Photosensitive adhesive composition, photosensitive adhesive dry film, pattern formation method, and laminate production method

Abstract

The present invention employs a photosensitive adhesive composition that contains an acrylic resin, an epoxy group-containing compound (excluding those corresponding to acrylic resins), and a photocationic polymerization initiator. The acrylic resin has a constituent unit that is derived from an acrylic monomer including a functional group which reacts with a carboxy group (-COOH), and has a glass transition temperature of not higher than 0°C and a weight average molecular weight of not less than 200,000. The photosensitive adhesive composition makes it possible to bond a transparent substrate and another substrate, makes whitening of the transparent substrate less likely to occur during bonding, and provides good resolution in pattern formation.

Description

Photosensitive adhesive composition, photosensitive adhesive dry film, pattern forming method, and method for manufacturing laminate.

[0001] The present invention relates to a photosensitive adhesive composition, a photosensitive adhesive dry film, a pattern forming method, and a method for manufacturing a laminate. This application claims priority under Japanese Patent Application No. 2024-165595, filed in Japan on September 24, 2024, the contents of which are incorporated herein by reference.

[0002] As electronic components become more sophisticated, semiconductor devices are becoming smaller and more powerful. In response to this, device integration and various package configurations are being proposed. For example, one package configuration that utilizes a hollow structure in which the wiring substrate on which electrodes are formed remains hollow (hollow package) is being used.

[0003] A photosensitive adhesive is used when manufacturing the aforementioned hollow package. A photosensitive adhesive is applied to a substrate, exposed to light, and developed to form a pattern for the side walls that will serve as spacers. Then, the substrate with this pattern and another substrate that will serve as the top plate are bonded together by thermocompression to create a hollow structure. Subsequently, the hollow package is manufactured by mold molding. As the photosensitive adhesive, for example, a photocurable composition containing an acrylic resin, an epoxy group-containing compound, and a cationic polymerization initiator has been proposed (see, for example, Patent Document 1).

[0004] International Publication No. 2023 / 120274

[0005] In the manufacturing of electronic components, photosensitive adhesives are required to have various properties. When manufacturing the hollow package described above, the photosensitive adhesive is used as the material for the side walls that act as spacers. For the formation of these side walls, the photosensitive adhesive needs to have pattern-forming properties that enable the formation of high-resolution patterns in a good shape. In addition, the side walls also need to have sufficient adhesion to the top plate. On the other hand, during mold molding and bump formation in the manufacturing of hollow packages, the parts where the photosensitive adhesive is used are subjected to high temperature and high pressure. Conventional photosensitive adhesives, such as those described in Patent Document 1, have the problem that whitening occurs in the transparent substrate bonded via the photosensitive adhesive layer due to the effects of the thermal history.

[0006] The present invention has been made in view of the above circumstances, and aims to provide a photosensitive adhesive composition that can bond a transparent substrate to another substrate, is less likely to cause whitening of the transparent substrate during bonding, and has good resolution in pattern formation; a photosensitive adhesive dry film using the same; a method for forming various patterns using the photosensitive adhesive composition and the photosensitive adhesive dry film; and a method for manufacturing a laminate using the pattern formation method.

[0007] To solve the above problems, the present invention employs the following configuration. Specifically, the first aspect of the present invention is a photosensitive adhesive composition containing an acrylic resin, an epoxy group-containing compound (excluding those corresponding to the acrylic resin), and a photocationic polymerization initiator, wherein the acrylic resin has structural units derived from an acrylic monomer containing a functional group that reacts with a carboxyl group (-COOH), has a glass transition temperature of 0°C or lower, and has a weight-average molecular weight of 200,000 or more.

[0008] A second aspect of the present invention is a photosensitive adhesive dry film made using the photosensitive adhesive composition according to the first aspect.

[0009] A third aspect of the present invention is a pattern forming method comprising the steps of forming a photosensitive resin film on a support using a photosensitive adhesive composition according to the first aspect or a 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-type pattern.

[0010] A fourth aspect of the present invention is a method for manufacturing a laminate, comprising the steps of obtaining a support having a negative pattern by using the pattern forming method according to the third aspect, and obtaining a laminate by bonding the support having the negative pattern with another support by thermocompression bonding.

[0011] According to the present invention, it is possible to provide a photosensitive adhesive composition that can bond a transparent substrate to another substrate, is less likely to cause whitening of the transparent substrate during bonding, and has good resolution in pattern formation; a photosensitive adhesive dry film using the same; a pattern formation method using the photosensitive adhesive composition and the photosensitive adhesive dry film; and a method for manufacturing a laminate using the pattern formation method.

[0012] In this specification and in these claims, “aliphatic” is defined as a concept relative to aromatic, meaning a group that does not possess aromaticity, a compound that does not possess aromaticity, etc. Unless otherwise specified, “alkyl group” includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups in alkoxy groups. Unless otherwise specified, “alkylene group” includes linear, branched, and cyclic divalent saturated hydrocarbon groups. “Halogenated alkyl group” is a group in which some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms, and examples of such halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. “Fluorinated alkyl group” means a group in which some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. “Constituent unit” means a monomer unit (monomer unit) that constitutes a polymer compound (resin, polymer, copolymer). When it is stated that “may have substituents,” this refers to the case where a hydrogen atom (-H) is substituted with a monovalent group, and the case where a methylene group (-CH) is substituted with a monovalent group. ２ This includes both cases where the negative (-) is substituted with a divalent group. "Exposure" is a concept that includes all forms of radiation irradiation.

[0013] (Photosensitive adhesive composition) One embodiment of the photosensitive adhesive composition contains an acrylic resin, an epoxy group-containing compound (excluding those corresponding to the acrylic resin), and a photocationic polymerization initiator. The acrylic resin has structural units derived from an acrylic monomer containing a functional group that reacts with a carboxyl group (-COOH), has a glass transition temperature of 0°C or lower, and has a weight-average molecular weight of 200,000 or more.

[0014] When a photosensitive resin film is formed using such a photosensitive adhesive composition and selectively exposed to light, in the exposed areas of the photosensitive resin film, the cation portion of the photocationic polymerization initiator decomposes to generate acid. This acid causes ring-opening polymerization of the epoxy group-containing compound, reducing the solubility of the epoxy group-containing compound in a developer containing an organic solvent. In contrast, in the unexposed areas of the photosensitive resin film, the solubility of the epoxy group-containing compound in a developer containing an organic solvent remains unchanged. As a result, a difference in solubility in a developer containing an organic solvent occurs 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-type pattern.

[0015] <Acrylic Resin> The acrylic resin contained in the photosensitive adhesive composition of this embodiment (hereinafter also referred to as "component (AC)") has a constituent unit (hereinafter also referred to as "constituent unit (ac1)") derived from an acrylic monomer containing a functional group that reacts with a carboxyl group (-COOH). In addition, the (AC) component has a glass transition temperature of 0°C or lower and a weight-average molecular weight of 200,000 or more.

[0016] "Acrylic resin" refers to a polymer produced by the polymerization of at least acrylic acid ester as a monomer. "Acrylic acid ester" may have a hydrogen atom bonded to the α-carbon atom substituted with a substituent. Substituents that replace the hydrogen atom bonded to the α-carbon atom (R αｘ ) is an atom or group other than a hydrogen atom. Note that, unless otherwise specified, the α-carbon atom of an acrylic acid ester refers to the carbon atom to which the carbonyl group of acrylic acid is bonded. Substituents (R αｘ Examples of these include alkyl groups having 1 to 5 carbon atoms, halogen atoms, or halogenated alkyl groups having 1 to 5 carbon atoms.

[0017] The glass transition temperature Tg of acrylic resin is calculated using the following formula (Fox's formula): 1 / (Tg+273) = {W1 / (Tg1+273)+W2 / (Tg2+273)+...} / 100 Tg: Glass transition temperature (°C) of the copolymer which is acrylic resin Tg1: Glass transition temperature (°C) of the homopolymer consisting of a repeating structure of constituent unit (1) derived from monomer (1) Tg2: Glass transition temperature (°C) of the homopolymer consisting of a repeating structure of constituent unit (2) derived from monomer (2) W1: Percentage (mass%) of constituent unit (1) constituting the acrylic resin W2: Percentage (mass%) of constituent unit (2) constituting the acrylic resin W1+W2+...=100

[0018] The glass transition temperatures of homopolymers will be based on values ​​disclosed on the website of KTR Corporation (Kaji Test Research) (www.kaji-tr.com), the Polymer Materials Handbook (edited by the Society of Polymer Science, Corona Publishing Co., Ltd., first edition, published February 20, 1973), the Acrylic Products Catalog of Kyoeisha Chemical Co., Ltd., and the Polymer Data Handbook Basic Edition (edited by the Society of Polymer Science, Baifukan Publishing Co., Ltd., published January 30, 1986).

[0019] For example, the glass transition temperature Tg (°C) of an acrylic resin copolymer of a structural unit derived from 2-methoxyethyl acrylate, a structural unit derived from methyl methacrylate, and a structural unit derived from glycidyl methacrylate can be calculated as follows: Let monomer (1) be 2-methoxyethyl acrylate. The glass transition temperature of the homopolymer consisting of a repeating structure of structural unit (1) derived from monomer (1) is -55°C, and the proportion of structural unit (1) is 70% by mass. Let monomer (2) be methyl methacrylate. The glass transition temperature of the homopolymer consisting of a repeating structure of structural unit (2) derived from monomer (2) is 105°C, and the proportion of structural unit (2) is 25% by mass. Let monomer (3) be glycidyl methacrylate. The glass transition temperature of the homopolymer consisting of a repeating structure of structural unit (3) derived from monomer (3) is 41°C, and the proportion of structural unit (3) is 5% by mass. The glass transition point Tg (°C) of the acrylic resin, which is a copolymer of the constituent units (1), (2), and (3), is calculated using the following formula: 1 / (Tg + 273) = {70 / (-55 + 273) + 25 / (105 + 273) + 5 / (41 + 273)} / 100 Tg ≈ -25°C

[0020] The glass transition temperature Tg of the (AC) component is 0°C or lower, preferably between -100°C and 0°C, more preferably between -75°C and less than 0°C, even more preferably between -50°C and -2°C, and particularly preferably between -30°C and -5°C. If the glass transition temperature Tg of the (AC) component is below the upper limit of the above range, the adhesion between the transparent substrate and other substrates can be easily improved when a cured film is formed. Reliability is also improved. On the other hand, if it is above the lower limit of the above range, the lithography characteristics during pattern formation are improved. Furthermore, the chemical resistance of the photosensitive resin film pattern can be more easily improved.

[0021] The glass transition temperature Tg of the (AC) component can be controlled by selecting the type of constituent units that make up the (AC) component or by adjusting the content ratio of those constituent units.

[0022] The weight-average molecular weight (Mw) of acrylic resin is determined by gel permeation chromatography (GPC) and is expressed as a value equivalent to standard polystyrene.

[0023] The weight-average molecular weight (Mw) of the (AC) component is 200,000 or more, preferably between 200,000 and 750,000, more preferably between 200,000 and 600,000, and even more preferably between 220,000 and 550,000. If the weight-average molecular weight (Mw) of the (AC) component is above the lower limit of the above range, the resolution in pattern formation tends to improve. On the other hand, if it is below the upper limit of the above range, the adhesion to the object when it becomes a cured film can be improved, and reliability can be improved.

[0024] The weight-average molecular weight (Mw) of component (AC) can be controlled by adjusting the polymerization conditions during the production of component (AC).

