Photosensitive composition, method for manufacturing laminate, cured pattern forming method, and laminate

Abstract

To provide a photosensitive composition which can form a cured pattern of a good shape by enhancing adhesion between a support and the cured pattern, and to provide a method for manufacturing a laminate, a laminate, and a cured pattern.SOLUTION: The photosensitive composition is employed which contains a polyfunctional aromatic epoxy compound and a photoacid generator. The polyfunctional aromatic epoxy compound contains a novolac type epoxy resin having a constituent unit (a01) represented by the following general formula (a0-1) and a constituent unit (a02) represented by the following general formula (a0-2). In the formulae, R01 represents a C1-5 alkyl group; n01 represents an integer of 1-4; RE0 represents an epoxy group-containing group; and R02 and R03 each independently represent a C1-5 alkyl group or a halogen atom.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] 2. Description of the Related Art Wire-wound inductors having an insulating portion made of a cured resin film and a coil pattern made of a plating layer of copper or the like are used as inductors, which are one type of passive element in electric and electronic circuits. Fig. 5 is a partial cross-sectional view showing an example of a wire-wound inductor. The wire-wound inductor 200 shown in Fig. 5 is made of a coil-shaped cured pattern 120 formed on a support 20 and a plating layer 30 that fills the space between the cured pattern 120. A wire-wound inductor is manufactured by forming a resist layer on a support, selectively exposing this resist layer through a photomask, developing it, and then curing it to form a coil-shaped cured pattern (cured resin film) that serves as the insulating part, and then plating is applied between the insulating parts.

[0003] As a technology for manufacturing a wire-wound inductor, a manufacturing method for a coil component including a first insulating layer, a coil pattern formed on the first insulating layer and wound in a spiral shape, an intralayer insulating pattern formed on the first insulating layer and arranged along the coil pattern, and a second insulating layer covering the coil pattern and the intralayer insulating pattern has been proposed (see Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2020-136466 A [Patent Document 2] JP 2020-136467 A Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, as electric and electronic components have become more multifunctional, inductors are required to be smaller and to maintain their current capacity. To meet such demands, it is necessary to make the cured pattern finer. However, conventional manufacturing methods may not be able to form a cured pattern with a good shape. For example, when forming a cured pattern in the shape of a spirally wound coil, the cured pattern may become distorted, making it impossible to form a uniform shape, or the cured pattern may peel off from the support. Pattern distortion refers to a state in which a pattern leans against an adjacent pattern.

[0006] The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide a photosensitive composition that can improve adhesion between a support and a cured pattern and form a cured pattern with a good shape, a method for producing a laminate using the photosensitive composition, a laminate, and a cured pattern formed by the laminate. [Means for solving the problem]

[0007] The present invention includes the following aspects. A first aspect of the present invention is a photosensitive composition comprising a polyfunctional aromatic epoxy compound and a photoacid generator, wherein the polyfunctional aromatic epoxy compound comprises a novolac-type epoxy resin having a structural unit (a01) represented by the following general formula (a0-1) and a structural unit (a02) represented by the following general formula (a0-2):

[0008] [ka] [In the formula, R 01 is an alkyl group having 1 to 5 carbon atoms. 01 is an integer from 1 to 4. 01 If is 2 or more, multiple R 01 may be the same or different from each other. R E0 is an epoxy group-containing group. 02 and R03 are each independently an alkyl group having 1 to 5 carbon atoms or a halogen atom. 02 and n 03 are integers from 0 to 3. 0≦n 02 +n 03 ≦3. n 02 If is 2 or more, multiple R 02 may be the same or different. 03 If is 2 or more, multiple R 03 may be the same or different.

[0009] A second aspect of the present invention is a method for producing a laminate, comprising the steps of forming a first resist layer on a support using a first photosensitive composition, and forming a second resist layer on the first resist layer using a second photosensitive composition, wherein the photosensitive composition according to the first aspect is used as the first photosensitive composition.

[0010] A third aspect of the present invention is a method for forming a cured pattern, comprising the steps of exposing a laminate produced by the laminate production method according to the second aspect, developing the exposed laminate to form a resist pattern, and curing the resist pattern to obtain a cured pattern.

[0011] A fourth aspect of the present invention is a laminate of a first resist layer and a second resist layer, wherein the first resist layer is a resist layer formed from the photosensitive composition according to the first aspect. Effect of the Invention

[0012] According to the present invention, it is possible to provide a photosensitive composition that can improve adhesion between a support and a cured pattern and form a cured pattern with a good shape, a method for producing a laminate using the photosensitive composition, a laminate, and a cured pattern formed by the laminate. [Brief description of the drawings]

[0013] [Figure 1] 1 is a cross-sectional view showing one embodiment of a laminate 10 formed on a support 20. FIG. [Diagram 2] FIG. 2 is a schematic diagram for illustrating the step (iv) of exposing the laminate 10 formed on the support 20 to light. [Diagram 3] FIG. 2 is a schematic diagram illustrating the step (v) of developing the exposed laminate 10 to form a resist pattern 110. [Figure 4] FIG. 13 is a schematic diagram illustrating a step (vi) of curing resist pattern 110 to obtain cured pattern 120 made of cured resin film 10c. [Diagram 5] FIG. 1 is a partial cross-sectional view showing an example of a wire-wound inductor. [Figure 6] 1 shows optical microscope images of cured patterns obtained in examples and comparative examples of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] In this specification and the claims, the term "aliphatic" is a relative concept to aromaticity and is defined as meaning a group or compound that does not have aromaticity. Unless otherwise specified, the term "alkyl group" includes linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in an alkoxy group. Unless otherwise specified, the term "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups. The term "halogenated alkyl group" refers to an alkyl group in which some or all of the hydrogen atoms have been substituted with halogen atoms, and examples of the halogen atoms include fluorine, chlorine, bromine and iodine atoms. The term "fluorinated alkyl group" refers to an alkyl group in which some or all of the hydrogen atoms have been substituted with fluorine atoms. The term "structural unit" refers to a monomer unit that constitutes a polymeric compound (resin, polymer, copolymer). The phrase "optionally has a substituent" includes both the case where a hydrogen atom (-H) is replaced with a monovalent group and the case where a methylene group (-CH2-) is replaced with a divalent group. The term "exposure" is intended to include any concept including irradiation with radiation.

[0015] The present invention is characterized by the photosensitive material for forming the bottom layer (layer in contact with the support) of the cured pattern which can constitute the insulating portion of the inductor, and known techniques can be applied to the configurations other than the bottom layer. 1 to 4 are schematic diagrams illustrating an embodiment of a process for forming a hardened pattern that constitutes an insulating portion in an inductor. The process of forming a hardened pattern will now be described with reference to the accompanying drawings. In the drawings, components may be shown diagrammatically to make them easier to see, and some components may be shown on different scales.

[0016] (Photosensitive composition) The photosensitive composition of the present embodiment contains a polyfunctional aromatic epoxy compound (hereinafter also referred to as "component (A)") and a photoacid generator (hereinafter also referred to as "component (I)"). When a photosensitive film (resist layer) is formed using such a photosensitive composition and the photosensitive film is selectively exposed to light, an acid is generated from component (I) in the exposed part of the photosensitive film, and the epoxy group in component (A) undergoes ring-opening polymerization due to the action of the acid, and the solubility of the photosensitive film in the developer containing an organic solvent decreases, while the solubility of the photosensitive film in the developer containing an organic solvent does not change in the unexposed part of the photosensitive film, so that a difference in solubility in the developer containing an organic solvent occurs between the exposed part and the unexposed part of the photosensitive film.Therefore, when the photosensitive film is developed with the developer containing an organic solvent, the unexposed part is dissolved and removed, and a negative pattern is formed.

[0017] <Polyfunctional aromatic epoxy compound (component (A))> The component (A) can be a compound having a sufficient number of epoxy groups in one molecule to form a negative pattern upon exposure. In this specification, the term "multifunctional epoxy compound" refers to a compound containing three or more epoxy groups in one molecule. When the multifunctional epoxy compound is a polymer, the term "multifunctional epoxy compound" refers to a polymer containing three or more epoxy groups per polymer molecule. In this specification, the polyfunctional epoxy compound includes polyfunctional aromatic epoxy compounds and polyfunctional aliphatic compounds.

[0018] Examples of the component (A) used in the photosensitive composition of this embodiment include a novolac-type epoxy resin (hereinafter also referred to as "component (A0)") having a structural unit (a01) represented by the following general formula (a0-1) and a structural unit (a02) represented by the following general formula (a0-2):

[0019] [ka] [In the formula, R 01 is an alkyl group having 1 to 5 carbon atoms. 01 is an integer from 1 to 4. 01 If is 2 or more, multiple R 01 may be the same or different from each other. R E0 is an epoxy group-containing group. 02 and R 03 are each independently an alkyl group having 1 to 5 carbon atoms or a halogen atom. 02 and n 03 are integers from 0 to 3. 0≦n 02 +n 03 ≦3. n 02 If is 2 or more, multiple R 02 may be the same or different. 03 If is 2 or more, multiple R 03 may be the same or different.

