhesive composition according to claim 1, wherein the epoxy resin (A1) is a bisphenol A type epoxy resin.

7. The negative photosensitive adhesive composition according to claim 1, wherein the epoxy resin (A1) is a bisphenol F type epoxy resin.

8. The negative photosensitive adhesive composition according to claim 1, wherein the epoxy resin (A1) is a hydrogenated bisphenol A epoxy resin.

9. The negative photosensitive adhesive composition according to claim 1, wherein the other epoxy resin (A2) is an epoxy resin having at least one structure selected from the group consisting of a structure represented by the following general formula (A2-r-1) and a structure represented by the following general formula (A2-r-2): [In the formula, R ａ２０ ~R ａ２３ are each independently an alkyl group or a hydrogen atom. m1 and m2 are each independently an integer of 1 to 15.

10. The negative photosensitive adhesive composition according to claim 9, wherein the other epoxy resin (A2) is an epoxy resin further having a linking group derived from a bisphenol.

11. A photosensitive adhesive dry film produced using the negative photosensitive adhesive composition according to any one of claims 1 to 10.

12. A pattern forming method comprising the steps of: forming a photosensitive resin film on a support using the negative photosensitive adhesive composition according to any one of claims 1 to 10; exposing the photosensitive resin film; and developing the exposed photosensitive resin film with a developer containing an organic solvent to form a negative pattern.

13. A method for manufacturing a laminate, comprising the steps of: obtaining a support having a negative pattern by using the pattern forming method described in claim 12; and bonding the support having the negative pattern to another support by thermocompression bonding to obtain a laminate.

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