[0025] The dispersion degree (Mw / Mn) of the (AC) component is not particularly limited, but is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and particularly preferably 1.0 to 2.0. Mn represents the number-average molecular weight.

[0026] ≪Constituent Unit (ac1)≫ The (AC) component has a constituent unit (constituent unit (ac1)) derived from an acrylic monomer containing a functional group that reacts with a carboxyl group (-COOH). "Constituent unit derived from an acrylic monomer" means a constituent unit formed by the cleavage of the ethylenic double bond of the acrylic monomer.

[0027] A "functional group that reacts with a carboxyl group (-COOH)" refers to an atomic group that undergoes a reaction that deactivates the carboxyl group (-COOH) upon heating. Examples of "functional groups that react with a carboxyl group (-COOH)" include epoxy groups, alcoholic hydroxyl groups, and amino groups (-NH). ２ Examples include thiol groups (-SH), isocyanate groups (-N=C=O), and halogenated alkyl groups.

[0028] In the constituent unit (ac1), the acrylic monomer providing the constituent unit (ac1) (the acrylic monomer from which the constituent unit (ac1) is derived) is an epoxy group, an alcoholic hydroxyl group, and an amino group (-NH ２It is preferable that the monomer contains at least one functional group selected from the group consisting of ).

[0029] Alternatively, the constituent unit (ac1) may be, for example, a constituent unit derived from an acrylic acid ester containing a functional group that reacts with a carboxyl group, or a constituent unit derived from acrylamide.

[0030] In this context, "acrylic acid ester" may have a hydrogen atom bonded to the α-carbon atom substituted with a substituent. In this context, "acrylamide" may have a hydrogen atom bonded to the α-carbon atom substituted with a substituent.

[0031] A substituent (R) that replaces the hydrogen atom bonded to the carbon atom at the α position αｘ Examples include alkyl groups having 1 to 5 carbon atoms, halogen atoms, or halogenated alkyl groups having 1 to 5 carbon atoms. αｘ The alkyl group having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically including methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl groups. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Fluorine atoms are particularly preferred as the halogen atoms. αｘ Preferably, the element is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, with a hydrogen atom or a methyl group being particularly preferred.

[0032] ・Acrylic monomers containing epoxy groups For example, an acrylic monomer containing epoxy groups from which the constituent unit (ac1) is derived is an epoxy group-containing acrylic monomer that is a (meth)acrylic acid ester in which the ester portion is an epoxy group-containing group. Note that "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid (the same applies hereinafter). The "epoxy group-containing group" is not particularly limited and includes groups consisting only of epoxy groups; groups consisting only of alicyclic epoxy groups; and groups having an epoxy group or an alicyclic epoxy group and a divalent linking group.

[0033] An alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure, which is a three-membered ring ether. Specifically, it is a group having an alicyclic group and an oxacyclopropane structure. The alicyclic group that forms the basic skeleton of an 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. Furthermore, the hydrogen atoms of these alicyclic groups may be substituted with alkyl groups, alkoxy groups, hydroxyl groups, etc. 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 alicyclic epoxy group is bonded via a divalent linking group bonded to the oxygen atom (-O-) in the (meth)acryloyloxy group.

[0034] Here, the divalent linking group is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have substituents, a divalent linking group which contains a heteroatom, and so on.

[0035] Regarding the divalent hydrocarbon group which may have a substituent: 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 it is usually preferred to be saturated. More specifically, examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in its structure, etc.

[0036] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred. Specifically, a methylene group [-CH ２ -], an ethylene group [-(CH ２ ) ２ -], a trimethylene group [-(CH ２ ) ３ -], a tetramethylene group [-(CH ２ ) ４ -], a pentamethylene group [-(CH ２ ) ５ -], etc. may be mentioned. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms, and most preferably 2 or 3 carbon atoms. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, -CH(CH ３ )-, -CH(CH ２ CH ３ )-, -C(CH ３ ) ２ -, -C(CH ３ )(CH ２ CH ３ )-, -C(CH ３ )(CH ２ CH ２ CH ３ )-, -C(CH ２ CH ３ ) ２ - and other alkylmethylene groups; -CH(CH ３ )CH ２ -, -CH(CH ３ )CH(CH３ )-,-C(CH ３ ) ２ CH ２ -, -CH(CH ２ CH ３ )CH ２ -, -C(CH ２ CH ３ ) ２ -CH ２ - Alkyl ethylene groups such as -CH(CH ３ )CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ - Alkyl trimethylene groups such as -CH(CH ３ )CH ２ CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ CH ２ Examples include alkylalkylene groups such as alkyltetramethylene groups. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0037] Examples of aliphatic hydrocarbon groups containing a ring in the structure include alicyclic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group are 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. As a monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferred. The monocycloalkane preferably has 3 to 6 carbon atoms, and specifically examples include cyclopentane and cyclohexane. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferred, and as the polycycloalkane, those having 7 to 12 carbon atoms are preferred, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like.

[0038] The aromatic hydrocarbon group in a divalent hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n+2) π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. Specific examples of aromatic hydrocarbon groups include: a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); a group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) in which one hydrogen atom is replaced by an alkylene group (e.g., a group obtained by removing one more hydrogen atom from the aryl group in an arylalkyl group such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). 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.

[0039] The divalent hydrocarbon group may have substituents. The linear or branched aliphatic hydrocarbon group, as the divalent hydrocarbon group, may or may not have substituents. Examples of substituents include fluorine atoms, fluorinated alkyl groups having 1 to 5 carbon atoms substituted with fluorine atoms, and carbonyl groups.

[0040] 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 substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, and carbonyl groups. Preferably, the alkyl group as a substituent has 1 to 5 carbon atoms, and most preferably it is a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. Preferably, the alkoxy group as a substituent has 1 to 5 carbon atoms, and preferably it is a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, or tert-butoxy group, with methoxy and ethoxy groups being the most preferred. Examples of halogen atoms as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred. Examples of alkyl halides as substituents include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms. Alicyclic hydrocarbon groups may have some of the carbon atoms constituting their ring structure substituted with substituents containing heteroatoms. Examples of such substituents containing heteroatoms include -O-, -C(=O)-O-, -S-, and -S(=O). ２ -, -S (=O) ２ -O- is preferred.

[0041] As a divalent hydrocarbon group, the aromatic hydrocarbon group may have its hydrogen atoms substituted with substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, and hydroxyl groups. As the alkyl group substituent, alkyl groups having 1 to 5 carbon atoms are preferred, and methyl groups, ethyl groups, propyl groups, n-butyl groups, and tert-butyl groups are most preferred. Examples of alkoxy groups, halogen atoms, and alkyl halides substituents include those exemplified as substituents that substitute for hydrogen atoms in the alicyclic hydrocarbon group.

[0042] Regarding divalent linking groups containing heteroatoms: In divalent linking groups containing heteroatoms, the heteroatom is an atom other than carbon and hydrogen atoms, such as oxygen, nitrogen, sulfur, halogen, etc.

[0043] In a divalent linking group containing a heteroatom, preferred linking groups include -O-, -C(=O)-O-, -C(=O)-, -O-C(=O)-O-; -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)- (H may be substituted with substituents such as alkyl groups or acyl groups); -S-, -S(=O) ２ -, -S (=O) ２ -O-, general formula -Y ２１ -O-Y ２２ -, -Y ２１ -O-, -Y ２１ -C(=O)-O-, -C(=O)-O-Y ２１ ,-[Y ２１ -C (=O) -O] ｍ” -Y ２２ - or - Y ２１ -OC(=O)-Y ２２ - is represented by the base [wherein Y ２１ and Y ２２ Each of these is a divalent hydrocarbon group which may independently have substituents, O is an oxygen atom, and m'' is an integer from 1 to 3. For example, when the divalent linking group containing the heteroatom is -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)-, the H may be substituted with substituents such as alkyl groups or acyl groups. 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. Formula -Y ２１ -O-Y ２２ -, -Y ２１ -O-, -Y ２１ -C(=O)-O-, -C(=O)-O-Y ２１ -, -[Y ２１ -C (=O) -O] ｍ” -Y ２２ - or - Y ２１ -OC(=O)-Y ２２ - Middle, Y２１ and Y ２２ is each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same ones as the "divalent hydrocarbon group which may have a substituent" described as the divalent linking group above. Y ２１ is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group. 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, as the group represented by the formula -[Y ２１ -C(=O)-O] ｍ” -Y ２２ -, the group represented by the formula -Y ２１ -C(=O)-O-Y ２２ - is particularly preferred. Among them, the group represented by the formula -(CH ２ ) ａ’ -C(=O)-O-(CH ２ ) ｂ’ - is preferred. 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, still 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, still more preferably 1 or 2, and most preferably 1.

[0044] Among them, as the epoxy group-containing group, a glycidyl group is preferred. That is, as the acrylic monomer containing an epoxy group, glycidyl acrylate and glycidyl methacrylate are preferred.

[0045] - Acrylic monomers containing an alcoholic hydroxyl group. For example, an acrylic monomer containing an alcoholic hydroxyl group derived from the constituent unit (ac1) is a (meth)acrylic acid ester, where the ester portion is a hydroxyalkyl group, and this is a (meth)acrylic acid hydroxyalkyl ester. The number of carbon atoms in the hydroxyalkyl group is preferably 1 to 5. Preferred acrylic monomers containing an alcoholic hydroxyl group include (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate.

[0046] • Amino group (-NH ２ Acrylic monomers containing ) For example, an amino group (-NH) derived from the constituent unit (ac1) ２ Examples of acrylic monomers containing ) include primary amide compounds such as acrylamide and methacrylamide.

[0047] The constituent unit (ac1) of component (AC) may be one type or two or more types. The constituent unit (ac1) may be an acrylic monomer containing an epoxy group, an acrylic monomer containing an alcoholic hydroxyl group, and an amino group (-NH ２ A structural unit derived from at least one acrylic monomer selected from the group consisting of acrylic monomers containing ) is preferred, a structural unit derived from at least one acrylic monomer selected from the group consisting of epoxy group-containing acrylic monomers, (meth)acrylate hydroxyalkyl esters and primary amide compounds is more preferred, and a structural unit derived from at least one acrylic monomer selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, acrylamide and methacrylamide is even more preferred.

[0048] The content ratio of the constituent unit (ac1) in the (AC) component is preferably more than 0% by mass and less than 50% by mass, more preferably 0.5% by mass or more and 45% by mass or less, even more preferably 1% by mass or more and 40% by mass or less, and particularly preferably 2% by mass or more and 35% by mass or less, based on the total (100% by mass) of all constituent units that make up the (AC) component. If the content ratio of the constituent unit (ac1) exceeds the lower limit of the above range, whitening of the transparent substrate is less likely to occur when bonding the transparent substrate to other substrates. On the other hand, if it is below the upper limit of the above range, the adhesion between the transparent substrate and other substrates can be improved when a cured film is formed, and reliability can be improved.

[0049] <<Constituent Unit (ac2)>> The (AC) component has a constituent unit (ac2) such that the glass transition temperature of the acrylic resin, which is a copolymer of the above-mentioned constituent unit (ac1), is 0°C or lower. Examples of such constituent units (ac2) include constituent units derived from acrylic acid esters other than the above-mentioned constituent unit (ac1), and constituent units derived from other polymerizable compounds.

