Negative photosensitive adhesive composition, photosensitive adhesive dry film, patterning process, and method for producing laminate

Abstract

To provide a negative photosensitive adhesive composition or the like capable of bonding substrates to each other, suppressing warpage of a laminate after bonding, and reducing the amount of liberated halogen atoms.SOLUTION: The negative photosensitive adhesive composition contains epoxy resins selected from the group consisting of bisphenol type epoxy resins and hydrogenated bisphenol type epoxy resins, epoxy resins exhibiting a tensile modulus of 100MPa or less when formed into a cured product alone, and a compound containing an anion represented by formula (I-an). In the 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 linked to each other to form an organic group having a valency of two or more that coordinates to A. L / (k + l) is 0 or more and less than 0.7. [Chemical Formula 1] SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a negative photosensitive adhesive composition, a photosensitive adhesive dry film, a pattern forming method, and a method for producing a laminate. [Background technology]

[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 substrates to be stacked together or a hollow structure to be formed (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2017-161837 Summary of the Invention [Problem to be solved by the invention]

[0005] However, when substrates are bonded together by thermocompression using a conventional photosensitive adhesive, there is a problem that warping (deformation) occurs in the laminate after bonding. Furthermore, when a conventional photosensitive adhesive is 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. [Means for solving the problem]

[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), in which the 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) contains a compound (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):

[0008] [ka] [wherein A is a hetero element selected from the group consisting of boron, aluminum, gallium, phosphorus, arsenic and bismuth; X is a halogen atom; R 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, 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. 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. [Effects of the Invention]

[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. DETAILED DESCRIPTION OF THE INVENTION

[0013] In this specification and claims, the term "aliphatic" is a relative concept to aromatic, and is defined to mean a group or compound that does not have aromaticity. Unless otherwise specified, the term "alkyl group" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups in alkoxy groups. Unless otherwise specified, the term "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups. A "halogenated alkyl group" is an alkyl group in which some or all of the hydrogen atoms have been substituted with halogen atoms, and examples of the halogen atoms include fluorine, chlorine, bromine, and iodine atoms. The term "fluorinated alkyl group" refers to an alkyl group in which some or all of the hydrogen atoms have been substituted with fluorine atoms. The term "structural unit" refers to a monomer unit that constitutes a polymeric compound (resin, polymer, copolymer). The phrase "optionally substituted" includes both cases where a hydrogen atom (-H) is replaced with a monovalent group and where a methylene group (-CH2-) is replaced with a divalent group. The term "exposure" is a general concept that includes 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 "blended epoxy equivalent") is calculated by the following formula.

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

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

[0017] denominator: Sum of the epoxy values ​​of each epoxy-containing compound (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 elasticity of an epoxy group-containing compound when it is cured alone is measured as follows. A test piece is prepared as a cured product obtained by curing only the epoxy group-containing compound to be measured, by molding it into a dumbbell or rectangular shape as specified in JIS K 7139. The test piece is subjected to the same film formation step, exposure step, and development step as in <Pattern formation> described in [Examples] below, and then molded by heat treatment at 100°C for 2 minutes. The molding material used to prepare the test specimens was 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 the solvent 3-methoxybutyl acetate. Then, a test piece having an arbitrary film thickness and molded into a dumbbell or 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), and the elastic modulus is calculated.

[0019] (Negative Photosensitive Adhesive Composition) One embodiment of the negative-type 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), which exhibits a tensile modulus of elasticity of 100 MPa or less when cured by itself. The component (B) contains a compound (B1) consisting of a cation moiety and an anion moiety, the anion moiety containing an anion represented by the general formula (I-an).

[0020] When a photosensitive resin film is formed using this negative photosensitive adhesive composition and selectively exposed to light, the cationic moiety of component (B) decomposes in the exposed areas of the photosensitive resin film to generate an acid, which then causes ring-opening polymerization of the epoxy groups in component (A), 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 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 by itself.

[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-type epoxy resins and hydrogenated bisphenol-type epoxy resins.

[0023] The epoxy equivalent of the (A1) component 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] Bisphenol-type epoxy resins: Examples of bisphenol-type epoxy resins include epoxy resins represented by the following general formula (abp1).

[0026] [ka] [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 between 1 and 50.