[0020] <Structural unit (a01)> The structural unit (a01) is a structural unit represented by the above general formula (a0-1).

[0021] In the formula (a0-1), R 01 The alkyl group having 1 to 5 carbon atoms is, for example, a straight-chain, branched-chain, or cyclic alkyl group having 1 to 5 carbon atoms. Examples of the straight-chain or branched-chain alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. Examples of the cyclic alkyl group include a cyclobutyl group, and a cyclopentyl group. Among them, R 01 As the alkyl group, a linear or branched alkyl group is preferable, a linear alkyl group is more preferable, and a methyl group is particularly preferable.

[0022] In the formula (a0-1), n 01 is preferably an integer of 1 to 3, and more preferably 2.

[0023] Specific examples of the structural unit (a01) are shown below.

[0024] [ka]

[0025] Structural unit (a02) The structural unit (a02) is a structural unit represented by the above general formula (a0-2).

[0026] In the formula (a0-2), R 02 , R 03 As the alkyl group having 1 to 5 carbon atoms in R 01 Examples of the alkyl group include those exemplified as the alkyl group having 1 to 5 carbon atoms in the above. R 02 , R 03 The halogen atom is preferably a chlorine atom or a bromine atom. n 02 and n03 Each of is preferably 0.

[0027] In the formula (a0-2), R E0 is an epoxy group-containing group. R E0 The epoxy group-containing group is not particularly limited, and examples thereof include a group consisting of only epoxy groups; a group consisting of only alicyclic epoxy groups; and a group having an epoxy group or an alicyclic epoxy group and a divalent linking group. The alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure which is a three-membered ring ether, and specifically, is a group having an alicyclic group and an oxacyclopropane structure. The alicyclic group that is the basic skeleton of the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. The hydrogen atom of these alicyclic groups may be substituted with an alkyl group, an alkoxy group, a hydroxyl group, or the like. In the case of a group having an epoxy group or an alicyclic epoxy group and a divalent linking group, it is preferable that the epoxy group or the alicyclic epoxy group is linked via the divalent linking group bonded to an oxygen atom (—O—) in the formula.

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

[0029] Regarding the optionally substituted divalent hydrocarbon group: Such a divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group in the divalent hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. More specifically, the aliphatic hydrocarbon group may be a straight-chain or branched-chain aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in the structure.

[0030] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, further preferably 1 to 4, and most preferably 1 to 3. The linear aliphatic hydrocarbon group is preferably a linear alkylene group, and specific examples thereof include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], and a pentamethylene group [-(CH2)5-]. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms, and most preferably 2 or 3 carbon atoms. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specific examples thereof include alkyl alkylene groups such as alkyl methylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-, etc.; alkyl ethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-, etc.; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

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

[0032] The aromatic hydrocarbon group in the divalent hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The 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, further preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring. Specific examples of the aromatic hydrocarbon group include a group in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); a group in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); a group in which one hydrogen atom of a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) has been substituted with an alkylene group (e.g., a group in which one hydrogen atom has been further removed from the aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The number of carbon atoms of the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

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

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

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

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

[0037] In the divalent linking group containing a hetero atom, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-; -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)- (H may be substituted by a substituent such as an alkyl group or an acyl group); -S-, -S(=O)2-, -S(=O)2-O-, and the general formula -Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 , -[Y 21 -C(=O)-O] m” -Y 22 -or-Y 21 -OC(=O)-Y 22 -, wherein Y 21 and Y 22 each independently represents a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m″ is an integer of 1 to 3. When the divalent linking group containing a hetero atom is -C(=O)-NH-, -NH-, -NH-C(=O)-O-, or -NH-C(=NH)-, the H may be substituted with a substituent such as an alkyl group, acyl, etc. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5 carbon atoms. Formula-Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -, -[Y 21 -C(=O)-O] m” -Y 22 -or-Y 21 -OC(=O)-Y 22 -Medium, Y 21 and Y 22 are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same ones as the "divalent hydrocarbon group which may have a substituent" listed above in the description of the divalent linking group. Y 21 As the alkyl group, a straight-chain aliphatic hydrocarbon group is preferable, a straight-chain alkylene group is more preferable, a straight-chain alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or ethylene group is particularly preferable. 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, more preferably 1 or 2, and particularly preferably 1. That is, the group represented by the formula -[Y 21 -C(=O)-O] m” -Y 22 The group represented by the formula -Y 21 -C(=O)-OY 22 Particularly preferred is a group represented by the formula -(CH2) a’ -C(=O)-O-(CH2) b’ In the formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, 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.

[0038] Among them, R E0 As the epoxy group-containing group in the formula (I), a glycidyl group is preferred.

[0039] Specific examples of the structural unit (a02) are shown below.

[0040] [ka]

[0041] The component (A0) may be a resin consisting only of the structural units (a01) and (a02), or it may be a resin having the structural units (a01) and (a02) in addition to other structural units. Examples of other structural units include structural units represented by the following general formulas (anv2) to (anv3).

[0042] [ka] [In the formula, R a24 R is a hydrocarbon group which may have a substituent. a25 ~R a26 , R a28 ~R a30 R each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. a27 is an epoxy group-containing group or a hydrocarbon group which may have a substituent.

[0043] In the above formula (anv2), R a24 is a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group which may have a substituent include a linear or branched alkyl group, and a cyclic hydrocarbon group. The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Among these, a methyl group, an ethyl group, or an n-butyl group is preferred, and a methyl group or an ethyl group is more preferred.

[0044] The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group, and is preferably an isopropyl group.

[0045] R a24When 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. The monocyclic aliphatic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The aliphatic hydrocarbon group that is a polycyclic group is preferably a group in which one hydrogen atom has been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0046] R a24 When the cyclic hydrocarbon group is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The 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, further preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring. R a24Specific examples of the aromatic hydrocarbon group in include a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); a group in which one hydrogen atom has been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocycle has been substituted with an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, and 2-naphthylethyl group). The number of carbon atoms of 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.

[0047] In the above formulas (anv2) and (anv3), R a25 ~R a26 , R a28 ~R a30 are each 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 defined as R a22 , R a23 is the same as:

[0048] In the above formula (anv3), R a27 R is an epoxy group-containing group or a hydrocarbon group which may have a substituent. a27 The epoxy group-containing group is R EP Same as R a27 The hydrocarbon group which may have a substituent is R a24 is the same as:

[0049] Specific examples of the structural units represented by the above formulas (anv2) to (anv3) are shown below.

[0050] [ka]

[0051] The component (A0) is preferably a novolac-type epoxy resin consisting only of repeating structures of the structural units (a01) and (a02).

[0052] In the component (A0), the proportion of the structural unit (a01) is preferably 40 to 80 mol %, more preferably 40 to 70 mol %, and even more preferably 50 to 60 mol %, based on the total (100 mol %) of all structural units constituting the novolac epoxy resin. In the component (A0), the proportion of the structural unit (a02) is preferably 20 to 60 mol %, more preferably 30 to 60 mol %, and even more preferably 40 to 50 mol %, based on the total (100 mol %) of all structural units constituting the novolac epoxy resin.

[0053] In the component (A0), the total amount of the structural units (a01) and the structural units (a02) is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, and even more preferably 90 to 100 mol%, based on the total amount (100 mol%) of all structural units constituting the novolac epoxy resin.

[0054] In the component (A0), the compositional ratio (molar ratio) of the structural unit (a01) to the structural unit (a02), expressed as structural unit (a01) / structural unit (a02), is preferably from 80 / 20 to 50 / 50, more preferably from 70 / 30 to 50 / 50, and even more preferably from 60 / 40 to 50 / 50.

[0055] The epoxy equivalent of the component (A0) is preferably from 200 to 400 g / eq, more preferably from 250 to 350 g / eq, and even more preferably from 250 to 300 g / eq.

[0056] The softening point of the component (A0) is preferably from 45 to 100°C, more preferably from 50 to 85°C, and even more preferably from 55 to 75°C.

[0057] An example of a commercially available product of the component (A0) is YX7700 (manufactured by Mitsubishi Chemical Corporation). YX7700 is a novolac-type epoxy resin represented by the following chemical formula (A0-1) that has structural units (a01) and (a02).

[0058] [ka]

[0059] The novolac epoxy resin represented by the formula (A0-1) can be produced, for example, by the method exemplified below. As a production method, for example, a method can be mentioned in which xylene, a phenol and formaldehyde are reacted to obtain a novolak type phenolic resin, and the obtained novolak type phenolic resin is reacted with epichlorohydrin to convert it into a glycidyl ether.

[0060] As the component (A0), one type may be used alone, or two or more types may be used in combination. In the photosensitive composition of this embodiment, the content of the component (A0) relative to the total mass (mass %) of the component (A) may be 30 to 100 mass%, 50 to 100 mass%, 70 to 100 mass%, 90 to 100 mass%, or 100 mass%.