[0050] The term "acrylic acid ester" as used herein may have a substituent that replaces the hydrogen atom bonded to the α-carbon atom. αｘ Examples of these include alkyl groups having 1 to 5 carbon atoms, halogen atoms, or halogenated alkyl groups having 1 to 5 carbon atoms.

[0051] Examples of monomers from which the constituent unit (ac2) is derived include alkyl (meth)acrylates such as 2-ethylhexyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl acrylate, methyl acrylate, 2-ethylhexyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, ethyl methacrylate, and methyl methacrylate; alkoxyalkyl (meth)acrylates such as 2-methoxyethyl acrylate and 2-methoxyethyl methacrylate; phenyl acrylate, benzyl acrylate, phenyl methacrylate, and benzyl methacrylate. Examples include aryl (meth)acrylates such as ethyl ester; 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; polymerizable compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; and chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride.

[0052] The constituent unit (ac2) of component (AC) may be one type or two or more types. Among the above, alkyl (meth)acrylates and alkoxyalkyl (meth)acrylates are preferred as monomers from which the constituent unit (ac2) is derived. In alkyl (meth)acrylates, the number of carbon atoms of the alkyl group in the alkyl ester portion is preferably 1 to 5. In alkoxyalkyl (meth)acrylates, the number of carbon atoms of the alkoxy group in the alkoxyalkyl ester portion is preferably 1 to 3, and the number of carbon atoms of the alkylene group is preferably 1 to 5.

[0053] The content of the constituent unit (ac2) is preferably more than 50% by mass, more preferably 55% by mass or more and 99.5% by mass or less, even more preferably 60% by mass or more and 99% by mass or less, and particularly preferably 65% ​​by mass or more and 98% by mass or less, based on the total (100% by mass) of all constituent units that make up the (AC) component. If the content of the constituent unit (ac2) is above the lower limit of the above range, the adhesion between the transparent substrate and other substrates can be improved when a cured film is formed, and reliability can be improved. On the other hand, if it is below the upper limit of the above range, whitening of the transparent substrate is less likely to occur when the transparent substrate is bonded to other substrates.

[0054] The acrylic resin (AC) contained in the photosensitive adhesive composition of this embodiment includes a copolymer having the aforementioned structural unit (ac1), a glass transition temperature of 0°C or lower, and a weight-average molecular weight of 200,000 or more. One type of this copolymer may be used alone, or two or more types may be used in combination. Preferred (AC) components include copolymers having structural unit (ac1) and structural units derived from alkyl (meth)acrylate, and copolymers having structural unit (ac1) and structural units derived from alkoxyalkyl (meth)acrylate. Alternatively, preferred (AC) components include copolymers having structural unit (ac1) and structural units derived from alkoxyalkyl (meth)acrylate and structural units derived from alkyl (meth)acrylate.

[0055] For example, in a copolymer having a constituent unit (ac1) and other constituent units (ac2), it is preferable that the content of constituent unit (ac1) is 2% by mass or more and 35% by mass or less, and the content of constituent unit (ac2) is 65% by mass or more and 98% by mass or less, relative to the total amount (100% by mass) of all constituent units constituting the copolymer. Alternatively, in a copolymer having a constituent unit (ac1) and other constituent units (ac2), it is preferable that the content of constituent unit (ac1) is 2% by mass or more and 35% by mass or less, relative to the total amount (100% by mass) of all constituent units constituting the copolymer, the content of constituent units derived from (meth)acrylate alkoxyalkyl esters is 35% by mass or more and 75% by mass or less, and the content of constituent units derived from (meth)acrylate esters is 20% by mass or more and 35% by mass or less.

[0056] The (AC) component can be produced by dissolving monomers derived from constituent unit (ac1) and monomers derived from constituent unit (ac2) in a polymerization solvent, and then adding a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601) to carry out polymerization.

[0057] In the photosensitive adhesive composition of this embodiment, the content of component (AC) is preferably 5% to 40% by mass, more preferably 10% to 35% by mass, and even more preferably 10% to 30% by mass, based on the total content (100% by mass) of component (AC) and the epoxy group-containing compound (component (A)) described later. If the content of component (AC) is above the lower limit of the preferred range described above, the adhesion to the object and the adhesion between the transparent substrate and other substrates can be more easily improved when a cured film is formed. On the other hand, if it is below the upper limit of the preferred range described above, the resolution in pattern formation can be easily improved. In addition, the strength of the formed cured film can be sufficiently increased.

[0058] In the photosensitive adhesive composition of this embodiment, the content of component (AC) is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, and even more preferably 10 to 30% by mass, based on the total solid content (100% by mass) of the photosensitive adhesive composition.

[0059] <Epoxy Group-Containing Compounds> The epoxy group-containing compound contained in the photosensitive adhesive composition of this embodiment (hereinafter also referred to as "component (A)") is a compound having a sufficient number of epoxy groups in one molecule to form a negative pattern by exposure. However, component (A) excludes those corresponding to the acrylic resin (AC) described above. Examples of such component (A) include bisphenol-type epoxy resin (hereinafter also referred to as "component (A1)"), novolac-type epoxy resin (hereinafter also referred to as "component (A2)"), aliphatic epoxy resin, etc. Component (A) may be used alone or in combination of two or more.

[0060] ≪Bisphenol-type epoxy resin≫ The bisphenol-type epoxy resin (hereinafter also referred to as "component (A1)") can be any resin having structural units containing a bisphenol skeleton, and among these, solid bisphenol-type epoxy resin is preferred. A solid bisphenol-type epoxy resin is a resin that is solid at 25°C and has structural units containing a bisphenol skeleton. The epoxy equivalent of component (A1) is preferably 500 g / eq. or more, and more preferably 500 to 1000 g / eq.

[0061] (A1) Component is preferably an epoxy resin represented by the following general formula (abp1).

[0062] [In the formula, R ＥＰ This is an epoxy group-containing group. Multiple R ＥＰ They may be identical or different from one another. ａ３１ and R ａ３２ Each of these is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. ３１ [This is an integer between 1 and 50.]

[0063] In the above formula (abp1), R ＥＰ R is an epoxy group-containing group. ＥＰ The epoxy group-containing group is not particularly limited and includes groups consisting solely of epoxy groups; groups consisting solely of alicyclic epoxy groups; and groups having an epoxy group or an alicyclic epoxy group and a divalent linking group. ＥＰ The explanation of epoxy group-containing groups is the same as the explanation of "epoxy group-containing groups" in the explanation of acrylic monomers containing epoxy groups. In particular, R ＥＰ A glycidyl group is preferred as the epoxy group-containing group in this product.

[0064] In the above formula (abp1), R ａ３１ and R ａ３２ The alkyl groups having 1 to 5 carbon atoms in this are, for example, linear, branched, or cyclic alkyl groups having 1 to 5 carbon atoms. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl groups. Examples of cyclic alkyl groups include cyclobutyl and cyclopentyl groups. Among these, R ａ３１ , R ａ３２ Preferably, each R is a hydrogen atom or a linear or branched alkyl group, more preferably a hydrogen atom or a linear alkyl group, and particularly preferably a hydrogen atom or a methyl group. In formula (abp1), multiple R ａ３１ These may be identical or different from one another. ａ３２ They may be identical or different from one another. ａ３１ , R ａ３２ The fluorinated alkyl group having 1 to 5 carbon atoms in the above R ａ３１ , R ａ３２ Examples include groups in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms are substituted with fluorine atoms. In formula (abp1), na ３１ is an integer between 1 and 50, preferably between 4 and 15, and more preferably between 4 and 8.

[0065] (A1) Examples of commercially available products that can be used as components include jER-4005, jER-4007, jER-4010 (all manufactured by Mitsubishi Chemical Corporation); jER-827, jER-828, jER-834, jER-1001, jER-1002, jER-1003, jER-1055, jER-1007, jER-1009, jER-1010 (all manufactured by Mitsubishi Chemical Corporation); EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (all manufactured by DIC Corporation), etc.

[0066] Component (A1) may be used alone or in combination of two or more. In the photosensitive adhesive composition of this embodiment, the content of component (A1) is preferably 50% by mass or more, more preferably 60% by mass or more, and may be 70% by mass or more, 80% by mass or more, 90% by mass or more, or 100% by mass, based on 100% by mass of the total amount of component (A).

[0067] <<Novolac-type epoxy resin>> As the novolac-type epoxy resin (component (A2)), epoxy resins represented by the following general formula (anv0) are preferred.

[0068] [In the formula, R ｐ１ and R ｐ２ Each of these is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ｐ１ These may be identical or different from one another. ｐ２ n may be identical or different from each other. １ R is an integer between 1 and 5. ＥＰ This is an epoxy group-containing group. Multiple R ＥＰ They may be identical or different from one another.

[0069] In the above formula (anv0), R ｐ１ , R ｐ２ The alkyl group having 1 to 5 carbon atoms in the above formula (abp1) is R ａ３１ , R ａ３２ This is similar to alkyl groups with 1 to 5 carbon atoms in [the given text]. In particular, R ｐ１ , Rｐ２ Preferably, these are a hydrogen atom or a methyl group. ｐ１ , R ｐ２ The fluorinated alkyl group having 1 to 5 carbon atoms in the above R ｐ１ , R ｐ２ Examples include groups in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms are substituted with fluorine atoms. In formula (anv0), multiple R ｐ１ These may be identical or different from one another. ｐ２ They may be identical or different from one another.

[0070] In the above formula (anv0), n １ is an integer from 1 to 5, preferably 2 or 3, and more preferably 2.

[0071] In the above formula (anv0), R ＥＰ is an epoxy group containing R in formula (abp1). ＥＰ Similar to the above, a glycidyl group is preferred.

[0072] Furthermore, as component (A2), resins having constituent units represented by the following general formula (anv1) are also preferred.

[0073] [In the formula, R ＥＰ R is an epoxy group-containing group. ａ２２ and R ａ２３ These are, independently, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.

[0074] In the above formula (anv1), R ａ２２ , R ａ２３ The alkyl group having 1 to 5 carbon atoms is R in the above formula (anv0). ｐ１ , R ｐ２ This is similar to alkyl groups with 1 to 5 carbon atoms. ａ２２ , R ａ２３ The halogen atom is preferably a chlorine atom or a bromine atom. In the above formula (anv1), R ＥＰ R in the above formula (anv0) is ＥＰ Similar to the above, a glycidyl group is preferred.

[0075] The following are specific examples of the constituent units represented by the above formula (anv1).

[0076]

[0077] Component (A2) may be a resin consisting only of the aforementioned constituent unit (anv1), or it may be a resin having constituent unit (anv1) and other constituent units. Examples of these other constituent units include those represented by the following general formulas (anv2) to (anv3).

[0078] [In the formula, R ａ２４ R is a hydrocarbon group which may have substituents. ａ２５ ~R ａ２６ , R ａ２８ ~R ａ３０ Each of these is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. ａ２７ This is an epoxy group-containing group or a hydrocarbon group which may have substituents.

[0079] In the above formula (anv2), R ａ２４ This is a hydrocarbon group which may have substituents. Examples of hydrocarbon groups which may have substituents include linear or branched alkyl groups or cyclic hydrocarbon groups. The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specifically, examples include methyl groups, ethyl groups, n-propyl groups, n-butyl groups, n-pentyl groups, etc. Among these, methyl groups, ethyl groups, or n-butyl groups are preferred, and methyl groups or ethyl groups are more preferred.

[0080] The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5. Specifically, examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, etc., with isopropyl group being preferred.