[0027] In the formula (abp1), R EP is an epoxy group-containing group. R 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. The alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure, which is a three-membered ring ether, and 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, alkoxy, or hydroxyl groups. 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 linked 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 optionally substituted divalent hydrocarbon groups: Such a 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 straight-chain or branched-chain 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, even more preferably 1 to 4, and most preferably 1 to 3. The linear aliphatic hydrocarbon group is preferably a linear alkylene group, and specific examples thereof include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], and a pentamethylene group [-(CH2)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. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkyl alkylene groups such as alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. 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 an alicyclic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. Examples of the straight-chain or branched-chain aliphatic hydrocarbon group include the same as those described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and 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 thereof 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 the aromatic ring 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 the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic heterocycle 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 hydrogen atom has been further 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.

[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, such as a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, or 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, such as an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, or 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, more 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, with a fluorine atom being 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 have been 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 heteroatom, and the heteroatom-containing substituent is preferably -O-, -C(=O)-O-, -S-, -S(=O)2-, or -S(=O)2-O-.

[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 the hydrogen atom of the alicyclic hydrocarbon group.

[0036] Regarding divalent linking groups containing heteroatoms: The heteroatom in the divalent linking group containing a heteroatom 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)-, -OC(=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-, and groups represented by the general formula -Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 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, acyl, etc. 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 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -, -[Y 21 -C(=O)-O] m” -Y 22 -or- Y 21 -OC(=O)-Y 22 -Medium, Y 21 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 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. Y 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. Formula − [Y 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 - is a group represented by the formula -Y 21-C(=O)-OY 22 Particularly preferred is a group represented by the formula -(CH2) a’ -C(=O)-O-(CH2) 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 a32 The 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 them, R a31 , R a32 As the alkyl group, a hydrogen atom or a linear or branched alkyl group is preferred, a hydrogen atom or a linear alkyl group is more preferred, and a hydrogen atom or a methyl group is particularly preferred. The plurality of R present in the formula (abp1) a31 may be the same or different. a32 may be the same as or different from each other. R a31 and R a32 When all of the groups are methyl groups, the epoxy resin represented by general formula (abp1) is a bisphenol A type epoxy resin. R a31 and R a32 When both are hydrogen atoms, it 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] About hydrogenated bisphenol epoxy resins: The hydrogenated bisphenol type epoxy resin may be an epoxy resin represented by the following general formula (Aep-1).

[0042] [ka] [In the formula, Rep 1 ~Rep 4 Rep 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 Rep each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a trifluoromethyl group. 1 ~Rep 4 are each preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group. Rep 1 ~Rep 4 When all of the groups are 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 may be the same or different. 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 different compounds. Of 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, or a bisphenol F epoxy resin, or 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-type photosensitive adhesive composition of this embodiment, the epoxy resin (A2) (hereinafter also referred to as "component (A2)") is an epoxy resin that exhibits a tensile modulus of 100 MPa or less when cured alone. However, component (A2) does not fall under the category of component (A1) above; that is, component (A2) is different from component (A1).

[0048] The epoxy equivalent of 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 elasticity of the component (A2) when cured alone is 100 MPa or less, preferably 90 MPa or less, and may be 1 MPa or more and 80 MPa or less, or 2 MPa or more and 70 MPa or less. If the tensile modulus of the component (A2) is equal to or less than the upper limit of the above range, warping of the laminate after application can be suppressed, whereas if it is equal to or greater than the lower limit of the above preferred range, the strength of the cured product can be 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] [ka] [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 above formula (A2-r-1), R a20 ~R a21 are each independently an alkyl group or a hydrogen atom. a20 ~R a21 The alkyl group in is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group or an ethyl group. In the 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 above formula (A2-r-2), R a22 ~R a23 are each independently an alkyl group or a hydrogen atom. a22 ~R a23The alkyl group in is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group or an ethyl group. In the 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 the general formula (A2-r-1) and the structure represented by the general formula (A2-r-2) in the molecular chain, the sum 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 that have 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 further have a linking group derived from bisphenol. Examples of the linking group derived from bisphenol include a linking group derived from bisphenol A (-O-C6H4-C(CH3)2-C6H4-O-), a linking group derived from bisphenol F (-O-C6H4-CH2-C6H4-O-), and the like.