[0061] In addition to the component (A0), the component (A) may contain, for example, a novolac type epoxy resin, a bisphenol type epoxy resin, or the like, other than the component (A0).

[0062] <Novolac type epoxy resin> Suitable examples of novolac-type epoxy resins other than the component (A0) (hereinafter also referred to as "component (A1)") include epoxy resins represented by the following general formula (anv0).

[0063] [ka] [In the formula, R p1 and Rp2 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p1 may be the same or different. p2 may be the same or different. n1 is an integer of 1 to 5. R EP is an epoxy group-containing group. EP may be the same or different.

[0064] In the above formula (anv0), R p1 , R p2 As the alkyl group having 1 to 5 carbon atoms in the formula (a0-1), 01 Examples of the alkyl group include those exemplified as the alkyl group having 1 to 5 carbon atoms in the above. R p1 , R p2 As the alkyl group, a hydrogen atom or a linear or branched alkyl group is preferable, a hydrogen atom or a linear alkyl group is more preferable, and a hydrogen atom or a methyl group is particularly preferable.

[0065] In the above formula (anv0), n1 is an integer of 1 to 5, preferably 2 or 3, and more preferably 2. In the above formula (anv0), R EP is an epoxy group-containing group. R EP The epoxy group-containing group is R E0 and a glycidyl group is preferred.

[0066] Additionally, suitable examples of the component (A1) include resins having the structural unit (a02).

[0067] As the component (A1), one type may be used alone, or two or more types may be used in combination. Commercially available products of the component (A1) include, for example, novolac type epoxy resins such as jER-152, jER-154, jER-157S70, and 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, and EPICLON HP5000 (all manufactured by DIC Corporation), and EOCN-1020 (all manufactured by Nippon Kayaku Co., Ltd.).

[0068] <Bisphenol-type epoxy resin> The bisphenol-type epoxy resin (hereinafter also referred to as "component (A2)") may be any resin having a structural unit containing a bisphenol skeleton, and among these, solid bisphenol-type epoxy resins are preferred. The solid bisphenol-type epoxy resin refers to a resin that is solid at 25°C and has a structural unit that includes a bisphenol skeleton. The epoxy equivalent in the component (A2) is, for example, preferably 800 g / eq. or more, more preferably 800 to 1200 g / eq., and even more preferably 900 to 1100 g / eq.

[0069] Suitable examples of the component (A2) include epoxy resins represented by the following general formula (abp1):

[0070] [ka] [In the formula, R EP is an epoxy group-containing group. EP may be the same or different. a31 and R a32 are each 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 is an integer from 1 to 50.

[0071] In the above formula (abp1), R EP R in the formula (a0-2) E0 and a glycidyl group is preferred. In the above formula (abp1), R a31 , R a32 The alkyl group having 1 to 5 carbon atoms is R 01 The alkyl groups having 1 to 5 carbon atoms are the same as those in R a31 , R a32 Each of them is preferably a hydrogen atom or a methyl group. R a31 , R a32 The fluorinated alkyl group having 1 to 5 carbon atoms in the formula (I) is the same as the formula (I) above. a31 , R a32 In the above formula, some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with fluorine atoms. In the above formula (abp1), na 31 is an integer from 1 to 50, preferably an integer from 4 to 15, and more preferably an integer from 5 to 8.

[0072] As the component (A2), one type may be used alone, or two or more types may be used in combination. Examples of commercially available products that can be used as the component (A2) include jER-4005, jER-4007, and 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, and jER-1010 (all manufactured by Mitsubishi Chemical Corporation); and EPICLON 860, EPICLON 1050, EPICLON 1051, and EPICLON 1055 (all manufactured by DIC Corporation).

[0073] In addition, as polyfunctional aromatic epoxy compounds other than the above components (A0), (A1), and (A2), a compound represented by the following chemical formula (A3-1) and a compound represented by the following chemical formula (A3-2) may be used. An example of a commercially available product that can be used as the compound represented by the following chemical formula (A3-1) is 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 (A3-2) include Showfree (registered trademark) BATG (manufactured by Showa Denko KK).

[0074] [ka]

[0075] The polystyrene-equivalent weight average molecular weight of the component (A) is preferably 100 to 300,000, more preferably 200 to 200,000, and even more preferably 300 to 200,000.

[0076] The content of the component (A) in the photosensitive composition of the embodiment may be adjusted according to the thickness of the resist layer to be formed, etc.

[0077] <Other epoxy group-containing compounds> In the photosensitive composition of this embodiment, other epoxy group-containing compounds may be used in addition to the component (A0). Other epoxy group-containing compounds include, for example, acrylic resins, aliphatic epoxy compounds, and the like.

[0078] Examples of the acrylic resin include resins having epoxy group-containing units represented by the following general formulas (a1-1) and (a1-2).

[0079] [ka] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. 41 is a divalent hydrocarbon group which may have a substituent. 41 is an integer between 0 and 2. a41 , R a42 is an epoxy group-containing group.42 is 0 or 1. 41 Is (na 43 +1)valent aliphatic hydrocarbon group. 43 is an integer between 1 and 2.

[0080] In the above formula (a1-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms represented by R is preferably linear or branched, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The halogenated alkyl group having 1 to 5 carbon atoms for R is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferred. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is most preferable.

[0081] In the formula (a1-1), Va 41 R in the formula (a0-2) is a divalent hydrocarbon group which may have a substituent. E0 Examples of the divalent hydrocarbon group which may have a substituent include the same groups as those explained in the above. Among the above, Va 41 The hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably a linear or branched aliphatic hydrocarbon group, further preferably a linear aliphatic hydrocarbon group, and particularly preferably a linear alkylene group.

[0082] In formula (a1-1), na 41 is an integer of 0 to 2, and preferably 0 or 1.

[0083] In formulas (a1-1) and (a1-2), R a41 , R a42is an epoxy group-containing group, and R E0 is the same as:

[0084] In formula (a1-2), Wa 41 In (na 43 The aliphatic hydrocarbon group having a valence of +1 means a hydrocarbon group having no aromaticity, and may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in its structure, or a group in which a linear or branched aliphatic hydrocarbon group and an aliphatic hydrocarbon group containing a ring in its structure are combined.

[0085] Furthermore, the acrylic resin may have a structural unit derived from another polymerizable compound for the purpose of appropriately controlling the physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anion polymerizable compounds. Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxyl group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; meth ... Examples of suitable polymerizable compounds include (meth)acrylic acid aryl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and amide bond-containing polymerizable compounds such as acrylamide and methacrylamide.

[0086] The aliphatic epoxy compound may be a monofunctional aliphatic epoxy compound, a difunctional aliphatic epoxy compound, or a polyfunctional aliphatic epoxy compound.

[0087] In this specification, the polyfunctional epoxy compound includes polyfunctional aromatic epoxy compounds and polyfunctional aliphatic compounds.

[0088] Suitable examples of the aliphatic epoxy compound include the compound represented by the following general formula (m-01) (hereinafter, this compound will also be referred to as "component (m01)").

[0089] [ka] [In the formula, R EP is an epoxy group-containing group. EP may be the same or different.

[0090] In the formula (m-01), R EP is an epoxy group-containing group, and R in the formula (a0-2) E0 is the same as:

[0091] Commercially available products that can be used as the (m01) component include, for example, the TEPIC series (manufactured by Nissan Chemical Industries, Ltd.), such as TEPIC, TEPIC-VL, TEPIC-PAS, TEPIC-G, TEPIC-S, TEPIC-SP, TEPIC-SS, TEPIC-HP, TEPIC-L, TEPIC-FL, and TEPIC-UC; MA-DGIC, DA-MGIC, and TOIC (manufactured by Shikoku Chemical Industries, Ltd.);

[0092] As the component (m01), one type may be used alone, or two or more types may be used in combination. In the photosensitive composition used in this embodiment, the content of the (m01) component is preferably 1 to 15 parts by mass, and more preferably 3 to 10 parts by mass, relative to 100 parts by mass of the total parts by mass of the polyfunctional epoxy compound.

[0093] As the aliphatic epoxy compound, for example, a compound having a structure represented by the following general formula (m-02) (hereinafter, this compound is also referred to as "(m02) component"). The (m02) component may form a condensed ring. The (m02) component may be, for example, a bifunctional aliphatic epoxy compound.

[0094] [ka] [In the formula, n2 is an integer of 1 to 4.]

[0095] In the above formula (m-02), n2 is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2.

[0096] The (m02) component may be a compound in which a plurality of partial structures represented by the above general formula (m-02) are bonded via a divalent linking group or a single bond. Among these, a compound in which a plurality of partial structures represented by the above general formula (m-02) are bonded via a divalent linking group is preferred. The divalent linking group here is not particularly limited, but preferred examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom. Here, the divalent hydrocarbon group which may have a substituent and the divalent linking group which contains a hetero atom are R E0 The divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom are the same as those described in (epoxy group-containing group), and among these, the divalent linking group containing a hetero atom is preferred. 21 A group represented by -C(=O)-O-, -C(=O)-OY 21 A group represented by Y - is more preferred. 21 As the alkyl group, a straight-chain aliphatic hydrocarbon group is preferable, a straight-chain alkylene group is more preferable, a straight-chain alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or ethylene group is particularly preferable.