[0081] R ａ２４When the group is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. As a monocyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. As a polycyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferred, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0082] R ａ２４ When the cyclic hydrocarbon group becomes an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. ａ２４Specific examples of aromatic hydrocarbon groups in this context include: a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); a group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0083] In the above formulas (anv2) and (anv3), R ａ２５ ~R ａ２６ , R ａ２８ ~R ａ３０ Each of these is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. The alkyl group having 1 to 5 carbon atoms and the halogen atom are each R ａ２２ , R ａ２３ It is similar to that.

[0084] In the above formula (anv3), R ａ２７ R is an epoxy group-containing group or a hydrocarbon group which may have substituents. ａ２７ The epoxy group-containing group is R in formula (anv0). ＥＰ It is similar to R. ａ２７ The hydrocarbon group which may have substituents is R in formula (anv2). ａ２４ It is similar to that.

[0085] The following are specific examples of the constituent units represented by the above formulas (anv2) to (anv3).

[0086]

[0087] If component (A2) has other constituent units in addition to constituent unit (anv1), the proportion of each constituent unit in component (A2) is not particularly limited, but the total amount of constituent units having epoxy groups is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and even more preferably 30 to 70 mol% relative to the total amount of all constituent units of component (A2).

[0088] (A2) Examples of commercially available components include, for example, novolac-type epoxy resins such as jER-152, jER-154, jER-157S70, jER-157S65 (all manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695, EPICLON Examples include HP5000 (manufactured by DIC Corporation) and EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.).

[0089] (A2) Component may be used alone or in combination of two or more. In the photosensitive adhesive composition of this embodiment, the content of component (A2) is preferably 25% by mass or more, more preferably 40% by mass or more, and may be 50% by mass or more, 75% by mass or more, 90% by mass or more, or 100% by mass, based on 100% by mass of the total amount of component (A).

[0090] When using components (A1) and (A2) in combination, the ratio of components (A1) to (A2), expressed as a mass ratio of component (A2) / component (A1), is preferably 1 / 9 to 7 / 3, more preferably 2 / 8 to 6 / 4, and even more preferably 3 / 7 to 5 / 5. If such a mass ratio falls within the above preferred range, resolution can be more easily improved during pattern formation. Chemical resistance can also be improved.

[0091] <<Aliphatic epoxy resin>> As an aliphatic epoxy resin, for example, a compound represented by the following general formula (ta1) (hereinafter this compound is also referred to as "component (A3)") is preferred.

[0092] [In the formula, R ＥＰ This is an epoxy group-containing group. Multiple R ＥＰ They may be identical or different from one another.

[0093] In the above formula (ta1), R ＥＰ is an epoxy group containing R in the above formula (anv0). ＥＰ It is similar to that.

[0094] (A3) Examples of commercially available products that can be used as components include the TEPIC series (manufactured by Nissan Chemical Corporation), such as TEPIC, TEPIC-VL, TEPIC-PAS, TEPIC-G, TEPIC-S, TEPIC-SP, TEPIC-SS, TEPIC-HP, TEPIC-L, TEPIC-FL, and TEPIC-UC; and MA-DGIC, DA-MGIC, and TOIC (manufactured by Shikoku Chemicals, Inc.). (A3) One component may be used alone, or two or more may be used in combination.

[0095] Furthermore, aliphatic epoxy resins also include compounds containing a substructure represented by the following general formula (m1) (hereinafter also referred to as "(m1) component").

[0096] [In the formula, n ２ [The integers are 1 to 4. * indicates a combination.]

[0097] In the above formula (m1), n ２ is an integer between 1 and 4, preferably between 1 and 3, and more preferably 2.

[0098] Component (m1) includes compounds in which multiple substructures represented by the above general formula (m1) are bonded via a divalent linking group or a single bond. Among these, compounds in which multiple substructures represented by the above general formula (m1) are bonded via a divalent linking group are preferred. The divalent linking group here is not particularly limited, but divalent hydrocarbon groups which may have substituents and divalent linking groups which contain heteroatoms are preferred. The divalent hydrocarbon groups which may have substituents and divalent linking groups which contain heteroatoms here are the same as the divalent hydrocarbon groups which may have substituents and divalent linking groups which contain heteroatoms described in the above "epoxy group-containing group", and among these, divalent linking groups which contain heteroatoms are preferred, -Y ２１ The group represented by -C(=O)-O-, -C(=O)-O-Y ２１ A group represented by - is more preferable. Y ２１ Preferably, the group is a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, even more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group.

[0099] Examples of commercially available aliphatic epoxy resins that can be used include ADEKA RESIN EP-4080S, EP-4085S, and EP-4088S (all manufactured by ADEKA Corporation); Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 8000, Celoxide 8010, EHPE-3150, EPOLEAD PB 3600, and EPOLEAD PB 4700 (all manufactured by Daicel Corporation); and Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (all manufactured by Nagase ChemteX Corporation).

[0100] In addition, the epoxy group-containing compound (A) may be any compound represented by the following chemical formula (A4-1) or the following chemical formula (A4-2), in addition to the resin described above. Examples of commercially available products that can be used as the compound represented by the following chemical formula (A4-1) include TECHMORE VG-3101L (manufactured by Printec Co., Ltd.). Examples of commercially available products that can be used as the compound represented by the following chemical formula (A4-2) include Showfree® BATG (manufactured by Showa Denko K.K.).

[0101]

[0102] Examples of epoxy group-containing compounds (A) include trimethylolpropane triglycidyl ether, glycerin triglycidyl ether; pentaerythritol tetraglycidyl ether, ditrimethylolpropane tetraglycidyl ether, diglycerin tetraglycidyl ether, erythritol tetraglycidyl ether; xylitol pentaglycidyl ether, dipentaerythritol pentaglycidyl ether, inositol pentaglycidyl ether; dipentaerythritol hexaglycidyl ether, sorbitol hexaglycidyl ether, inositol hexaglycidyl ether, and the like.

[0103] In the photosensitive adhesive composition of this embodiment, component (A) preferably contains at least one epoxy resin selected from the group consisting of bisphenol-type epoxy resin (A1) and novolac-type epoxy resin (A2). Among these, component (A) is more preferably a bisphenol-type epoxy resin (A1), and even more preferably a component containing an epoxy resin represented by the general formula (abp1).

[0104] The weight-average molecular weight of component (A) in terms of polystyrene is preferably 500 to 10000, more preferably 750 to 5000, and even more preferably 1000 to 2500. By using such a weight-average molecular weight, the strength of the formed cured film can be sufficiently increased. In addition, the chemical resistance of the photosensitive resin film pattern can be easily improved.

[0105] The content of component (A) in the photosensitive adhesive composition of this embodiment may be adjusted according to the thickness of the photosensitive resin film to be formed. In the photosensitive adhesive composition of this embodiment, the content of component (A) is preferably 40 to 99% by mass, more preferably 50 to 95% by mass, and even more preferably 60 to 90% by mass, based on the total solid content (100% by mass) of the photosensitive adhesive composition.

[0106] In the photosensitive adhesive composition of this embodiment, the mixing ratio of the acrylic resin (AC) and the epoxy group-containing compound (A) is preferably, as a mass ratio, (A) component / (AC) component = 60 / 40 to 95 / 5, more preferably 65 / 35 to 90 / 10, and even more preferably 70 / 30 to 90 / 10. If such a mass ratio is above the lower limit of the preferred range described above, the resolution in pattern formation tends to improve. Also, the strength of the formed cured film is sufficiently increased. On the other hand, if it is below the upper limit of the preferred range described above, the adhesion to the object and the adhesion between the transparent substrate and other substrates tend to improve when the cured film is formed.

[0107] <Photocationic Polymerization Initiator> The photocationic polymerization initiator contained in the photosensitive adhesive composition of this embodiment (hereinafter also referred to as "component (B)") is a compound that generates cations when irradiated with active energy rays such as ultraviolet light, far ultraviolet light, excimer laser light such as KrF and ArF, X-rays, electron beams, etc., and these cations can act as polymerization initiators. Examples of this component (B) include the compound represented by the following general formula (B1-3) (hereinafter referred to as "component (B13)"), the compound represented by the following general formula (B1-2) (hereinafter referred to as "component (B12)"), the compound represented by the following general formula (B1-1) (hereinafter referred to as "component (B11)").

[0108] ≪Component (B13)≫ Component (B13) is a compound represented by the following general formula (B1-3).

[0109] [In the formula, R ｂ０６ ~R ｂ０９ Each is independently an aryl group which may have substituents, or a fluorine atom. q is an integer of 1 or more, where Qｑ＋ This is a q-valent organic cation.

[0110] - In the anion part of formula (B1-3), R ｂ０６ ~R ｂ０９ The aryl group in is preferably 5 to 30 carbon atoms, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specifically, examples include naphthyl, phenyl, and anthracenyl groups, with the phenyl group being preferred due to its availability. ｂ０６ ~R ｂ０９ The aryl group in formula (B1-3) may have substituents. These substituents are not particularly limited, but are preferably halogen atoms, hydroxyl groups, alkyl groups (linear or branched alkyl groups are preferred, and the number of carbon atoms is preferably 1 to 5), halogenated alkyl groups, more preferably halogen atoms or halogenated alkyl groups having 1 to 5 carbon atoms, and particularly preferably fluorine atoms or fluorinated alkyl groups having 1 to 5 carbon atoms. The presence of a fluorine atom in the aryl group is preferable because it increases the polarity of the anionic moiety. Among these, R in formula (B1-3) is particularly preferred. ｂ０６ ~R ｂ０９ As for the groups, fluorinated phenyl groups are preferred, and perfluorophenyl groups are particularly preferred.

[0111] A preferred specific example of the anionic moiety of the compound represented by formula (B1-3) is tetrakis(pentafluorophenyl)gallate ([Ga(C ６ F ５ ) ４ ] － ); Tetrakis[(trifluoromethyl)phenyl]gallate([Ga(C) ６ H ４ CF ３ ) ４ ] － ); difluorobis(pentafluorophenyl) gallate ([(C ６ F ５ ) ２ GaF ２ ] － ); Tetrakis(difluorophenyl) gallate ([Ga(C ６ H ３ F ２ ) ４] － Examples include tetrakis(pentafluorophenyl) gallate ([Ga(C) ６ F ５ ) ４ ] － ) is particularly preferable.

[0112] ≪Component (B12)≫ Component (B12) is a compound represented by the following general formula (B1-2).

[0113] [In the formula, R ｂ０５ R is a fluorinated alkyl group which may have substituents, or a fluorine atom. ｂ０５ They may be the same or different from each other. q is an integer greater than or equal to 1, and Q ｑ＋ This is a q-valent organic cation.

[0114] - In the anion part of formula (B1-2), R ｂ０５ R is a fluorinated alkyl group which may have substituents, or a fluorine atom. ｂ０５ They may be identical or different from one another. ｂ０５ The fluorinated alkyl group in is preferably having 1 to 10 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 5 carbon atoms. Specifically, examples include alkyl groups having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are substituted with fluorine atoms. Among these, R ｂ０５ Preferably, the element is 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 even more preferably, a fluorine atom, a trifluoromethyl group, or a pentafluoroethyl group.