[0056] Furthermore, the component (A2) may be 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 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] [ka]

[0059] [ka]

[0060] [ka]

[0061] In the negative photosensitive adhesive composition of this embodiment, the component (A2) may be used alone or in combination of two or more different compounds. Among the above, as the component (A2), 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 a bisphenol, is preferred. 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 general formula (A2-r-1) above and the structure represented by general formula (A2-r-2) above, and a linking group derived from bisphenol A (-O-C6H4-C(CH3)2-C6H4-O-). 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 general formula (A2-r-1) above and the structure represented by general formula (A2-r-2) above, and a linking group derived from bisphenol F (-O-C6H4-CH2-C6H4-O-). Alternatively, component (A2) is preferably at least one selected from the group consisting of epoxy resins represented by chemical formula (A2-X), epoxy resins represented by chemical formula (A2-Y), epoxy resins represented by chemical formula (A2-P), epoxy resins represented by chemical formula (A2-Q), epoxy resins represented by chemical formula (A2-R), and epoxy group-containing compounds represented by chemical formulas (A2-Z1) to (A2-Z5), more preferably at least one selected from the group consisting of epoxy resins represented by chemical formula (A2-X), epoxy resins represented by chemical formula (A2-Y), and epoxy resins represented by chemical formula (A2-R), and even more preferably at least one selected from the group consisting of epoxy resins represented by chemical formula (A2-X) and epoxy resins represented by chemical formula (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 other epoxy group-containing compounds in addition to the above-mentioned components (A1) and (A2). Other examples of epoxy group-containing compounds include alicyclic epoxy resins (A3) and acrylic resins.

[0064] About cycloaliphatic 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] [ka] [In the formula, n2 is an integer of 1 to 4.]

[0066] In formula (A3-m1), n2 represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2.

[0067] The compound containing the partial structure represented by general formula (A3-m1) includes a compound in which a plurality of partial structures represented by the general formula (A3-m1) are bonded via a divalent linking group or a single bond. Among these, a compound in which a plurality of partial structures represented by the general formula (A3-m1) are bonded via a divalent linking group is preferred. The divalent linking group here is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, etc. The divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom are represented by R in the above formula (abp1). 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)—OY 21 A group represented by Y - 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 the 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), and n1 and n2 each represent an integer of 1 to 30.

[0069] [ka]

[0070] Furthermore, suitable examples of the alicyclic epoxy resin include compounds represented by the following general formula (A3-m2).

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

[0072] In the above 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 components (A1) and (A2), one type of component (A3) may be used alone, or two or more types may be used in combination. Of 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 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] About Acrylic Resin: Examples of the acrylic resin include resins having epoxy group-containing units represented by the following general formula (a1-1) or (a1-2).

[0076] [ka] [wherein 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.] 41is a divalent hydrocarbon group which may have a substituent. 41 is an integer between 0 and 2. a41 , R a42 is an epoxy group-containing group. 42 is 0 or 1. 41 (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 for 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 is most preferably a hydrogen atom or a methyl group from the viewpoint of industrial availability.

[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 groups include the same groups as those explained in the above section, which may have a substituent. Among the above, Va 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 41is an integer of 0 to 2, with 0 or 1 being preferred.

[0080] In formulas (a1-1) and (a1-2), R a41 , R a42 is an epoxy group-containing group. R a41 , R a42 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. The alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure, which is a three-membered ring ether, and 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, alkoxy, or hydroxyl groups. 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 linked 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 optionally substituted divalent hydrocarbon groups: Such a 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 straight-chain or branched-chain 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, even more preferably 1 to 4, and most preferably 1 to 3. The linear aliphatic hydrocarbon group is preferably a linear alkylene group, and specific examples thereof include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], and a pentamethylene group [-(CH2)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. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkyl alkylene groups such as alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. 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 an alicyclic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. Examples of the straight-chain or branched-chain aliphatic hydrocarbon group include the same as those described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and 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 thereof 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 the aromatic ring 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 the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic heterocycle 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 hydrogen atom has been further 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, aromatic hydrocarbon groups in the divalent hydrocarbon groups are preferably aromatic ring hydrocarbon groups that do not contain a fused ring, from the viewpoint of reducing autofluorescence.

[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, such as a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, or 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, such as an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, or 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, more 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, with a fluorine atom being 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 have been 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 heteroatom, and the heteroatom-containing substituent is preferably -O-, -C(=O)-O-, -S-, -S(=O)2-, or -S(=O)2-O-.

[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 the hydrogen atom of the alicyclic hydrocarbon group.

[0089] Regarding divalent linking groups containing heteroatoms: The heteroatom in the divalent linking group containing a heteroatom 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)-, -OC(=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-, and groups represented by the general formula -Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 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, acyl, etc. 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 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -, -[Y 21 -C(=O)-O] m” -Y 22 -or- Y 21 -OC(=O)-Y 22 -Medium, Y 21 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 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. Y 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. Formula − [Y 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 - is a group represented by the formula -Y 21 -C(=O)-OY 22 Particularly preferred is a group represented by the formula -(CH2) a’ -C(=O)-O-(CH2) 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 (na 43The aliphatic hydrocarbon group having a valence of +1 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 a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in its structure, and a group formed by combining a linear or branched aliphatic hydrocarbon group with an aliphatic hydrocarbon group containing a ring in its 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; and hydroxypropyl acrylate. (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. or less. When the combined epoxy equivalent of the entire component (A) is at least as large as the lower limit of the above-mentioned preferred range, a pattern with high rectangularity is more likely to be formed.