[0097] Examples of the (m02) component include compounds represented by the following chemical formula: In the following formula, l represents an integer of 1 to 10, and m represents an integer of 1 to 30. R represents an alkylene group having 1 to 8 carbon atoms (preferably an alkylene group having 1 to 3 carbon atoms, such as a methylene group, an ethylene group, a propylene group, or an isopropylene group). n1 and n2 each represent an integer of 1 to 30.

[0098] [ka]

[0099] Examples of commercially available products that can be used as the (m02) component include Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, Celloxide 8000, and Celloxide 8010 (all manufactured by Daicel Corporation); Epocalic THI-DE, DE-102, and DE-103 (all manufactured by ENEOS Corporation).

[0100] As the component (m02), one type may be used alone, or two or more types may be used in combination. In the photosensitive composition used in this embodiment, the content of the (m02) component is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 6 parts by mass, relative to 100 parts by mass of the total parts by mass of the polyfunctional epoxy compounds.

[0101] As a polyfunctional aliphatic epoxy compound, for example, a compound represented by the following general formula (m-03) (hereinafter, this compound is also referred to as "(m03) component") is preferably used. The compound represented by the following general formula (m-03) is a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol.

[0102] [ka] [In the formula, n represents an integer of 1 or more.]

[0103] The polystyrene-equivalent weight average molecular weight (Mw) of the (m03) component is, for example, 1000 to 5000, or may be 1500 to 3000, or may be 1500 to 2500. The polystyrene-equivalent number average molecular weight (Mn) of the (m03) component is, for example, 300 to 1500, or may be 500 to 1000, or may be 600 to 800. The polystyrene-equivalent dispersion (Mw / Mn) of the (m03) component is, for example, 0.8 to 4.0. In the formula (m-03), n is an integer of 2 to 500, and may be 10 to 300, 20 to 200, or 30 to 100.

[0104] An example of a commercially available product that can be used as the component (m03) is EHPE-3150 (manufactured by Daicel Corporation).

[0105] Examples of the bifunctional aliphatic epoxy compound include hydrogenated bisphenol A type glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,4-cyclohexanedimethanol diglycidyl ether. Commercially available products include ADEKA RESIN EP-4080S, EP-4085S, and EP-4088S (all manufactured by ADEKA Corporation); Denacol EX-211L, EX-212L, EX-214L, EX-216L, and EX-850L (all manufactured by Nagase ChemteX Corporation).

[0106] Examples of the polyfunctional aliphatic epoxy compound include epoxidized polybutadiene, 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, etc. Commercially available products include EPOLEAD PB 3600, PB 4700 (all manufactured by Daicel Corporation); Denacol EX-321L, EX-622, (manufactured by Nagase Chemtex Corporation), etc.

[0107] As the component (m03), one type may be used alone, or two or more types may be used in combination. In the photosensitive composition used in this embodiment, the content of the (m03) component is preferably 0 to 80 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 50 parts by mass, relative to 100 parts by mass of the total parts by mass of the polyfunctional epoxy compounds.

[0108] As the aliphatic epoxy compound, the component (m02) or the component (m03) is preferred. The aliphatic epoxy compound is preferably a difunctional aliphatic epoxy compound or a polyfunctional aliphatic epoxy compound.

[0109] In the photosensitive composition used in the present embodiment, the content of the bifunctional aliphatic epoxy compound is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 6 parts by mass, relative to 100 parts by mass of the total parts by mass of the polyfunctional epoxy compounds. In the photosensitive composition used in the present embodiment, the content of the polyfunctional aliphatic epoxy compound is preferably 0 to 80 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 50 parts by mass, relative to 100 parts by mass of the total parts by mass of the polyfunctional epoxy compounds.

[0110] <Photoacid generator> The photoacid generator (hereinafter also referred to as "component (I)") contained in the photosensitive composition of the present embodiment is a compound that generates cations upon irradiation with active energy rays, such as ultraviolet rays, far ultraviolet rays, excimer laser light such as KrF or ArF, X-rays, electron beams, and the like, and the cations can serve as polymerization initiators. Examples of the component (I) include onium borate salts (hereinafter also referred to as "component (I1)") and photoacid generators other than the component (I1) (other photoacid generators).

[0111] Onium borate salts Onium borate salts (component (I1)) generate a relatively strong acid upon exposure to light. Therefore, by forming a pattern using a photosensitive composition containing component (I1), sufficient sensitivity is obtained and a good pattern is formed. In addition, the use of component (I1) is less likely to cause toxicity or metal corrosion. Suitable examples of the component (I1) include compounds represented by the following general formula (I1).

[0112] [ka] [In the formula, R b01 ~R b04 are each independently an aryl group which may have a substituent, or a fluorine atom; q is an integer of 1 or more; q+ is a q-valent organic cation.

[0113] Anion section In the formula (I1), R b01 ~R b04 The aryl group in the formula (I) preferably has 5 to 30 carbon atoms, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. Specific examples include a naphthyl group, a phenyl group, and an anthracenyl group, and the phenyl group is preferred because of its easy availability. R b01 ~R b04 The aryl group in may have a substituent. The substituent is not particularly limited, but is preferably a halogen atom, a hydroxyl group, an alkyl group (preferably a linear or branched alkyl group, preferably having 1 to 5 carbon atoms), or a halogenated alkyl group, more preferably a halogen atom or a halogenated alkyl group having 1 to 5 carbon atoms, and particularly preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. When the aryl group has a fluorine atom, the polarity of the anion moiety is increased, which is preferable. Among them, R in formula (I1) b01 ~R b04 As each of these, a fluorinated phenyl group is preferable, and a perfluorophenyl group is particularly preferable.

[0114] A preferred example of the anion portion of the compound represented by formula (I1) is tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - );Tetrakis[(trifluoromethyl)phenyl]borate ([B(C6H4CF3)4] - );Difluorobis(pentafluorophenyl)borate ([(C6F5)2BF2] - );Trifluoro(pentafluorophenyl)borate ([(C6F5)BF3] - );Tetrakis(difluorophenyl)borate ([B(C6H3F2)4] - ) etc. Among them, tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - ) is particularly preferred.

[0115] ·Cation part In the formula (I1), Q q+ Suitable examples of the cation include a sulfonium cation and an iodonium cation, and the organic cations represented by the following general formulas (ca-1) to (ca-5) are particularly preferred.

[0116] [ka] [In the formula, R 201 ~R 207 , and R 211 ~R 212 R each independently represents an aryl group, a heteroaryl group, an alkyl group or an alkenyl group which may have a substituent. 201 ~R 203 , R 206 ~R 207 , R 211 ~R 212 may be bonded to each other to form a ring together with the sulfur atom in the formula. 208 ~R 209 R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 210is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. 201 represents -C(=O)- or -C(=O)-O-. 201 each independently represents an arylene group, an alkylene group, or an alkenylene group; x is 1 or 2. W 201 represents a (x+1)-valent linking group.

[0117] R 201 ~R 207 , and R 211 ~R 212 The aryl group in the formula (I) may be an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. R 201 ~R 207 , and R 211 ~R 212 The heteroaryl group in the above formula (I) may be one in which a part of the carbon atoms constituting the aryl group is replaced with a heteroatom. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the heteroaryl group include a group in which one hydrogen atom has been removed from 9H-thioxanthene; examples of the substituted heteroaryl group include a group in which one hydrogen atom has been removed from 9H-thioxanthen-9-one. R 201 ~R 207 , and R 211 ~R 212 The alkyl group in is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. R 201 ~R 207 , and R 211 ~R 212 The alkenyl group in the formula (I) preferably has 2 to 10 carbon atoms. R 201 ~R 207 , and R 210 ~R 212Examples of the substituent that may be possessed by the group include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an oxo group (=O), an aryl group, and groups represented by the following formulas (ca-r-1) to (ca-r-10).

[0118] [ka] [In the formula, R' 201 each independently represents a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.

[0119] In the above formulas (ca-r-1) to (ca-r-10), R' 201 each independently represents a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.

[0120] Optionally substituted cyclic groups: The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0121] R' 201 The aromatic hydrocarbon group in the formula (I) 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, further preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. R' 201Specific examples of the aromatic ring possessed by the aromatic hydrocarbon group in the above 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 the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom, etc. R' 201 Specific examples of the aromatic hydrocarbon group in the above include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: for example, phenyl group, naphthyl group, anthracenyl group, etc.), a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.), a group in which one hydrogen atom has been removed from a ring in which some of the hydrogen atoms constituting the aromatic ring have been substituted with an oxo group or the like (for example, anthraquinone, etc.), and a group in which one hydrogen atom has been removed from an aromatic heterocycle (for example, 9H-thioxanthene, 9H-thioxanthen-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.