[0115] A preferred specific example of the anionic portion of the compound represented by formula (B1-2) is (CF ３ CF ２ ) ２ PF ４ － (CF ３ CF ２ ) ３ PF ３ － , ((CF ３ ) ２ CF)２ PF ４ － , ((CF ３ ) ２ CF) ３ PF ３ － (CF ３ CF ２ CF ２ ) ２ PF ４ － (CF ３ CF ２ CF ２ ) ３ PF ３ － , ((CF ３ ) ２ CFCF ２ ) ２ PF ４ － , ((CF ３ ) ２ CFCF ２ ) ３ PF ３ － (CF ３ CF ２ CF ２ CF ２ ) ２ PF ４ － and (CF ３ CF ２ CF ２ CF ２ ) ３ PF ３ － Examples include anions represented by (CF ３ CF ２ ) ３ PF ３ － It is preferable.

[0116] ≪Component (B11)≫ Component (B11) is a compound represented by the following general formula (B1-1).

[0117] [In the formula, R ｂ０１ ~R ｂ０４ Each is independently an aryl group which may have substituents, or a fluorine atom. q is an integer of 1 or more, where Q ｑ＋This is a q-valent organic cation.

[0118] - In the anion part of formula (B1-1), R ｂ０１ ~R ｂ０４ Each of these is independently an aryl group which may have substituents, or a fluorine atom. ｂ０１ ~R ｂ０４ The explanation of the aryl group in the above formula (B1-3) is as follows: ｂ０６ ~R ｂ０９ It is similar to the above. In particular, R in equation (B1-1) ｂ０１ ~R ｂ０４ As for the groups, fluorinated phenyl groups are preferred, and perfluorophenyl groups are particularly preferred.

[0119] A preferred specific example of the anionic moiety of the compound represented by formula (B1-1) is tetrakis(pentafluorophenyl)borate ([B(C ６ F ５ ) ４ ] － ); tetrakis[(trifluoromethyl)phenyl]borate([B(C ６ H ４ CF ３ ) ４ ] － ); difluorobis(pentafluorophenyl)borate ([(C ６ F ５ ) ２ BF ２ ] － ); tetrakis(difluorophenyl) borate ([B(C ６ H ３ F ２ ) ４ ] － Examples include ) and others. Among them, tetrakis(pentafluorophenyl) borate ([B(C ６ F ５ ) ４ ] － ) is particularly preferable.

[0120] - In the cation portion of formulas (B1-3), (B1-2), and (B1-1), Q ｑ＋Sulfonium cations and iodonium cations are preferred, and organic cations represented by the following general formulas (ca-1) to (ca-5) are particularly preferred.

[0121] [In the formula, R ２０１ ~R ２０７ , and R ２１１ ~R ２１２ Each of these independently represents an optionally substituted aryl group, heteroaryl group, alkyl group, or alkenyl group. ２０１ ~R ２０３ , R ２０６ ~R ２０７ , R ２１１ ~R ２１２ These atoms may bond to each other to form a ring with the sulfur atom in the formula. ２０８ ~R ２０９ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ２１０ This may be an aryl group having a substituent, an alkyl group having a substituent, an alkenyl group having a substituent, or an -SO group having a substituent. ２ - Contains a cyclic group. L ２０１ This represents -C(=O)- or -C(=O)-O-. ２０１ Each of these independently represents an arylene group, an alkylene group, or an alkenylene group. x is either 1 or 2. W ２０１ This represents a (x+1) valence linking group.

[0122] R ２０１ ~R ２０７ , and R ２１１ ~R ２１２ Examples of aryl groups in this compound include unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. ２０１ ~R ２０７ , and R ２１１ ~R ２１２Examples of heteroaryl groups in this context include those in which some of the carbon atoms constituting the aryl group are substituted with heteroatoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, etc. Examples of such heteroaryl groups include a group obtained by removing one hydrogen atom from 9H-thioxanthene; and examples of substituted heteroaryl groups include a group obtained by removing one hydrogen atom from 9H-thioxanthene-9-one. ２０１ ~R ２０７ , and R ２１１ ~R ２１２ The alkyl group in is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. ２０１ ~R ２０７ , and R ２１１ ~R ２１２ The alkenyl group in is preferably one with 2 to 10 carbon atoms. ２０１ ~R ２０７ , and R ２１０ ~R ２１２ Examples of substituents that may be present include alkyl groups, halogen atoms, alkyl halides, carbonyl groups, cyano groups, amino groups, oxo groups (=O), aryl groups, and groups represented by the following formulas (ca-r-1) to (ca-r-10).

[0123] [In the formula, R' ２０１ Each of these is independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group.

[0124] In the above equations (ca-r-1) to (ca-r-10), R' ２０１ Each of these is independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group.

[0125] A cyclic group which may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, which 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. The aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferred to be saturated.

[0126] R' ２０１ The aromatic hydrocarbon group in R' is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in substituents. ２０１ Specifically, examples of aromatic rings in aromatic hydrocarbon groups include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms, or rings in which some of the hydrogen atoms constituting these aromatic rings or aromatic heterocycles are substituted with oxo groups, etc. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc. R' ２０１ Specific examples of aromatic hydrocarbon groups in this context include groups obtained by removing one hydrogen atom from the aromatic ring (aryl groups: for example, phenyl groups, naphthyl groups, anthracenyl groups, etc.), groups in which one of the hydrogen atoms of the aromatic ring is substituted with an alkylene group (for example, arylalkyl groups such as benzyl groups, phenethyl groups, 1-naphthylmethyl groups, 2-naphthylmethyl groups, 1-naphthylethyl groups, 2-naphthylethyl groups, etc.), groups obtained by removing one hydrogen atom from a ring in which some of the hydrogen atoms constituting the aromatic ring are substituted with oxo groups, etc. (for example, anthraquinones, etc.), and groups obtained by removing one hydrogen atom from an aromatic heterocycle (for example, 9H-thioxanthene, 9H-thioxanthene-9-one, etc.). The number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0127] R' ２０１ The cyclic aliphatic hydrocarbon group in this context refers to an aliphatic hydrocarbon group that contains a ring in its structure. Examples of aliphatic hydrocarbon groups containing a ring in their structure include alicyclic hydrocarbon groups (groups from which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched 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. A preferred monocyclic alicyclic hydrocarbon group is a group from which one or more hydrogen atoms have been removed from a monocycloalkane. The preferred monocycloalkane has 3 to 6 carbon atoms, and specifically includes cyclopentane and cyclohexane. A preferred polycyclic alicyclic hydrocarbon group is a group from which one or more hydrogen atoms have been removed from a polycycloalkane, and the preferred polycycloalkane has 7 to 30 carbon atoms. Among these, polycycloalkanes having a cross-linked ring polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane are more preferred; polycycloalkanes having a fused ring polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferred.

[0128] Among them, R' ２０１ The cyclic aliphatic hydrocarbon group in is preferably a monocycloalkane or polycycloalkane from which one or more hydrogen atoms have been removed, more preferably a polycycloalkane from which one hydrogen atom has been removed, with adamantyl and norbornyl groups being particularly preferred, and the adamantyl group being the most preferred.

[0129] The linear or branched aliphatic hydrocarbon group, which may be bonded to the alicyclic hydrocarbon group, preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. A linear alkylene group is preferred as the linear aliphatic hydrocarbon group, specifically a methylene group [-CH]. ２ -], ethylene group [- (CH ２ )２ -], trimethylene group [-(CH ２ ) ３ -], tetramethylene group [-(CH ２ ) ４ -], pentamethylene group [-(CH ２ ) ５ Examples include -CH(CH ３ )-,-CH(CH ２ CH ３ )-,-C(CH ３ ) ２ -, -C(CH ３ ) (CH ２ CH ３ )-,-C(CH ３ ) (CH ２ CH ２ CH ３ )-,-C(CH ２ CH ３ ) ２ - Alkyl methylene groups such as -CH(CH ３ )CH ２ -, -CH(CH ３ )CH(CH ３ )-,-C(CH ３ ) ２ CH ２ -, -CH(CH ２ CH ３ )CH ２ -, -C(CH ２ CH ３ ) ２ -CH ２ - Alkyl ethylene groups such as -CH(CH ３ )CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ - Alkyl trimethylene groups such as -CH(CH ３ )CH ２ CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ CH ２Examples include alkylalkylene groups such as alkyltetramethylene groups. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0130] A chain-like alkyl group which may have substituents: R' ２０１ The linear alkyl group may be linear or branched. Linear alkyl groups preferably have 1 to 20 carbon atoms, more preferably 1 to 15, and most preferably 1 to 10. Specifically, examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, and docosyl groups. Branched alkyl groups preferably have 3 to 20 carbon atoms, more preferably 3 to 15, and most preferably 3 to 10. Specifically, examples include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group.

[0131] A chain-like alkenyl group which may have substituents: R' ２０１ The linear alkenyl group may be linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 3. Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butynyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups. Among the linear alkenyl groups listed above, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0132] R' ２０１ Examples of substituents in the cyclic group, linear alkyl group, or alkenyl group include alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, oxo groups, and the above R' ２０１ Examples include cyclic groups, alkylcarbonyl groups, and thienylcarbonyl groups.

[0133] Among them, R' ２０１ The preferably substituted cyclic group and the preferably substituted linear alkyl group are both cyclic and linear alkyl groups.

[0134] R ２０１ ~R ２０３ , R ２０６ ~R ２０７ , R ２１１ ~R ２１２ When these atoms bond to each other and form a ring with the sulfur atom in the formula, they can be heteroatoms such as sulfur, oxygen, and nitrogen atoms, or carbonyl groups, -SO-, -SO ２ -, -SO ３ -, -COO-, -CONH- or -N(R Ｎ )-(the R Ｎ is an alkyl group having 1 to 5 carbon atoms. ) may be bonded via functional groups such as ). The formed ring is preferably a 3 to 10-membered ring, and particularly preferably a 5 to 7-membered ring, including the sulfur atom in its ring skeleton. Specific examples of the formed ring include, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthlene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthlene ring, a phenoxatiyine ring, a tetrahydrothiophenium ring, a tetrahydrothiopyranium ring, and the like.

[0135] In the above formula (ca-3), R ２０８ ~R ２０９ Each of these 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. If an alkyl group is present, it may bond to each other to form a ring.

[0136] In the above formula (ca-3), R２１０ This may be an aryl group having a substituent, an alkyl group having a substituent, an alkenyl group having a substituent, or an -SO group having a substituent. ２ - Contains a cyclic group. R ２１０ Examples of aryl groups in this compound include unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. ２１０ The alkyl group in is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. ２１０ The alkenyl group in this compound preferably has 2 to 10 carbon atoms.

[0137] In the above equations (ca-4) and (ca-5), Y ２０１ These independently represent an arylene group, an alkylene group, or an alkenylene group. ２０１ The arylene group in this case is R' ２０１ An example of an aromatic hydrocarbon group in this context is the aryl group exemplified above, with one hydrogen atom removed. ２０１ In this case, the alkylene group and alkenylene group are R' ２０１ Examples of the chain-like alkyl groups and chain-like alkenyl groups mentioned above include groups obtained by removing one hydrogen atom from the exemplified groups.

[0138] In the above equations (ca-4) and (ca-5), x is either 1 or 2. ２０１ This is a (x+1) valence, i.e., a divalent or trivalent linking group. ２０１ In this, a divalent linking group is preferably a divalent hydrocarbon group which may have substituents. ２０１ The divalent linking group in may be linear, branched, or cyclic, but cyclic is preferred. Among these, a group in which two carbonyl groups are combined at both ends of an arylene group, or a group consisting only of an arylene group, is preferred. Examples of arylene groups include phenylene groups and naphthylene groups, with phenylene groups being particularly preferred. ２０１ The trivalent linking group in is the aforementioned W ２０１Examples include a group obtained by removing one hydrogen atom from a divalent linking group, and a group in which another divalent linking group is bonded to the aforementioned divalent linking group. ２０１ In this compound, a trivalent linking group is preferably a group in which two carbonyl groups are bonded to an arylene group.