[0095] In the negative photosensitive adhesive composition of this embodiment, the component (A) comprises the components (A1) and (A2), and the content of the component (A1) in the 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 the component (A). The content of the component (A2) in the 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 the component (A). When the contents of the components (A1) and (A2) are within the above-mentioned preferred ranges, the effects of the present invention are easily obtained, 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. Additionally, 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. Additionally, the alicyclic epoxy resin (A3) is preferably a compound containing a partial structure represented by the above general formula (A3-m1). Additionally, the epoxy resin (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 a bisphenol.

[0097] It is preferable 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 application is likely to be suppressed, and the sensitivity of pattern formation and rectangularity of the pattern are likely to be improved.

[0098] In the negative photosensitive adhesive composition of this embodiment, the content of component (A) is preferably 50 mass% or more, or may be 60 mass% or more, or may be 60 to 99.9 mass%, relative to the total mass (100 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 solid content concentration is 100% by mass), the content of component (A) is preferably 90% by mass or more, or may be 95% by mass or more, or may be 95 to 99.9% by mass, relative to the total mass of the solid content (100% by mass). The solid content of the negative photosensitive adhesive composition refers 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, where 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 these cations can serve as polymerization initiators.

[0100] [ka] [wherein A is a hetero element selected from the group consisting of boron, aluminum, gallium, phosphorus, arsenic and bismuth; X is a halogen atom; R 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, 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. 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 of these hetero elements may be selected, or two or more 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, and is preferably a fluorine atom.

[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 Rb1 is R b1 They may be linked together to form a divalent or higher organic group that coordinates to A. The term "organic group" as used herein refers to a group containing carbon atoms, and may 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 has 1 to 10 carbon atoms, and particularly preferably has 1 to 8 carbon atoms. R b1 may be free of halogen atoms.

[0104] R b1 Specific examples of when is a monovalent organic group include a fluorinated alkyl group, a fluorinated aryl group, a pentafluorophenyl group, a 3,5-ditrifluoromethylphenyl group, an alkoxylate, and nonafluoro-tert-butylalkoxylate ((CF3)3C—O—). R b1 Specific 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 equal to or greater than 0 and less than 0.7. The upper limit of l / (k+l) is preferably less than 0.6, and more preferably 0.5 or less. The value of l / (k+l) is an index of 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 (B1) component 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] <(B11) ingredient> The component (B11) is a compound represented by the following general formula (B1-1).

[0108] [ka] [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 section In the formula (B1-1), R b01 ~R b04 are each independently an aryl group which may have a substituent, or a fluorine atom. R b01 ~R b04 The aryl group in the formula (I) preferably has 5 to 30 carbon atoms, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples include a naphthyl group, a phenyl group, and an anthracenyl group, with a phenyl group being preferred because of its easy availability. R b01 ~R b04The aryl group in 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 enhanced, which is preferable. Among them, R in formula (B1-1) 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(C6F5)4] - );Tetrakis[(trifluoromethyl)phenyl]borate ([B(C6H4CF3)4] - );Difluorobis(pentafluorophenyl)borate ([(C6F5)2BF2] - );Tetrakis(difluorophenyl)borate ([B(C6H3F2)4] - ) etc. Among them, tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - ) is particularly preferred. Among the above anions, the anion with zero fluorine atoms directly bonded to borane ([B(C6F5)4] - ), ([B(C6H4CF3)4] - ), ([B(C6H3F2)4] - ), ([B(C6F5)4] - In the above formula, 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 with two fluorine atoms directly bonded to borane ([(C6F5)2BF2] -)), l / (k+l) is 0.5. In addition, the anion ([(C6F5)BF3]) has three fluorine atoms directly bonded to borane. - For compounds such as ), l / (k+l) is 0.75.

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

[0112] [ka] [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 from each other, 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 section 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 as or different from each other. R b05 The fluorinated alkyl group in the formula (I) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 5. 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 them, R b05 is preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and further preferably a fluorine atom, a trifluoromethyl group or a pentafluoroethyl group.