[0122] R' 201 The cyclic aliphatic hydrocarbon group in the formula (I) is an aliphatic hydrocarbon group containing a ring in the structure. Examples of aliphatic hydrocarbon groups that contain a ring in their structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is present in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, specifically, cyclopentane, cyclohexane, etc. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, the polycycloalkane is more preferably a polycycloalkane having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.; or a polycycloalkane having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton.

[0123] Among them, R' 201 The cyclic aliphatic hydrocarbon group in is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, particularly preferably an adamantyl group or a norbornyl group, and most preferably an adamantyl group.

[0124] The linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], etc. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specific examples thereof include alkyl alkylene groups such as alkyl methylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-, etc.; alkyl ethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-, etc.; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0125] Optionally substituted chain alkyl groups: R' 201 The chain alkyl group may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decanyl group, an undecyl group, a dodecyl group, a tridecyl group, an isotridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, an isohexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a henicosyl group, and a docosyl group. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10. Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0126] An optionally substituted chain alkenyl group: R' 201 The chain alkenyl group may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, further preferably 2 to 4, and particularly preferably 3. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butynyl group. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, and a 2-methylpropenyl group. Of the above chain alkenyl groups, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0127] R' 201 Examples of the substituent in the cyclic group, chain alkyl group or alkenyl group include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, an oxo group, the above-mentioned R' 201 In the above formula, examples include a cyclic group, an alkylcarbonyl group, and a thienylcarbonyl group.

[0128] Among them, R' 201 is preferably a cyclic group which may have a substituent, or a chain alkyl group which may have a substituent.

[0129] R 201 ~R 203 , R 206 ~R 207 , R 211 ~R 212 When they are bonded to each other to form a ring together with the sulfur atom in the formula, they do not include a heteroatom such as a sulfur atom, an oxygen atom, or a nitrogen atom, a carbonyl group, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R N )-(the R Nis an alkyl group having 1 to 5 carbon atoms.) The ring formed is preferably a 3- to 10-membered ring, including the sulfur atom, and particularly preferably a 5- to 7-membered ring, in which a ring containing a sulfur atom in the ring skeleton in the formula is a 3- to 10-membered ring, inclusive of the sulfur atom. Specific examples of the ring formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthrene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0130] In the above formula (ca-3), R 208 ~R 209 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when they are alkyl groups they may be bonded to each other to form a ring.

[0131] In the above formula (ca-3), R 210 is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. R 210 The aryl group in the formula (I) may be an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. R 210 The alkyl group in is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. R 210 The alkenyl group in the formula (I) preferably has 2 to 10 carbon atoms.

[0132] In the above formula (ca-4) and formula (ca-5), Y 201 each independently represents an arylene group, an alkylene group, or an alkenylene group. Y 201 The arylene group in R' 201Examples of the aromatic hydrocarbon group in the above formula include groups in which one hydrogen atom has been removed from the aryl groups exemplified above. Y 201 The alkylene group and alkenylene group in R' 201 Examples of the chain alkyl group and the chain alkenyl group in the above formula (I) include groups in which one hydrogen atom has been removed from the groups exemplified as the chain alkyl group and the chain alkenyl group in the above formula (I).

[0133] In the above formulas (ca-4) and (ca-5), x is 1 or 2. W 201 is a (x+1)-valent linking group, that is, a divalent or trivalent linking group. W 201 The divalent linking group in the formula (a0-2) is preferably a divalent hydrocarbon group which may have a substituent. E0 The divalent hydrocarbon groups which may have a substituent are preferably the same as those exemplified by W. 201 The divalent linking group in may be linear, branched, or cyclic, and is preferably cyclic. Among them, a group in which two carbonyl groups are combined at both ends of an arylene group, or a group consisting of an arylene group alone is preferred. Examples of the arylene group include a phenylene group and a naphthylene group, and the phenylene group is particularly preferred. W 201 The trivalent linking group in 201 and a group in which one hydrogen atom has been removed from the divalent linking group represented by the formula: W 201 As the trivalent linking group in the formula (I), a group in which two carbonyl groups are bonded to an arylene group is preferable.

[0134] Specific examples of suitable cations represented by the formula (ca-1) include cations represented by the following formulas (ca-1-1) to (ca-1-24).

[0135] [ka]

[0136] [ka] [In the formula, R” 201 is a hydrogen atom or a substituent. The substituent may be any of the above-mentioned R 201 ~R 207 and R 210 ~R 212 The substituents are the same as those exemplified as the substituents that may be possessed by the

[0137] As the cation represented by the formula (ca-1), the cations represented by the following general formulas (ca-1-25) to (ca-1-35) are also preferable.

[0138] [ka]

[0139] [ka] [In the formula, R' 211 is an alkyl group. hal is a hydrogen atom or a halogen atom.

[0140] 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 preferable.

[0141] [ka]

[0142] As the cation represented by the formula (ca-1), cations having a benzoylphenyl group represented by the following chemical formulas (ca-1-49) to (ca-1-54) are also preferable.

[0143] [ka]

[0144] Specific examples of suitable cations represented by the formula (ca-2) include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, and the like.

[0145] Specific examples of suitable cations represented by the formula (ca-3) include cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0146] [ka]

[0147] Specific examples of suitable cations represented by the formula (ca-4) include cations represented by the following formulas (ca-4-1) to (ca-4-2).

[0148] [ka]

[0149] As the cation represented by the formula (ca-5), the cations represented by the following general formulas (ca-5-1) to (ca-5-3) are also preferable.

[0150] [ka] [In the formula, R' 212 R' is an alkyl group or a hydrogen atom. 211 is an alkyl group.

[0151] Among the above, the cationic part [(Q q+ ) 1 / q ] is preferably a cation represented by general formula (ca-1), more preferably a cation represented by formulas (ca-1-1) to (ca-1-54), and even more preferably a cation represented by formulas (ca-1-49) to (ca-1-54).

[0152] Specific examples of suitable components (I1) are given below.

[0153] [ka]

[0154] <Other photoacid generators> Examples of photoacid generators other than the above component (I1) include a compound represented by the following general formula (I2-1) or (I2-2) (hereinafter referred to as "component (I2)"); and a compound represented by the following general formula (I3-1) or (I3-2) (hereinafter referred to as "component (I3)").

[0155] Regarding component (I2): The component (I2) is a compound represented by the following general formula (I2-1) or (I2-2). The component (I2) generates a relatively strong acid upon exposure to light, so that when a photosensitive composition containing the component (I) is used to form a pattern, sufficient sensitivity is obtained and a good pattern is formed.

[0156] [ka] [In the formula, R b05 is a fluorine atom or a fluorine-containing alkyl group which may have a substituent. b05 may be the same or different. q is an integer of 1 or more, and Q q+ is a q-valent organic cation.

[0157] [ka] [In the formula, R b06 is a fluorine atom or a fluorine-containing alkyl group which may have a substituent. b06 may be the same or different. q is an integer of 1 or more, and Q q+ is a q-valent organic cation.

[0158] Anion section In the above formula (I2-1), R b05 is a fluorine atom or a fluorine-containing alkyl group which may have a substituent. b05 may be the same or different from each other. R b05 The fluorinated alkyl group in the above formula preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 5. Specific examples include alkyl groups having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms. Among them, R b05 is preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and further preferably a fluorine atom, a trifluoromethyl group or a pentafluoroethyl group.

[0159] The anion moiety of the compound represented by formula (I2-1) is preferably represented by the following general formula (b0-2a).

[0160] [ka] [In the formula, R bf05 is a fluorinated alkyl group which may have a substituent. 1 is an integer from 1 to 5.

[0161] In formula (b0-2a), R bf05 The optionally substituted fluorinated alkyl group in R b05 The substituents are the same as the optionally substituted fluorinated alkyl groups listed under 1. In formula (b0-2a), nb 1 is preferably an integer of 1 to 4, more preferably an integer of 2 to 4, and most preferably 3.

[0162] In the above formula (I2-2), R b06 is a fluorine atom or a fluorine-containing alkyl group which may have a substituent. b06 may be the same or different from each other. Rb06 The fluorinated alkyl group in the above formula preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 5. Specific examples include alkyl groups having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms. Among them, R b06 As the group, a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms is more preferable, and a fluorine atom is even more preferable.

[0163] ·Cation part In formula (I2-1) and formula (I2-2), q is an integer of 1 or more, q+ is a q-valent organic cation. This Q q+ As the above, Q in the formula (I1) q+ Among them, the cations represented by general formula (ca-1) are preferred, and the cations represented by formulas (ca-1-1) to (ca-1-54) are more preferred.

[0164] Regarding the (I3) ingredient: The component (I3) is a compound represented by the following general formula (I3-1) or (I3-2).

[0165] [ka] [In the formula, R b11 ~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. m is an integer of 1 or more, and M m+ are each independently an m-valent organic cation.