[0139] Specific examples of suitable cations represented by the above formula (ca-1) include the cations represented by the following formulas (ca-1-1) to (ca-1-24).

[0140]

[0141] [In the formula, R” ２０１ is a hydrogen atom or a substituent. The substituent is R. ２０１ ~R ２０７ and R ２１０ ~R ２１２ These are the same as those listed as substituents that may be present.

[0142] Furthermore, 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.

[0143]

[0144] [In the formula, R' ２１１ R is an alkyl group. ｈａｌ This is a hydrogen atom or a halogen atom.

[0145] Furthermore, as the cation represented by the formula (ca-1), the cations represented by the following chemical formulas (ca-1-36) to (ca-1-48) are also preferred.

[0146]

[0147] Furthermore, as the cation represented by the formula (ca-1), cations represented by the following chemical formulas (ca-1-49) to (ca-1-56), each having a benzoylphenyl group, are also preferred.

[0148]

[0149] Specific examples of suitable cations represented by the formula (ca-2) include diphenyliodonium cation and bis(4-tert-butylphenyl)iodonium cation.

[0150] Specific examples of suitable cations represented by the above formula (ca-3) include the cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0151]

[0152] Specific examples of suitable cations represented by the above formula (ca-4) include the cations represented by the following formulas (ca-4-1) to (ca-4-2).

[0153]

[0154] Furthermore, 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.

[0155] [In the formula, R' ２１２ R' is an alkyl group or a hydrogen atom. ２１１ It is an alkyl group.

[0156] Among the above, the cation part [(Q ｑ＋ ) １／ｑ The cation represented by the general formula (ca-1) is preferred, the cations represented by formulas (ca-1-1) to (ca-1-56) are more preferred, and the cations represented by formulas (ca-1-25) to (ca-1-56) are even more preferred.

[0157] Furthermore, as component (B), for example, a compound represented by the following general formula (I3-1) (component (I3-1)) or a compound represented by the following general formula (I3-2) (component (I3-2)) may be used.

[0158] [In the formula, R ｂ１１ ~R ｂ１２is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom. m is an integer of 1 or more, and M ｍ＋ is, independently of each other, an m-valent organic cation. ]

[0159] {(I3-1) component} ・In the anion part formula (I3-1), R ｂ１２ is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom, and among the cyclic group, chain alkyl group, and chain alkenyl group in the description of R' ２０１ above, those having no substituent or those having a substituent other than a halogen atom are exemplified. R ｂ１２ is preferably a chain alkyl group which may have a substituent other than a halogen atom, or an aliphatic cyclic group which may have a substituent other than a halogen atom. As the chain alkyl group, it is preferably having 1 to 10 carbon atoms, more preferably 3 to 10 carbon atoms. As the aliphatic cyclic group, a group obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. (which may have a substituent other than a halogen atom); a group obtained by removing one or more hydrogen atoms from camphor, etc. is more preferable. The hydrocarbon group of R ｂ１２ may have a substituent other than a halogen atom. Here, "may have a substituent other than a halogen atom" not only excludes the case of having a substituent consisting only of halogen atoms, but also excludes the case of having a substituent containing even one halogen atom (for example, when the substituent is a fluorinated alkyl group, etc.).

[0160] Specific preferred examples of the anion part of the (I3-1) component are shown below.

[0161]

[0162] ・In the cation part formula (I3-1), M ｍ＋M is an organic cation with an m-valence. ｍ＋ Suitable organic cations include those similar to the cations represented by the general formulas (ca-1) to (ca-5) above, and among these, the cation represented by the general formula (ca-1) above is more preferred. Among these, R in the general formula (ca-1) above is preferred. ２０１ , R ２０２ , R ２０３ Sulfonium cations in which at least one of the groups is an organic group having 16 or more carbon atoms (aryl group, heteroaryl group, alkyl group, or alkenyl group) which may have substituents are particularly preferred because they improve resolution and roughness characteristics. The substituents that the organic group may have are the same as above, and include alkyl groups, halogen atoms, alkyl halides, carbonyl groups, cyano groups, amino groups, oxo groups (=O), aryl groups, and groups represented by the above formulas (ca-r-1) to (ca-r-10). The number of carbon atoms in the above organic group (aryl group, heteroaryl group, alkyl group, or alkenyl group) is preferably 16 to 25, more preferably 16 to 20, and particularly preferably 16 to 18. ｍ＋ Suitable organic cations include, for example, the cations represented by the above formulas (ca-1-25), (ca-1-26), (ca-1-28) to (ca-1-36), (ca-1-38), (ca-1-46), and (ca-1-47), respectively, and among these, the cation represented by the above formula (ca-1-29) is particularly preferred.

[0163] {(I3-2) component} - In the anionic component of formula (I3-2), R ｂ１１ R' is a cyclic group which may have substituents other than halogen atoms, a linear alkyl group which may have substituents other than halogen atoms, or a linear alkenyl group which may have substituents other than halogen atoms, as described above. ２０１ Examples of cyclic groups, linear alkyl groups, and linear alkenyl groups mentioned in the description include those without substituents and those with substituents other than halogen atoms.

[0164] Among these, R ｂ１１Preferred substituents are aromatic hydrocarbon groups which may have substituents other than halogen atoms, aliphatic cyclic groups which may have substituents other than halogen atoms, or linear alkyl groups which may have substituents other than halogen atoms. Examples of substituents these groups may have include hydroxyl groups, oxo groups, alkyl groups, aryl groups, lactone-containing cyclic groups, ether bonds, ester bonds, or combinations thereof. When ether bonds or ester bonds are included as substituents, they may be mediated via alkylene groups, and preferred substituents in this case are linking groups represented by the following general formulas (y-al-1) to (y-al-7). Note that in the following general formulas (y-al-1) to (y-al-7), R in formula (I3-2) above... ｂ１１ The combination with this is V' in the following general formulas (y-al-1) to (y-al-7). １０１ That is the case.

[0165] [In the formula, V' １０１ V' is a single bond or an alkylene group with 1 to 5 carbon atoms. １０２ This is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.

[0166] V' １０２ The divalent saturated hydrocarbon group in is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms.

[0167] V' １０１ and V' １０２ The alkylene group in V' may be a linear alkylene group or a branched alkylene group, but a linear alkylene group is preferred. １０１ and V' １０２ Specifically, the alkylene group in this case is the methylene group [-CH ２ -come; -CH(CH ３ )-,-CH(CH ２ CH ３ )-,-C(CH ３ ) ２ -, -C(CH ３ ) (CH ２ CH３ )-,-C(CH ３ ) (CH ２ CH ２ CH ３ )-,-C(CH ２ CH ３ ) ２ - Alkylmethylene groups such as; ethylene groups [-CH ２ CH ２ -come; -CH(CH ３ )CH ２ -, -CH(CH ３ )CH(CH ３ )-,-C(CH ３ ) ２ CH ２ -, -CH(CH ２ CH ３ )CH ２ - Alkylethylene groups such as; trimethylene group (n-propylene group) [-CH ２ CH ２ CH ２ -come; -CH(CH ３ )CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ - Alkyl trimethylene groups such as; tetramethylene groups [-CH ２ CH ２ CH ２ CH ２ -come; -CH(CH ３ )CH ２ CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ CH ２ - Alkyltetramethylene groups such as; pentamethylene groups [-CH ２ CH ２ CH ２ CH ２ CH ２ -] are some examples. Also, V' １０１ or V' １０２ Some of the methylene groups in the alkylene group may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is R' ２０１A divalent group is preferred, which is obtained by removing one more hydrogen atom from a cyclic aliphatic hydrocarbon group (monocyclic alicyclic hydrocarbon group, polycyclic alicyclic hydrocarbon group), and a cyclohexylene group, a 1,5-adamantilene group, or a 2,6-adamantilene group is more preferred.

[0168] The aromatic hydrocarbon group is more preferably a phenyl group or a naphthyl group. The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. The linear alkyl group is preferably having 1 to 10 carbon atoms, and specifically includes linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; and branched alkyl groups such as 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl groups.

[0169] R ｂ１１ As such, a cyclic group which may have substituents other than halogen atoms is preferred. The following are preferred specific examples of the anionic portion of component (I3-2).

[0170]

[0171] - In the cation component of formula (I3-2), M ｍ＋ is an m-valent organic cation, and M in formula (I3-1) above. ｍ＋ It is similar to that.

[0172] The following are specific examples of suitable (B) components.

[0173]

[0174] In the photosensitive adhesive composition of this embodiment, component (B) may be used alone or in combination of two or more. Component (B) preferably includes at least one selected from the group consisting of components (B13), (B12), and (B11), and more preferably includes component (B13). Alternatively, from the viewpoint of improving resolution in pattern formation, component (B) preferably includes a combination of at least one selected from the group consisting of components (B13), (B12), and (B11), and at least one selected from the group consisting of components (I3-1) and (I3-2); more preferably includes a combination of at least one selected from the group consisting of components (B13), (B12), and (B11), and component (I3-1).

[0175] In the photosensitive adhesive composition of this embodiment, the content of component (B) is preferably 0.1 parts by mass to 5 parts by mass, more preferably 0.2 to 4 parts by mass, and even more preferably 0.5 to 2 parts by mass, based on the total content (100 parts by mass) of the acrylic resin and the epoxy group-containing compound. If the content of component (B) is above the lower limit of the preferred range, sufficient sensitivity is obtained, and the lithography characteristics of the resist pattern are further improved. In addition, the strength of the resin-cured film is further increased. On the other hand, if it is below the upper limit of the preferred range, the sensitivity is appropriately controlled, and it becomes easier to obtain a resist pattern with a good shape.

[0176] In the photosensitive adhesive composition of this embodiment, photocatalytic polymerization initiators other than the above-mentioned components (B13), (B12), and (B11), as well as components (I3-1) and (I3-2), may also be used.

[0177] <Other Components> In addition to the acrylic resin, epoxy group-containing compound (excluding those corresponding to the acrylic resin) and photocationic polymerization initiator described above, the photosensitive adhesive composition of this embodiment may contain other components (optional components) as needed. The photosensitive adhesive composition of this embodiment may optionally contain miscible additives, such as metal oxides (M), sensitizer components, solvents, additional resins to improve film performance, dissolution inhibitors, basic compounds, plasticizers, stabilizers, colorants, and anti-halation agents.

[0178] ≪Metal Oxide (M)≫ In addition to the acrylic resin, epoxy group-containing compound (excluding those corresponding to the acrylic resin) and photocationic polymerization initiator, the photosensitive adhesive composition of this embodiment may further contain a metal oxide (M) (hereinafter also referred to as "(M) component"), as this makes it easier to obtain a cured film with increased strength. By including the (M) component, it is possible to form a high-resolution pattern with a good shape. Examples of the (M) component include metal oxides such as silicon (metallic silicon), titanium, zirconium, and hafnium. Among these, silicon oxide is preferred, and among these, silica is particularly preferred. The shape of the (M) component is preferably particulate. The particulate (M) component preferably consists of a group of particles with a volume average particle diameter of 5 to 40 nm, more preferably consists of a group of particles with a volume average particle diameter of 5 to 30 nm, and even more preferably consists of a group of particles with a volume average particle diameter of 10 to 20 nm.