[0114] A preferred example of the anion moiety of the compound represented by formula (B1-2) is (CF3CF2)2PF4 - , (CF3CF2)3PF3 - , ((CF3)2CF)2PF4 - , ((CF3)2CF)3PF3 - , (CF3CF2CF2)2PF4 - , (CF3CF2CF2)3PF3 - , ((CF3)2CFCF2)2PF4 - , ((CF3)2CFCF2)3PF3 - , (CF3CF2CF2CF2)2PF4 - and (CF3CF2CF2CF2)3PF3 - Examples of the anion include anions represented by the following formula: Among them, ((CF3)2CF)3PF3 - is preferred. Among the above anions, R is a fluorinated alkyl group which may have a substituent. 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. Among the above anions, R is a fluorinated alkyl group which may have a substituent. b05 In anions with "3" atoms, l / (k+l) is 0.5.

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

[0116] [ka] [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 section In the formula (B1-3), R b06 ~R b09 are each independently an aryl group which may have a substituent, or a fluorine atom. R b06 ~R b09 The aryl group in the formula (B1-1) is explained in detail below. b01 ~R b04 is the same as: 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(C6F5)4] - );Tetrakis[(trifluoromethyl)phenyl]gallate ([Ga(C6H4CF3)4] - );Difluorobis(pentafluorophenyl)gallate ([(C6F5)2GaF2] - );Tetrakis(difluorophenyl)gallate ([Ga(C6H3F2)4] - ) etc. Among them, tetrakis(pentafluorophenyl)gallate ([Ga(C6F5)4] - ) is particularly preferred. Among the above anions, the anion with zero fluorine atoms directly bonded to gallium ([Ga(C6F5)4] - ), ([Ga(C6H4CF3)4] - ), ([Ga(C6H3F2)4] - ), ([Ga(C6F5)4] - In the above formula, 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 with two fluorine atoms directly bonded to gallium ([(C6F5)2GaF2] - )), l / (k+l) is 0.5. In addition, the anion ([(C6F5)GaF3]) in which the number of fluorine atoms directly bonded to gallium is "3" - For compounds such as ), l / (k+l) is 0.75.

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

[0120] [ka] [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. 210 is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. 201 represents -C(=O)- or -C(=O)-O-. Y 201 each independently represents an arylene group, an alkylene group, or an alkenylene group. x is 1 or 2. W 201 represents a (x+1)-valent linking group.

[0121] R 201 ~R 207 , and R 211 ~R 212 The aryl group in the formula (I) includes an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. R 201 ~R 207 , and R 211 ~R 212 Examples of the heteroaryl group in the above 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; 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 the formula (I) is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. R 201 ~R 207 , and R 211 ~R 212 The alkenyl group in the formula (I) preferably has 2 to 10 carbon atoms. R 201 ~R 207 , and R 210 ~R 212 Examples 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 (ca-r-1) to (ca-r-10):

[0122] [ka] [In the formula, R' 201are 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 formulas (ca-r-1) to (ca-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 groups: 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. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. Furthermore, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0125] R' 201 The aromatic hydrocarbon group in the formula (I) is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. R' 201 Specific examples of the aromatic ring possessed by the aromatic hydrocarbon group in the above formula include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and 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, etc. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. R' 201Specific 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 to 2, and particularly preferably 1.

[0126] R' 201 The cyclic aliphatic hydrocarbon group in the formula (I) is an aliphatic hydrocarbon group containing a ring in the structure. Examples of aliphatic hydrocarbon groups that contain a ring in 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 straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and 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 one or more 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 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 bridged ring polycyclic skeleton, such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane; or a polycycloalkane having a fused ring polycyclic skeleton, 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 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred, and specific examples include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], and a pentamethylene group [-(CH2)5-]. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkyl alkylene groups such as alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0129] An optionally substituted chain alkyl group: R' 201 The chain alkyl group may be either a straight chain or a branched chain. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decanyl group, an undecyl group, a dodecyl group, a tridecyl group, an isotridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, an isohexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a heneicosyl group, and a docosyl group. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10. 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] An optionally substituted chain alkenyl group: 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 the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butynyl group. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, and a 2-methylpropenyl group. Of the chain alkenyl groups mentioned above, linear alkenyl groups are preferred, vinyl groups 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 may not contain a heteroatom such as a sulfur atom, an oxygen atom, or a nitrogen atom, or a carbonyl group, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R N )-(applicable R Nis 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 210 is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. R 210 The aryl group in the formula (I) includes an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. R 210 The alkyl group in the formula (I) is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. R 210 The alkenyl group in the formula (I) preferably has 2 to 10 carbon atoms.