[0166] {Component (I3-1)} Anion section In formula (I3-1), 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, and R' 201 Among the cyclic groups, chain alkyl groups, and chain alkenyl groups in the explanation of the 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. The chain alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10. The aliphatic cyclic group is preferably a group in which one or more hydrogen atoms have been removed from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like (which may have a substituent other than a halogen atom); R b12 The hydrocarbon group may have a substituent other than a halogen atom, and examples of the substituent include R b11 Examples of the substituents include those similar to the substituents other than halogen atoms that may be contained in the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in the above formula. The phrase "may have a substituent other than a halogen atom" as used herein not only excludes the case where a substituent consists of only halogen atoms, but also excludes the case where a substituent contains at least one halogen atom (for example, the case where the substituent is a fluorinated alkyl group, etc.).

[0167] Preferred specific examples of the anion portion of the component (I3-1) are shown below.

[0168] [ka]

[0169] ·Cation part In formula (I3-1), Mm+ is an m-valent organic cation. M m+ Suitable examples of the organic cation include the cations represented by the above general formulas (ca-1) to (ca-5), and among these, the cation represented by the above general formula (ca-1) is more preferred. 201 , R 202 , R 203 A sulfonium cation in which at least one of the above is an organic group having 16 or more carbon atoms (aryl group, heteroaryl group, alkyl group, or alkenyl group) which may have a substituent is particularly preferred because it improves the resolution and roughness characteristics. The substituents that the organic group may have are the same as those described above, and include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an oxo group (=O), an aryl group, and groups represented by the above formulas (ca-r-1) to (ca-r-10). The number of carbon atoms in the 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 examples of the organic cation include 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). Among these, the cation represented by the above formula (ca-1-29) is particularly preferred.

[0170] {Component (I3-2)} Anion section In formula (I3-2), R b11 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 R' 201Among the cyclic groups, chain alkyl groups, and chain alkenyl groups in the explanation of the above, those having no substituent or those having a substituent other than a halogen atom are exemplified.

[0171] Among these, R b11 As the substituent, an aromatic hydrocarbon group which may have a substituent other than a halogen atom, an aliphatic cyclic group which may have a substituent other than a halogen atom, or a chain alkyl group which may have a substituent other than a halogen atom are preferable. The substituent which these groups may have includes a hydroxyl group, an oxo group, an alkyl group, an aryl group, a lactone-containing cyclic group, an ether bond, an ester bond, or a combination thereof. When an ether bond or an ester bond is contained as a substituent, it may be connected via an alkylene group, and in this case, the substituent is preferably a linking group represented by each of the following general formulas (y-al-1) to (y-al-7). In the following general formulas (y-al-1) to (y-al-7), R b11 The bond to V' in the following general formulas (y-al-1) to (y-al-7) is 101 It is.

[0172] [ka] [In the formula, V' 101 V' is a single bond or an alkylene group having 1 to 5 carbon atoms. 102 is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.]

[0173] 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.

[0174] V' 101 and V' 102The alkylene group in may be a straight-chain alkylene group or a branched-chain alkylene group, and is preferably a straight-chain alkylene group. V' 101 and V' 102 Specific examples of the alkylene group in the formula (I) include a methylene group [-CH2-]; alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; an ethylene group [-CH2CH2-]; -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, and -CH(CH2CH3)CH2 -, etc.; a trimethylene group (n-propylene group) [-CH2CH2CH2-]; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; a tetramethylene group [-CH2CH2CH2CH2-]; alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and a pentamethylene group [-CH2CH2CH2CH2CH2-]. Also, V' 101 or V' 102 A part of the methylene groups in the alkylene group in the formula (I) may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is represented by R' 201 A divalent group in which one hydrogen atom has been further removed from a cyclic aliphatic hydrocarbon group (a monocyclic alicyclic hydrocarbon group, a polycyclic alicyclic hydrocarbon group) such as those mentioned above is preferred, and a cyclohexylene group, a 1,5-adamantylene group, or a 2,6-adamantylene group is more preferred.

[0175] The aromatic hydrocarbon group is more preferably a phenyl group or a naphthyl group. The aliphatic cyclic group is more preferably a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. The chain alkyl group preferably has 1 to 10 carbon atoms. Specific examples of the chain alkyl group include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group; and branched alkyl groups such as a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0176] R b11 is preferably a cyclic group which may have a substituent other than a halogen atom. Preferred specific examples of the anion moiety of the component (I3-2) are shown below.

[0177] [ka]

[0178] ·Cation part In formula (I3-2), M m+ is an m-valent organic cation, and M in the formula (I3-1) m+ is the same as:

[0179] Specific examples of suitable components (I3) are given below.

[0180] [ka]

[0181] As the component (I), one type may be used alone, or two or more types may be used in combination. In the photosensitive composition of this embodiment, the component (I) preferably contains the component (I1) and the component (I3), and more preferably consists of only the component (I1) and the component (I3).

[0182] In the component (I) of the photosensitive composition of this embodiment, the total content of the components (I1) and (I3) is preferably 90 mass% or more, more preferably 95 mass% or more, and even more preferably 98 mass% or more, relative to 100 mass% of the total amount of the component (I).

[0183] The content of the component (I) in the photosensitive composition of this embodiment is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, even more preferably 0.1 to 5 parts by mass, and particularly preferably 1 to 5 parts by mass, relative to 100 parts by mass of the polyfunctional epoxy compound. When the content of component (I) is equal to or greater than the lower limit of the preferred range, sufficient sensitivity is obtained, and the lithography properties of the resist pattern are further improved. In addition, the strength of the cured resin film is further increased. On the other hand, when the content is equal to or less than the upper limit of the preferred range, the sensitivity is appropriately controlled, and a resist pattern with a good shape is easily obtained.

[0184] The content of the component (I1) in the photosensitive composition of this embodiment is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the polyfunctional epoxy compound. When the content of the component (I0) is at least as large as the lower limit of the above-mentioned preferred range, a resist pattern with a good shape is more likely to be obtained, while when the content is at most the upper limit of the above-mentioned preferred range, both sensitivity and resist pattern shape can be achieved.

[0185] The content of the component (I3) in the photosensitive composition of this embodiment is preferably 0.005 to 1 part by mass, more preferably 0.005 to 0.1 part by mass, and even more preferably 0.01 to 0.05 part by mass, relative to 100 parts by mass of the polyfunctional epoxy compound. When the content of component (I3) is equal to or greater than the lower limit of the preferred range, the diffusion of the acid generated from component (I0) upon exposure becomes moderate, making it easier to obtain a resist pattern with a good shape. On the other hand, when the content is equal to or less than the upper limit of the preferred range, sufficient sensitivity is obtained, and the lithography properties of the resist pattern are further improved.

[0186] Regarding optional ingredients: The photosensitive composition of the present embodiment may contain other components (optional components) as necessary, in addition to the above-mentioned components (A) and (I). If desired, the photosensitive composition may contain suitable miscible additives, such as metal oxides, silane coupling agents, sensitizer components, solvents, additional resins for improving the performance of the film, dissolution inhibitors, basic compounds, plasticizers, stabilizers, colorants, and antihalation agents.

[0187] Examples of metal oxides (component (M)) include oxides of metals such as silicon (metallic silicon), titanium, zirconium, and hafnium. Of these, oxides of silicon are preferred, and among these, it is particularly preferred to use silica. By incorporating component (M), it becomes easier to obtain a cured resin film with improved film strength and heat resistance, and it is also possible to form a resist pattern with a good shape and high resolution. The shape of component (M) is preferably particulate.

[0188] Examples of the silane coupling agent include silane coupling agents having reactive substituents such as a carboxy group, a methacryloyl group, an isocyanate group, an epoxy group, etc. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc.

[0189] The sensitizer component is not particularly limited as long as it can absorb energy due to exposure and transmit the energy to other substances.Specific examples of the sensitizer component include benzophenone-based photosensitizers such as benzophenone and p,p'-tetramethyldiaminobenzophenone, carbazole-based photosensitizers, acetophene-based photosensitizers, naphthalene-based photosensitizers such as 1,4-diethoxynaphthalene and 1,5-dihydroxynaphthalene, phenol-based photosensitizers, anthracene-based photosensitizers such as 9-ethoxyanthracene, biacetyl, eosin, rose bengal, pyrene, phenothiazine, anthrone, and other known photosensitizers.

[0190] The photosensitive composition of the present embodiment may further contain a solvent (hereinafter sometimes referred to as "component (S)"). Examples of the (S) component include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds having an ester bond such as 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate; monoalkyl ethers or monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether of the above polyhydric alcohols or the above compounds having an ester bond; derivatives of polyhydric alcohols such as compounds having an ether bond, such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred among these; cyclic ethers such as dioxane; esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene; and dimethyl sulfoxide (DMSO).

[0191] The component (S) may be used alone or as a mixed solvent of two or more kinds.