[0179] <<Sensitizer Component>> The 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 other substances. Specifically, known photosensitizers such as benzophenone-based photosensitizers such as benzophenone and p,p'-tetramethyldiaminobenzophenone, carbazole-based photosensitizers, acetophene-based photosensitizers, naphthalene-based photosensitizers such as 1,5-dihydroxynaphthalene, phenol-based photosensitizers, anthracene-based photosensitizers such as 9-ethoxyanthracene, biacetyl, eosin, rose bengal, pyrene, phenothiazine, and anthrone can be used as sensitizer components.

[0180] ≪Solvent≫ The photosensitive adhesive composition of this embodiment may further contain a solvent (hereinafter sometimes referred to as "component (S)"). Examples of component (S) include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds having ester bonds such as 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether of the polyhydric alcohols or compounds having ester bonds; and Examples include derivatives of polyhydric alcohols such as compounds having ether bonds, such as nophenyl ether [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, phenethole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene, and dimethyl sulfoxide (DMSO).

[0181] Component (S) may be used alone or as a mixture of two or more solvents. The amount of component (S) used when included is not particularly limited and is set appropriately according to the film thickness, at a concentration that allows the photosensitive adhesive composition to be applied to a support or the like without dripping. For example, component (S) can be used so that the solid content concentration is 50% by mass or more, or so that the solid content concentration is 60% by mass or more. Furthermore, an embodiment that substantially does not contain component (S) (i.e., an embodiment in which the solid content concentration is 100% by mass) can also be adopted.

[0182] The photosensitive adhesive composition of this embodiment may have a viscosity at 23°C of 10 to 5000 mPa·s, 30 to 3000 mPa·s, or 50 to 2000 mPa·s.

[0183] The photosensitive adhesive composition of this embodiment described above contains an acrylic resin (component (AC)), an epoxy group-containing compound excluding component (component (A)), and a photocationic polymerization initiator (component (B)). Component (AC) is selected to have a constituent unit (constituent unit (ac1)) derived from an acrylic monomer containing a functional group that reacts with a carboxyl group (-COOH). This reduces the likelihood of whitening of the transparent substrate during bonding. In addition, component (AC) is selected to have a glass transition temperature of 0°C or lower. This modifies the cured film of the photosensitive adhesive composition, improving adhesion between the transparent substrate and other substrates. Furthermore, component (AC) is selected to have a weight-average molecular weight of 200,000 or more. This improves resolution during pattern formation.

[0184] Furthermore, the photosensitive adhesive composition of this embodiment enables the formation of high-resolution patterns with good shape during pattern formation, thereby improving lithography characteristics. The photosensitive adhesive composition of this embodiment is useful as a photosensitive adhesive material used in the manufacture of electronic components (e.g., MEMS, bio-use, etc.) that require various properties such as compatibility with adhesiveness and chemical resistance.

[0185] (Photosensitive Adhesive Dry Film) One embodiment of the photosensitive adhesive dry film is one in which a photosensitive adhesive composition layer (photosensitive resin film) and a cover film are laminated on a base film in that order. The photosensitive adhesive composition layer (photosensitive resin film) here is formed using the photosensitive adhesive composition of the embodiment described above.

[0186] A known base film can be used, such as a thermoplastic resin film. Examples of thermoplastic resins include polyesters such as polyethylene terephthalate. The thickness of the base film is preferably 2 to 150 μm.

[0187] The thickness of the photosensitive adhesive composition layer (photosensitive resin film) is preferably 100 μm or less, and more preferably 5 to 50 μm.

[0188] A known cover film can be used, such as a thermoplastic resin film. Examples of thermoplastic resins include polyethylene film and polypropylene film. The cover film is preferably one in which the adhesive strength to the photosensitive adhesive composition layer is less than the adhesive strength between the base film and the 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.

[0189] The photosensitive adhesive dry film of this embodiment can be produced, for example, by applying the photosensitive adhesive composition of the above-described embodiment onto a base film, drying it to form a photosensitive adhesive composition layer (photosensitive resin film), and then laminating a cover film on the photosensitive adhesive composition layer (photosensitive resin film). The application of the photosensitive adhesive composition onto the base film may be carried out by an appropriate method using a blade coater, a lip coater, a comma coater, a film coater, or the like. The photosensitive adhesive composition layer (photosensitive resin film) provided in the photosensitive adhesive dry film of this embodiment is typically composed of a B-stage (semi-cured state) material. The photosensitive adhesive dry film of this embodiment is provided, for example, as a roll body wound around a winding core.

[0190] (Pattern formation method) One embodiment of the pattern formation method is a pattern formation method having a step of forming a photosensitive resin film on a support using the 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 formation method of this embodiment can be carried out, for example, as follows.

[0191] [Film formation step] First, the photosensitive adhesive composition of the above-described embodiment is applied onto a support by a known method such as a spin coating method, a roll coating method, or a screen printing method, and a baking (post-apply bake (PAB)) treatment is performed at a temperature condition of, for example, 50 to 150°C for 2 to 60 minutes to form a photosensitive resin film. Alternatively, using the photosensitive adhesive dry film of the above-described embodiment, a photosensitive adhesive composition layer (photosensitive resin film) is formed on a support.

[0192] The support material is not particularly limited and conventionally known materials can be used, such as substrates for electronic components, substrates with predetermined wiring patterns formed thereon, or resin films suitable for forming microchannels. More specifically, silicon, silicon nitride, titanium, tantalum, lithium tantalate (LiTaO) ３ ), niobium, lithium niobate (LiNbO ３ Examples of substrates include metal substrates such as palladium, titanium tungsten, copper, chromium, iron, and aluminum, as well as glass substrates. For wiring patterns, materials such as copper, aluminum, nickel, and gold can be used. Examples of resin film materials include acrylic resin, polypropylene, polycarbonate resin, cycloolefin resin, polystyrene resin, polyester resin, urethane resin, vinyl chloride resin, silicone resin, and fluororesin.

[0193] The thickness of the photosensitive resin film formed by the photosensitive adhesive composition or the photosensitive adhesive dry film is not particularly limited, but is preferably about 10 to 100 μm. The photosensitive adhesive composition or the photosensitive adhesive dry film of the above-described embodiment can also obtain good properties even when a thick film is formed.

[0194] [Exposure Process] Next, the formed photosensitive resin film is subjected to selective exposure using a known exposure apparatus, either by exposure through a mask (mask pattern) on which a predetermined pattern has been formed, or by drawing by direct irradiation with an electron beam without going through a mask pattern. Then, if necessary, a bake (post-exposure bake (PEB)) process is performed for 40 to 1200 seconds, preferably 40 to 1000 seconds, more preferably 60 to 900 seconds, at a temperature of, for example, 80 to 150°C.

[0195] The wavelength used for exposure is not particularly limited; radiation, such as ultraviolet rays with wavelengths of 300-500 nm, i-rays (wavelength 365 nm), or visible light, is selectively irradiated (exposed). Low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, etc., can be used as radiation sources. Here, radiation refers to ultraviolet rays, visible light, far-ultraviolet rays, 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., but for example, when using an ultra-high-pressure mercury lamp, it is 100-2000 mJ / cm². ２ That is the case.

[0196] The exposure method for the photosensitive resin film may be conventional exposure (dry exposure) performed in an inert gas such as air or nitrogen, or it may be liquid immersion lithography.

[0197] The photosensitive resin film after the exposure process has high transparency, and for example, the haze value when irradiated with i-line light (wavelength 365 nm) is preferably 3% or less, more preferably 1.0 to 2.5%. Thus, the photosensitive resin film formed using the photosensitive adhesive composition of the above embodiment, or the photosensitive adhesive dry film of the above embodiment, has high transparency. Therefore, when exposed during pattern formation, light transmittance is increased, and it is easy to obtain a negative type pattern with good lithography characteristics. The haze value of the photosensitive resin film after the exposure process is measured using a method in accordance with JIS K 7136 (2000).

[0198] [Development Process] Next, the photosensitive resin film after exposure is developed with a developer containing an organic solvent (organic developer). After development, a rinsing treatment is preferably performed. A bake treatment (post-bake) may be performed if necessary.

[0199] The organic solvent contained in the organic developer can be any solvent capable of dissolving acrylic resin and epoxy group-containing compounds, and can be appropriately selected from known organic solvents. Specifically, examples include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents.

[0200] 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, and methyl amyl ketone (2-heptanone). Among these, methyl amyl ketone (2-heptanone) is preferred as the ketone solvent.

[0201] Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyethyl acetate, ethoxyethyl acetate, 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, pro 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 include ethyl acid, 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, propyl-3-methoxypropionate, and the like.Among these, butyl acetate or PGMEA is preferred as the ester solvent.

[0202] Examples of nitrile solvents include acetonitrile, propionitol, valeronitrile, and butyronitrile.

[0203] Organic developers may contain known additives as needed. Examples of such additives include surfactants. While the surfactant is not particularly limited, examples include ionic and nonionic fluorine-based and / or silicone-based surfactants. Nonionic surfactants are preferred, and nonionic fluorine-based surfactants or nonionic silicone-based surfactants are more preferred. When a surfactant is added, the amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, relative to the total amount of the organic developer.

[0204] The development process can be carried out by known development methods, such as the dipping method (immersing the support in a developer solution for a certain period of time), the paddle method (building up the developer solution on the surface of the support using surface tension and leaving it still for a certain period of time), the spray method (spraying the developer solution onto the surface of the support), and the dynamic dispensing method (continuously dispensing the developer solution while scanning a developer dispensing nozzle at a constant speed onto a support that is rotating at a constant speed.

[0205] Rinsing (cleaning) using a rinsing solution can be carried out by known rinsing methods. Examples of such rinsing methods include continuously applying the rinsing solution onto a support rotating at a constant speed (rotary coating method), immersing the support in the rinsing solution for a certain period of time (dip method), and spraying the rinsing solution onto the surface of the support (spray method). It is preferable to use a rinsing solution containing an organic solvent for the rinsing process.

[0206] A negative-type pattern can be formed by the film formation process, exposure process, and development process described above.

[0207] In the pattern forming method of the embodiment described above, since the photosensitive adhesive composition or the photosensitive adhesive dry film of the embodiment described above is used, good adhesion to the support is achieved during pattern formation, high resolution and a photosensitive resin film pattern with a good shape are formed, and the lithography characteristics are excellent.

[0208] (Laminate) One embodiment of the laminate is a laminate of a cured photosensitive resin film formed using the photosensitive adhesive composition of the above embodiment or the photosensitive adhesive dry film of the above embodiment, and a support equipped with a transparent substrate. The cured photosensitive resin film is typically obtained by obtaining a support equipped with a negative pattern using the pattern forming method of the above embodiment, and then curing the negative pattern (photosensitive resin film). Examples of transparent substrates include glass substrates made of quartz, alkali-free, borosilicate, white plate, optical, soda, etc.; sapphire substrates, gallium nitride substrates, aluminum nitride substrates, silicon carbide substrates, zinc oxide substrates, zinc sulfide substrates, zinc selenide substrates, zinc telluride substrates, cadmium sulfide substrates, magnesium oxide substrates, strontium titanate substrates, glass epoxy substrates, polyimide substrates, polyester substrates, PET substrates, etc. The support equipped with a transparent substrate may consist only of a transparent substrate, or it may be a laminate of a transparent substrate and other substrates. Other substrates include the support structures exemplified in the description of the [film formation process] mentioned above.