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

[0137] In the above formulas (ca-4) and (ca-5), x is 1 or 2. W 201 is an (x+1)-valent, i.e., a divalent or trivalent linking group. W 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 an arylene group alone is preferred. Examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is particularly preferred. W 201 The trivalent linking group in 201 Examples 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 (1), and a group in which the divalent linking group is further bonded to the divalent linking group shown in the formula (1). 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] [ka]

[0140] [ka] [In the formula, R” 201is 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 the group

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

[0142] [ka]

[0143] [ka] [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] [ka]

[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] [ka]

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

[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] [ka]

[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] [ka]

[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] [ka] [In the formula, R' 212 R' 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 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 extinction 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, whereas when the molar extinction 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 the value calculated by measuring the absorbance of component (B1) at a wavelength of 365 nm using a spectrophotometer and using the Beer-Lambert law. Specifically, component (B1) is dissolved in acetonitrile, the solution is placed in a cell with a 10 mm path length, and the UV spectrum is measured using a spectrophotometer (UV-3600, Shimadzu Corporation) to obtain the absorbance at a wavelength of 365 nm. Next, the molar extinction coefficient ε (L / mol cm) is calculated using the Beer-Lambert law from the absorbance and the solution concentration.

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

[0159] [ka]

[0160] In the negative photosensitive adhesive composition of this embodiment, the component (B1) may be used alone or in combination of two or more different types. In the negative 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 component (B1) is within the above-mentioned preferred range, sufficient sensitivity is easily obtained during pattern formation, the lithography properties of the pattern are further improved, and 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 is then bonded to a glass substrate 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 manufacture a microchannel device (silicon wafer / pattern (channel) / glass substrate).

[0162] Microfluidic devices and BioMEMS devices such as μ-TAS are often used to fluorescently stain cells flowing through the channels and observe them. When the negative photosensitive adhesive composition of this embodiment is used to manufacture 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 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 [C13] is a cation represented by general formula (ca-1) above.

[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 ingredients> The negative photosensitive adhesive composition of this embodiment may contain other components as needed in addition to the above-described components (A) and (B). If desired, the negative photosensitive adhesive composition of this embodiment may 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 agents> The negative photosensitive adhesive composition of this embodiment may further contain an adhesion aid to improve adhesion to the support or substrate. This adhesion aid is preferably a silane coupling agent. That is, the negative photosensitive adhesive composition of this embodiment may further contain a silane coupling agent. Examples of the silane coupling agent include silane coupling agents having a reactive substituent such as a carboxy group, a methacryloyl group, an isocyanate group, etc. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, etc. The silane coupling agents may be used alone or in combination of two or more. When a silane coupling agent is included, the content thereof 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 the 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 ingredient> 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 can absorb energy from exposure and transfer that energy to another substance. Specific examples of the sensitizer component that can be used 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 containing no 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 a 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 the component (A). When the content of the sensitizer component is within the above-mentioned preferred range, the sensitivity and resolution can be further improved.

[0167] <Metal oxides> The negative photosensitive adhesive composition of this embodiment may further contain a metal oxide (hereinafter also referred to as "component (M)") because this facilitates the formation of a cured film with increased strength. Furthermore, the inclusion of component (M) also enables the formation of a high-resolution pattern with a good shape. Examples of the component (M) include oxides of metals such as silicon (metallic silicon), titanium, zirconium, hafnium, etc. Among these, oxides of silicon are preferred, and among these, it is particularly preferred to use silica. Furthermore, the component (M) is preferably in the form of particles. Such particulate component (M) preferably comprises a particle group having a volume average particle diameter of 5 to 40 nm, more preferably a particle group having a volume average particle diameter of 5 to 30 nm, and even more preferably a particle group 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 tends to be increased. On the other hand, when the volume average particle diameter 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 component (M) may be appropriately selected depending on the exposure light source. Generally, it is considered that particles having a particle size of 1 / 10 or less of the wavelength of light are hardly affected by light scattering. For this reason, when forming a fine structure by photolithography using i-line (365 nm), for example, it is preferable to use particles (particularly preferably silica particles) with a primary particle size (volume average) of 10 to 20 nm as component (M). As the component (M), one type may be used alone, or two or more types may be used in combination. When the component (M) is contained, the content thereof is preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass, per 100 parts by mass of the component (A). When the content of component (M) is at least the lower limit of the above-mentioned preferred range, the strength of the cured film is further increased, whereas when the content is at most the upper limit of the above-mentioned preferred range, the transparency of the resin film is further increased.