[0192] When the component (S) is contained, its amount is not particularly limited, and is appropriately set according to the thickness of the coating film at a concentration that allows the photosensitive composition to be applied to a substrate or the like without dripping. For example, the (S) component can be used so that the solids concentration is 50% by mass or more, and the (S) component can be used so that the solids concentration is 60% by mass or more. Also, an embodiment that does not substantially contain the component (S) (that is, an embodiment in which the solids concentration is 100% by mass) can be employed.

[0193] The photosensitive composition of the present embodiment described above contains a polyfunctional aromatic epoxy compound and a photoacid generator, and the polyfunctional aromatic epoxy compound contains a novolac epoxy resin (component (A0)) having a structural unit (a01) that contains an epoxy group and a structural unit (a02) that does not contain an epoxy group. The first resist layer formed using the photosensitive composition of the present embodiment contains the component (A0), which can enhance the adhesion between the support and the first resist layer. As a result, the cured pattern is less likely to peel off from the support, and pattern collapse is suppressed, making it possible to stably produce a cured pattern with a good shape.

[0194] (Method of manufacturing laminate) The method for producing a laminate of this embodiment includes a step of forming a first resist layer on a support using a first photosensitive composition, and a step of forming a second resist layer on the first resist layer using a second photosensitive composition. The method for producing a laminate is characterized in that the photosensitive composition of the above-mentioned embodiment is used as the first photosensitive composition.

[0195] The second photosensitive composition may be, for example, a photosensitive composition containing a polyfunctional aromatic epoxy compound (excluding the component (A0)) and a photoacid generator. Examples of the photoacid generator include the same ones as the component (I) in the photosensitive composition of the above-mentioned embodiment. Examples of the photoacid generator include those similar to the component (I1) in the photosensitive composition of the above embodiment, and among these, the compound represented by the above chemical formula (I1-4) is more preferred.

[0196] When the second photosensitive composition contains the component (I1) as a photoacid generator, the content of the component (I1) is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and even more preferably 0.2 to 2 parts by mass, relative to 100 parts by mass of the polyfunctional epoxy compound.

[0197] As one embodiment of a method for producing such a laminate, for example, a method for producing a laminate 10 shown in FIG. 1 will be described. FIG. 1 is a cross-sectional view showing one embodiment of a laminate 10 formed on a support 20. As shown in FIG. The laminate 10 is formed by laminating a first resist layer 11 in contact with a support 20, a second resist layer 12, a third resist layer 13, and a fourth resist layer 14 in this order.

[0198] The laminate 10 can be produced by a production method including the steps of: (i) forming a first resist layer 11 on a support 20 using a first photosensitive composition; (ii) forming a second resist layer 12 on the first resist layer 11 using a second photosensitive composition; and (iii) forming a third resist layer 13 and a fourth resist layer 14 in this order on the second resist layer 12. Each of steps (i) to (iii) will be described below.

[0199] <Process (i)> In step (i), a first resist layer 11 is formed on a support 20 using a first photosensitive composition. In this embodiment, the first photosensitive composition is the photosensitive composition of the above-mentioned embodiment. The method for forming the first resist layer 11 on the support 20 may be, for example, a method in which the first photosensitive composition in a solution state is applied onto the support and a pre-baking (PAB) process is performed, or a method in which the first photosensitive composition in a film form is laminated onto the support.

[0200] When the first photosensitive composition in a solution state is used, the first photosensitive composition in a solution state is first applied onto the support 20 by a known method such as spin coating, roll coating, or screen printing, and then baked (post-applied bake (PAB)) for 2 to 60 minutes at a temperature condition of 50 to 150°C, for example, to form a first resist layer 11 (photosensitive film) on the support 20.

[0201] When a first photosensitive composition in the form of a film is used, a laminate film (1) in which a photosensitive film has been formed in advance on a base film in the same manner as described above is laminated so that the photosensitive film and the support 20 are adjacent to each other, thereby forming a first resist layer 11 (photosensitive film) on the support 20. The conditions for laminating the photosensitive film using the first photosensitive composition and the support 20 are preferably, for example, a temperature of 30 to 100° C., a pressure of 0.1 to 0.5 MPa, and a processing speed of 0.2 to 1.0 m / min.

[0202] The thickness of the first resist layer 11 (photosensitive film) is preferably 60 μm or less, more preferably 5 to 60 μm, and further preferably 20 to 50 μm.

[0203] The base film constituting the laminated film (1) may be a known one, for example, a thermoplastic resin film. Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate. The thickness of the base film is preferably 2 to 150 μm.

[0204] The support 20 may be any known material, such as a substrate for electronic components or a substrate having a predetermined wiring pattern formed thereon. More specifically, examples of substrates for electronic components include metal substrates such as silicon, silicon nitride, titanium, tantalum, lithium tantalate (LiTaO3), niobium, lithium niobate (LiNbO3), palladium, titanium tungsten, copper, chromium, iron, and aluminum, as well as glass substrates. Examples of materials for the wiring pattern include copper, aluminum, nickel, and gold. The support 20 may be a substrate having an organic material film provided thereon. Examples of the organic material film include organic anti-reflective coatings (organic BARCs) and organic films such as lower organic films in a multi-layer resist method. The support 20 may be a substrate such as the above impregnated with a thermosetting resin (a substrate containing a thermosetting resin). Examples of the thermosetting resin include bismaleimide triazine resin. In the present embodiment, from the standpoints of heat resistance, electrical properties, ease of processing, cost, etc., it is preferable to use a support 20 having a substrate containing a thermosetting resin, and it is more preferable to use a support having a substrate containing a bismaleimide triazine resin.

[0205] <Process (ii)> In step (ii), a second resist layer 12 is formed on the first resist layer 11 using a second photosensitive composition. As a method for forming the second resist layer 12 on the first resist layer 11, a method of laminating a film-shaped second photosensitive composition and the first resist layer 11 can be mentioned. A laminate film (2) in which a photosensitive film has been formed in advance on a base film in the same manner as described above using a second photosensitive composition in the form of a film is then laminated so that the photosensitive film using the second photosensitive composition and the first resist layer 11 are adjacent to each other, thereby forming a second resist layer 12 on the first resist layer 11. The conditions for laminating the photosensitive film using the second photosensitive composition and the first resist layer 11 are preferably, for example, a temperature of 30 to 100° C., a pressure of 0.1 to 0.5 MPa, and a processing speed of 0.2 to 1.0 m / min.

[0206] The thickness of the second resist layer 12 (photosensitive film) is not particularly limited, and may be, for example, 10 to 250 μm. The second resist layer 12, the third resist layer 13, and the fourth resist layer 14 do not need to be formed in three separate layers, and may be formed in one layer (i.e., only the second resist layer 12) to the required thickness, or in two layers (i.e., only the second resist layer 12 and the third resist layer 13), or in four or more layers.

[0207] The base film constituting the laminated film (2) may be a known one, for example, a thermoplastic resin film. Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate. The thickness of the base film is preferably 2 to 150 μm.

[0208] <Step (iii)> In step (iii), a third resist layer 13 and a fourth resist layer 14 are formed in this order on the second resist layer 12. The third photosensitive composition and the fourth photosensitive composition may each be the same as the second photosensitive composition used in the above step (ii). In the operation of step (iii), first, the second resist layer 12 and a film-shaped third photosensitive composition are laminated together to form a third resist layer 13 on the second resist layer 12. Next, the third resist layer 13 and a film-shaped fourth photosensitive composition are laminated together to form a fourth resist layer 14 on the third resist layer 13.

[0209] The lamination conditions for forming the third resist layer 13 and the lamination conditions for forming the fourth resist layer 14 are similar to the conditions for forming the second resist layer 12, respectively. The thickness of the third resist layer 13 (photosensitive film) is not particularly limited, but may be, for example, 10 to 250 μm. The thickness of the fourth resist layer 14 (photosensitive film) is not particularly limited, but may be, for example, 10 to 250 μm.

[0210] Next, the first to fourth resist layers laminated on the support 20 are subjected to a baking (post-apply bake (PAB)) treatment as required, for example, at a temperature of 30 to 50° C. for 20 to 80 minutes. As a result of the above, a laminate 10 in which a first resist layer 11, a second resist layer 12, a third resist layer 13, and a fourth resist layer 14 are laminated in this order can be produced on the support 20.

[0211] Regarding the laminate 10: The laminate 10 produced by the production method including the above-mentioned steps (i), (ii) and (iii) is formed by laminating four resist layers. In FIG. 1, the height of the laminate 10 from the surface of the support 20, ie, the total thickness of the four resist layers, is, for example, 60 to 260 μm.

[0212] In the laminate manufacturing method of the embodiment described above, the photosensitive composition of the above-mentioned embodiment is used as the first photosensitive composition for forming the first resist layer 11. Therefore, according to this laminate manufacturing method, a laminate 10 capable of forming a cured pattern of a uniform shape can be manufactured. Specifically, in the laminate 10 in which four resist layers are laminated, the photosensitive composition of the above-mentioned embodiment is used as the first photosensitive composition for forming the first resist layer 11, so that when the cured pattern is formed, the cured pattern is less likely to become twisted.