[0209] (Method for manufacturing a laminate) One embodiment of the method for manufacturing a laminate is a manufacturing method comprising the steps of obtaining a support having a negative pattern by using the pattern forming method of the embodiment described above, and obtaining a laminate by bonding the support having the negative pattern with another support by thermocompression bonding.

[0210] After obtaining a support with a pattern using the pattern-forming method of the embodiment described above, it is preferable to cure 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 under conditions of a nitrogen atmosphere.

[0211] According to the manufacturing method of the laminate of the above-described embodiment, since the photosensitive adhesive composition of the above-described embodiment or the photosensitive adhesive dry film of the above-described embodiment is used, good adhesion between the support and other supports is achieved, and a laminate can be manufactured in which whitening of the transparent substrate in a support equipped with a transparent substrate is suppressed. The laminate manufactured by the manufacturing method of this embodiment is suitable for semiconductor devices and can also be applied to microfluidic devices.

[0212] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0213] <Production of Acrylic Resin> Using the "acrylic monomers" shown in Table 1, acrylic resins (AC)-1 to (AC)-9 were obtained by known radical polymerization.

[0214] Table 1 shows the proportion (mass%) of each constituent unit of the acrylic resin, as well as the glass transition temperature Tg (°C) and weight-average molecular weight Mw of the acrylic resin, respectively.

[0215] The glass transition temperature Tg of the acrylic resin was calculated using the following formula: 1 / (Tg+273) = {W1 / (Tg1+273)+W2 / (Tg2+273)+...} / 100 Tg: Glass transition temperature (°C) of the copolymer which is acrylic resin Tg1: Glass transition temperature (°C) of the homopolymer consisting of a repeating structure of constituent unit (1) derived from monomer (1) Tg2: Glass transition temperature (°C) of the homopolymer consisting of a repeating structure of constituent unit (2) derived from monomer (2) W1: Percentage (mass%) of constituent unit (1) constituting the acrylic resin W2: Percentage (mass%) of constituent unit (2) constituting the acrylic resin W1+W2+...=100

[0216] The glass transition temperatures of homopolymers were adopted from the values ​​disclosed on the website of KTR Corporation (Kaji Test Research) (www.kaji-tr.com), the Polymer Materials Handbook (edited by the Society of Polymer Science, Corona Publishing Co., Ltd., first edition, published February 20, 1973), the Acrylic Products Catalog of Kyoeisha Chemical Co., Ltd., and the Polymer Data Handbook Basic Edition (edited by the Society of Polymer Science, Baifukan, published January 30, 1986).

[0217] For example, the glass transition temperature Tg (°C) of acrylic resin (AC)-1 was calculated as follows. Acrylic resin (AC)-1 is a copolymer of structural units derived from 2-methoxyethyl acrylate, structural units derived from methyl methacrylate, and structural units derived from glycidyl methacrylate. If monomer (1) is 2-methoxyethyl acrylate, the glass transition temperature of the homopolymer consisting of the repeating structure of structural unit (1) is -55°C, and the proportion of structural unit (1) is 70% by mass. If monomer (2) is methyl methacrylate, the glass transition temperature of the homopolymer consisting of the repeating structure of structural unit (2) is 105°C, and the proportion of structural unit (2) is 25% by mass. If monomer (3) is glycidyl methacrylate, the glass transition temperature of the homopolymer consisting of the repeating structure of structural unit (3) is 41°C, and the proportion of structural unit (3) is 5% by mass. The glass transition temperature Tg (°C) of acrylic resin (AC)-1 is calculated from the following formula. 1 / (Tg+273) = {70 / (-55+273)+25 / (105+273)+5 / (41+273)} / 100 Tg≒-25℃

[0218] For each acrylic resin obtained, the copolymerization composition ratio of the acrylic resin (the proportion (mass%) of each constituent unit that makes up the acrylic resin) is: １３ The molecular weight was determined by 13C-NMR. The weight-average molecular weight (Mw) of the acrylic resin was determined by gel permeation chromatography (GPC) and is shown as a value equivalent to standard polystyrene.

[0219]

[0220] <Preparation of Photosensitive Adhesive Compositions> (Examples 1-20, Comparative Examples 1-4) Each component shown in Tables 2-3 was mixed and dissolved in propylene glycol monomethyl ether acetate, and the mixture was filtered using a PTFE filter (pore size 1 μm, manufactured by PALL Inc.) to prepare the photosensitive adhesive compositions for each example (solution with a solid content concentration of 60% by mass, viscosity of 2000 mPa·s at 23°C).

[0221] In Tables 2 and 3, each abbreviation has the following meaning. The numbers in brackets [ ] represent the amount of each component (parts by mass; on a solid content basis).

[0222] Acrylic resins (AC)-1 to (AC)-9: Acrylic resins (AC)-1 to (AC)-9 shown in Table 1

[0223] Epoxy group-containing compound (A)-1: A bisphenol-type epoxy resin represented by the following chemical formula (abp1-0). n = 5-6, weight-average molecular weight Mw 1500, epoxy equivalent 500 g / eq.

[0224]

[0225] (A)-2: A novolac-type epoxy resin represented by the following chemical formula (anv0-0). Weight-average molecular weight Mw2900, epoxy equivalent 213 g / eq.

[0226]

[0227] Photocationic polymerization initiators (B)-1: A photocationic polymerization initiator represented by the following chemical formula (B1-3-1). (B)-2: A photocationic polymerization initiator represented by the following chemical formula (B1-2-1). (B)-3: A photocationic polymerization initiator represented by the following chemical formula (B1-1-1). (B)-4: A photocationic polymerization initiator represented by the following chemical formula (B1-4-1).

[0228]

[0229] <Evaluation> For each example of the photosensitive adhesive composition, the adhesion, substrate whitening, and pattern resolution were evaluated using the evaluation methods described below. The results are shown in Tables 2 and 3.

[0230] [Evaluation of Adhesion] ・Measuring substrate preparation film formation process: Each photosensitive adhesive composition was applied to a 6-inch silicon substrate by spin coating, and then baked in an oven at 100°C for 10 minutes to form a photosensitive resin film with a thickness of 20 μm. Exposure process: Next, using an exposure machine (SUSS-MA8), the photosensitive resin film was exposed to an exposure dose of 100 mJ / cm² through a mask. ２ Exposure was performed. Next, the photosensitive resin film after exposure was heated on a hot plate at 90°C for 5 minutes. Development process: Next, the photosensitive resin film after exposure and heating was paddle developed at room temperature (23°C) for 120 seconds using propylene glycol monomethyl ether acetate (PGMEA) as the developer to obtain a pattern of the photosensitive resin film. Thermocompression bonding process: Next, a 6-inch silicon substrate with the photosensitive resin film pattern and a colorless, transparent 4 mm square glass die were superimposed. After this, a die bonder (TRESKY Corporation, die bonder) was used to heat-bond the photosensitive resin film pattern and the 4 mm square glass die for 1 minute under a load of 3500 g while heated to 200°C, thereby creating a measurement substrate.

[0231] Measurement of Optimal Exposure (EOP): The optimal exposure (EOP) (mJ / cm²) is determined by the above-described film formation, exposure, and development processes to form a line and space pattern of the target size (space width 50 μm, pitch 100 μm). ２ The result was calculated as "EOP (mJ / cm²)". ２ This is shown in Tables 2-3.

[0232] For the measurement substrate, the interface between the cured photosensitive resin film pattern (cured film pattern) and the 4 mm square glass die was observed using an optical microscope (OM), and the adhesion was evaluated according to the following evaluation criteria. Evaluation Criteria A: Adhesion was achieved at the entire interface (100%) between the cured film pattern and the 4 mm square glass die. B: There were voids at the interface between the cured film pattern and the substrate, but the area of ​​the voids at the interface was 10% or less, and adhesion was achieved at 90% or more of the interface area. C: The area of ​​the voids at the interface exceeded 10%.

[0233] [Evaluation of substrate whitening] The adhesive surface of the 4 mm square glass die after thermocompression bonding of the measurement substrate was observed with an optical microscope (OM), and the whitening of the substrate was evaluated according to the following evaluation criteria. Evaluation Criteria A: The adhesive surface of the 4 mm square glass die was not whitened. C: The adhesive surface of the 4 mm square glass die was whitened.

[0234] [Evaluation of Pattern Resolution] A line and space pattern was formed as a pattern on a photosensitive resin film using the film formation process, exposure process, and development process described above. During the exposure process, the maximum resolvable pattern size was observed using an optical microscope (OM) as the exposure amount was reduced, and the pattern resolution was evaluated according to the following evaluation criteria. Evaluation Criteria A: Space width of 20 μm was resolved. B+: Space width up to 25 μm was resolved. B: Space width up to 30 μm was resolved. C: Space width of 30 μm was not removed.

[0235]

[0236]

[0237] The results shown in Tables 2 and 3 confirm that the photosensitive adhesive compositions of Examples 1 to 20 to which the present invention is applied can bond a transparent substrate (4 mm square glass die) to another substrate (6 inch silicon substrate), are less likely to cause whitening of the transparent substrate during bonding, and exhibit good resolution in pattern formation.

[0238] On the other hand, the photosensitive adhesive compositions of Comparative Examples 1 to 3, which are outside the scope of the present invention, specifically the photosensitive adhesive composition of Comparative Example 1, which contains acrylic resin (AC)-7 that does not have a constituent unit derived from an acrylic monomer containing a functional group that reacts with a carboxyl group (-COOH), were poorly evaluated in terms of substrate whitening. The photosensitive adhesive composition of Comparative Example 2, which contains acrylic resin (AC)-8 having a glass transition temperature higher than 0°C, was poorly evaluated in terms of adhesion. The photosensitive adhesive composition of Comparative Example 3, which contains acrylic resin (AC)-9 having a weight-average molecular weight lower than 200,000, was poorly evaluated in terms of pattern resolution.

[0239] Although preferred embodiments of the present invention have been described above, the present invention is not limited to these embodiments. Additions, omissions, substitutions, and other modifications to the configuration are possible without departing from the spirit of the present invention. The present invention is not limited by the foregoing description and is limited only by the appended claims.

Claims

1. A photosensitive adhesive composition comprising an acrylic resin, an epoxy group-containing compound (excluding those corresponding to the acrylic resin), and a photocationic polymerization initiator, wherein the acrylic resin has structural units derived from an acrylic monomer containing a functional group that reacts with a carboxyl group (-COOH), has a glass transition temperature of 0°C or lower, and has a weight-average molecular weight of 200,000 or more.

2. The acrylic monomer comprises an epoxy group, an alcoholic hydroxyl group and an amino group (-NH ２ The photosensitive adhesive composition according to claim 1, wherein the monomer comprises at least one functional group selected from the group consisting of ).

3. The photosensitive adhesive composition according to claim 1, wherein the content of the acrylic resin is 5% by mass or more and 40% by mass or less, based on the total content (100% by mass) of the acrylic resin and the epoxy group-containing compound.

4. A photosensitive adhesive dry film prepared using the photosensitive adhesive composition described in any one of claims 1 to 3.

5. A pattern forming method comprising the steps of: forming a photosensitive resin film on a support using the photosensitive adhesive composition according to any one of claims 1 to 3; 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.

6. A pattern forming method comprising the steps of: forming a photosensitive resin film on a support using the photosensitive adhesive dry film described in claim 4; 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-type pattern.

7. A method for manufacturing a laminate, comprising the steps of: obtaining a support having a negative pattern by using the pattern forming method described in claim 5; and obtaining a laminate by bonding the support having the negative pattern and another support by thermocompression bonding.

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