[0168] The negative photosensitive adhesive composition of this embodiment may further contain a solvent (hereinafter sometimes referred to as "component (S)"). Examples of the 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 above polyhydric alcohols or the above compounds having an ester bond such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether; Examples of suitable organic solvents 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) [among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred]; 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 types.

[0169] When component (S) is included, the amount used 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, and the (S) component may be used so that the solids concentration is 60% by mass or more. It is also possible to employ an embodiment in which the component (S) is substantially not contained (that is, an embodiment in which the solid content concentration is 100% by mass).

[0170] As described above, the negative photosensitive adhesive composition of this embodiment contains the epoxy group-containing compound (A) and the 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 general formula (I-an). For example, this negative photosensitive adhesive composition is a suitable material for forming an adhesive layer in a laminate including a support, another support, and an adhesive layer interposed between them to bond the two supports together. By using epoxy resin (A2) in combination with epoxy resin (A1), the elastic modulus of the cured film at room temperature (below 80°C) is reduced. This reduces the difference in thermal expansion between thermocompression bonding and subsequent bonding, thereby reducing warping of the laminate after bonding. In addition, a compound (B1) with a specific anionic structure is used as the photoacid generator (B), which reduces the amount of halogen atoms released.

[0171] In the negative-type photosensitive adhesive composition of this embodiment, the combined epoxy equivalent (g / eq.) of the entire epoxy group-containing compound (A) is preferably 600 or more, and when a negative-type photosensitive adhesive composition of this form 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 the function of emitting or receiving light, 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 embodiment described above.

[0173] The substrate film may be a known film, such as a thermoplastic resin film. Examples of the thermoplastic resin 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] The cover film may be a known film, such as a thermoplastic resin film. Examples of the thermoplastic resin 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 the 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 onto a substrate film, drying it to form a negative photosensitive adhesive composition layer (photosensitive resin film), and then laminating a cover film onto the negative photosensitive adhesive composition layer (photosensitive resin film). The negative photosensitive adhesive composition may be applied to the substrate film by a suitable method using a blade coater, lip coater, comma coater, film coater, or the like. The negative photosensitive adhesive composition layer (photosensitive resin film) included in the photosensitive adhesive dry film of this embodiment is typically made 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 formation method) One embodiment of the pattern formation method is a pattern formation method including 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 formation 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 process] First, the negative photosensitive adhesive composition of the above-described embodiment is applied onto a support by a known method such as spin coating, roll coating, or screen printing, and then baked (post-apply 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 resin film is formed on a support using the photosensitive adhesive dry film of the above-described embodiment.

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

[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 process] Next, the formed photosensitive resin film is selectively exposed using a known exposure device, either through a mask (mask pattern) on which a predetermined pattern has been formed, or by direct irradiation with an electron beam without using a mask pattern, and then baked (post-exposure bake (PEB)) as needed, for example, 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). As the radiation source for these radiations, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, etc. can be used. Here, radiation refers to ultraviolet light, visible light, far ultraviolet light, X-rays, electron beams, etc. The radiation dose varies depending on the type and amount of each component in the composition, the thickness of the coating film, etc. 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 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%. As described above, 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, which increases light transmittance during exposure in pattern formation, 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 process] Next, the exposed photosensitive resin film 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 component (A) (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-based 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] The organic developer may contain known additives as needed. Examples of such additives include surfactants. The surfactants are not particularly limited, but may include, for example, ionic or nonionic fluorine-based and / or silicon-based surfactants. The surfactant is preferably a nonionic surfactant, and more preferably a nonionic fluorine-based surfactant or a nonionic silicon-based surfactant. When a surfactant is added, the amount added is usually 0.001 to 5 mass %, preferably 0.005 to 2 mass %, and more preferably 0.01 to 0.5 mass %, based on the total amount of the organic developer.

[0190] The development process can be carried out by a known development method, such as 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), or 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).

[0191] The rinse treatment (cleaning treatment) using a rinse solution can be carried out by a known rinse method, such as 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 (dipping method), or a method in which the rinse solution is sprayed onto the surface of the support (spray method). The rinsing treatment is preferably carried out using a rinsing liquid 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 of a support and a cured 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 forming method of the above-described embodiment, and then curing the pattern (photosensitive resin film).

[0195] (Method of manufacturing laminate) One embodiment of a 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-described 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 provided with a pattern by the pattern forming method of the above-described embodiment, it is preferable to harden the photosensitive resin film. The curing treatment can be carried out, for example, at 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 released halogen atoms can be reduced, thereby suppressing corrosion of aluminum even when the laminate contains a metal such as aluminum. The laminate manufactured by the manufacturing method of this embodiment is suitable for semiconductor devices or can be applied to microfluidic devices. The laminate can also be applied to various measuring instruments such as image sensors, microscopes, and absorptiometers, displays, and other structures that have a function of emitting or receiving light. [Example]

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

[0200] [Table 1]

[0201] [Table 2]

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

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

[0204] [ka]

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

[0206] [ka]

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

[0208] [ka]

[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] [ka]

[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] [ka]

[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] [ka]

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

[0216] [ka]

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

[0218] <Pattern formation> Film formation process: Each negative photosensitive adhesive composition of the example was spin-coated onto an 8-inch silicon (Si) substrate, pre-baked (PAB) on a hot plate at 100°C for 10 minutes, and dried 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, with a line and space pattern (hereinafter referred to as "1:1 LS pattern") having a line width of 100 μm and a pitch width of 200 μm as the target. Thereafter, post-exposure baking was carried out on a hot plate at 100° C. for 2 minutes.

[0220] Development process: 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] <Manufacturing of laminate> Heat compression bonding process 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) at 200° C. for 5 minutes to obtain a laminate.

[0222] <Evaluation> The negative photosensitive adhesive composition of each example was used to form a pattern and produce a laminate, and the following evaluations were carried out.

[0223] [Evaluation of warpage of laminate] After bonding in the thermocompression bonding step, the warpage of the resulting 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 fluoride generation] Using each negative photosensitive adhesive composition of each example, the negative patterns formed in the above <Pattern formation> were heat-treated under vacuum at 1000 kgf (9800 N) - 200°C - 5 min to obtain cured products. 4 g of the cured negative photosensitive adhesive composition of each example was immersed in 40 mL of water and treated at 120°C for 20 hours (continuous immersion). The extract was then collected and quantitatively analyzed for free fluorine ions by ion chromatography. The results are shown in Table 3. A: No free fluoride ions were detected C: Free fluoride 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 50 mJ / cm 2 A pattern was formed with B: Exposure dose 100 mJ / cm 2 A pattern was formed with C: Exposure dose 200 mJ / cm 2 A pattern was formed with

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

[0227] [Table 3]

[0228] [Table 4]

[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 the 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. 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 have different contents 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 use of the negative photosensitive adhesive compositions of Examples 13 and 14 resulted in higher sensitivity during pattern formation than the use of the negative photosensitive adhesive composition of Example 16.

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

Claims

1. A negative photosensitive adhesive composition containing an epoxy group-containing compound (A) and a photoacid generator (B), the epoxy group-containing compound (A) comprises 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, The photoacid generator (B) contains a compound (B1) having a cation moiety and an anion moiety, The anion moiety contains an anion represented by the following general formula (I-an): 【Chemistry 1】 [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. 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 epoxy group-containing compound (A) is The epoxy resin (A1), an alicyclic epoxy resin (A3); Epoxy resins (A2″) other than these that exhibit a tensile modulus of elasticity of 100 MPa or less when cured alone; The negative photosensitive adhesive composition of claim 1 , comprising:

4. the content of the epoxy resin (A1) is 50% by mass or more and 80% by mass or less based on 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, based on the total mass (100% by mass) of the epoxy group-containing compound (A), 4. The negative photosensitive adhesive composition according to claim 3, wherein 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. 2. 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 epoxy resin.

7. The negative photosensitive adhesive composition according to claim 1 , wherein the epoxy resin (A1) is a bisphenol F 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. 2. The negative photosensitive adhesive composition according to claim 1, wherein the 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): 【Chemistry 2】 [In the formula, R ａ２０ ~R ａ２３ are each independently an alkyl group or a hydrogen atom. m1 and m2 each independently represent an integer from 1 to 15.

10. The negative photosensitive adhesive composition according to claim 9 , wherein the 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 step of forming a photosensitive resin film on a support using the negative photosensitive adhesive composition according to any one of claims 1 to 10; a step of exposing the photosensitive resin film to light; and A step of developing the exposed photosensitive resin film with a developer containing an organic solvent to form a negative pattern. A pattern forming method comprising the steps of:

13. A step of obtaining a support having a negative pattern by using the pattern forming method according to claim 12; and A step of bonding the support provided with the negative pattern to another support by thermocompression bonding to obtain a laminate. A method for producing a laminate comprising the steps of:

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