[0213] In one embodiment of the method for producing the laminate described above, the third photosensitive composition for forming the third resist layer 13 and the fourth photosensitive composition for forming the fourth resist layer 14 can be the same as the second photosensitive composition for forming the second resist layer 12, but the present invention is not limited to this. The third photosensitive composition and the fourth photosensitive composition can each be appropriately selected within the range in which the effects of the present invention are achieved.

[0214] In one embodiment of the method for producing the laminate described above, the method for laminating the second resist layer 12, the third resist layer 13, and the fourth resist layer 14 in the steps (ii) and (iii) is a method for laminating a film-shaped photosensitive composition, but the present invention is not limited to this. For example, the second resist layer 12, the third resist layer 13, and the fourth resist layer 14 can be laminated by selecting a solvent that does not easily dissolve the lower layer, applying a photosensitive composition in a solution state onto the lower layer, and performing a pre-baking (PAB) process.

[0215] In one embodiment of the method for manufacturing the laminate described above, the laminate has a four-layer structure, but this is not limited to this and may have a structure of two or more layers, and the number of layers may be set according to the desired height and aspect ratio. In one embodiment of the method for producing a laminate described above, a method including steps (i) to (iii) has been described, but the method is not limited thereto, and may include other steps as necessary.

[0216] (Method of forming a cured pattern) The method for forming a cured pattern of this embodiment includes the steps of exposing a laminate produced by the laminate production method of the above-mentioned embodiment, developing the exposed laminate to form a resist pattern, and curing the resist pattern to obtain a cured pattern.

[0217] The cured pattern can be produced by a manufacturing method including a step (iv) of exposing the laminate 10 formed on the support 20 shown in FIG. 1 to light, a step (v) of developing the exposed laminate 10 to form a resist pattern 110, and a step (vi) of curing the resist pattern 110 to obtain a cured pattern 120 consisting of a resin cured film 10c. Each of steps (iv) to (vi) will be described below.

[0218] <Process (iv)> In the step (iv), the laminate 10 formed on the support 20 is exposed to light. For example, using a known exposure device, the laminate 10 is selectively exposed through a photomask 90 on which a pattern of a spirally wound coil shape is formed, as shown in FIG. By the exposure treatment in the step (iv), the laminate 10 after exposure becomes an exposed portion 10b whose solubility in a developer has been changed by exposure, and an unexposed portion 10d that remains unchanged.

[0219] After the selective exposure, the exposed laminate 10 is subjected to a baking (post-exposure bake (PEB)) treatment, if necessary, at a temperature of 50 to 80° C. for 30 to 60 minutes.

[0220] The wavelength used for exposure is not particularly limited, and radiation such as ultraviolet rays having a wavelength of 300 to 500 nm, i-rays (wavelength 365 nm), or visible light is selectively irradiated (exposed). As the radiation source, a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. can be used. Here, radiation means ultraviolet light, visible light, far ultraviolet light, X-rays, electron beams, etc. The radiation dose varies depending on the type and amount of each component in the composition, the thickness of the coating film, etc. For example, when an ultra-high pressure mercury lamp is used, it is 100 to 2000 mJ / cm. 2 It is.

[0221] The method for exposing the laminate 10 may be normal exposure (dry exposure) performed in air or an inert gas such as nitrogen, or may be liquid immersion lithography.

[0222] <Process (v)> In the step (v), the exposed laminate 10 is developed to form a resist pattern 110 in the shape of a spirally wound coil. For example, by developing the exposed laminate 10 with a developer containing an organic solvent (organic developer), the unexposed portions 10d of the laminate 10 are dissolved and removed, and the exposed portions 10b remain as residual images, forming a negative resist pattern 110, as shown in FIG. 3. The content of the organic solvent in the developer containing the organic solvent is, for example, preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 99% by mass or more, relative to the total amount of the developer, and may be 100% by mass. After development, a rinse treatment is preferably carried out, and a bake treatment (post-bake) may be carried out as necessary.

[0223] The organic solvent contained in the organic developer may be any solvent capable of dissolving the components of the photosensitive composition, and may be appropriately selected from known organic solvents. Specific examples of the organic solvent include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, and hydrocarbon solvents.

[0224] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, methyl amyl ketone (2-heptanone), etc. Among these, methyl amyl ketone (2-heptanone) is preferred as the ketone solvent.

[0225] Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, 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, Pyrene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, milk Examples of the lactate include ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and propyl 3-methoxypropionate.Among these, the ester solvent is preferably butyl acetate or PGMEA.

[0226] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0227] The organic developer may contain known additives as necessary. Examples of such additives include surfactants. The surfactants are not particularly limited, but may include, for example, ionic or nonionic fluorine-based and / or silicon-based surfactants. The surfactant is preferably a non-ionic surfactant, and more preferably a non-ionic fluorine-based surfactant or a non-ionic silicon-based surfactant. When a surfactant is added, the amount added is usually from 0.001 to 5 mass %, preferably from 0.005 to 2 mass %, and more preferably from 0.01 to 0.5 mass %, based on the total amount of the organic developer.

[0228] The development process can be carried out by a known development method, for example, a method of immersing the laminate on a support in a developer for a certain period of time (dip method), a method of piling up the developer on the surface of the laminate by surface tension and leaving it to stand for a certain period of time (paddle method), a method of spraying the developer on the surface of the laminate (spray method), and a method of continuously applying the developer while scanning a developer application nozzle at a constant speed onto a laminate rotating at a constant speed (dynamic dispense method).

[0229] The rinse treatment (cleaning treatment) using a rinse liquid can be carried out by a known rinse method, such as a method of continuously applying the rinse liquid onto a laminate rotating at a constant speed (spin coating method), a method of immersing the laminate in the rinse liquid for a certain period of time (dip method), or a method of spraying the rinse liquid onto the surface of the laminate (spray method). The rinsing treatment is preferably carried out using a rinsing liquid containing an organic solvent.

[0230] <Process (vi)> In step (vi), the resist pattern 110 formed in step (v) is cured to obtain a cured pattern 120. For example, the resist pattern 110 formed in step (v) is subjected to a heat treatment (curing operation) to harden it, thereby obtaining a hardened pattern 120 made of a hardened resin film 10c as shown in FIG. In the cured resin film 10c, the first to fourth resist layers are cured and integrated. The heat treatment (curing operation) in the step (vi) can be carried out under conditions of, for example, a temperature of 100 to 250° C. and a time of 0.5 to 2 hours.

[0231] Regarding hardening pattern 120: 4, the cured pattern 120 is a coil-shaped pattern wound in a spiral shape, and can constitute an insulating part of an inductor as a permanent film. The space between the cured resin films 10c is plated with copper or the like. The height (h) of the cured pattern 120 is, for example, 60 to 260 μm. The width (w) of the cured pattern 120 is, for example, 1 to 100 μm. The distance (space) between the cured patterns 120 is, for example, 1 to 100 μm. The aspect ratio (h / w) of the cured pattern 120 is, for example, 1-80.

[0232] The method for forming a cured pattern according to the present embodiment described above uses the laminate 10 manufactured by the method for manufacturing a laminate according to the above embodiment. Therefore, according to the method for forming a cured pattern, it is possible to manufacture a cured resin film 10c having a good shape without twisting at the nodes between layers.

[0233] Moreover, according to the hardened pattern forming method, it is possible to stably realize finer insulating parts constituting an inductor, and therefore the hardened pattern forming method is useful for manufacturing insulating parts in inductors.

[0234] In one embodiment of the above-mentioned method for forming a cured pattern, in the step (v), the laminate 10 after exposure is developed with a developer containing an organic solvent (organic developer), but the present invention is not limited thereto, and depending on the characteristics of the photosensitive composition, development may be performed with an alkaline developer. As the alkaline developer, for example, a 0.1 to 10 mass % aqueous solution of tetramethylammonium hydroxide (TMAH) can be mentioned.

[0235] (Laminate) The laminate of this embodiment is a laminate of a first resist layer and a second resist layer, and the first resist layer is a resist layer formed from the photosensitive composition of the above-mentioned embodiment.

[0236] One embodiment of such a laminate includes a laminate of a first resist layer 11 and a second resist layer 12 produced by the steps (i) and (ii) in the above-mentioned (method for producing a laminate).

[0237] The laminate of the present embodiment described above has a resist layer formed from the photosensitive composition of the above-mentioned embodiment, and therefore can stably produce a cured pattern with a good shape. EXAMPLES

[0238] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0239] <Preparation of Photosensitive Composition> The components shown in Table 1 were mixed and dissolved in methyl ethyl ketone (MEK), and filtered using a PTFE filter (pore size 1 μm, manufactured by PALL Corporation) to prepare photosensitive compositions of each example (solutions with solid content of 70 to 90% by mass).

[0240] [Table 1]

[0241] In Table 1, the abbreviations have the following meanings. The numbers in brackets [ ] indicate the blending amount of each component (parts by mass; solid content equivalent).

[0242] (A)-1: Novolac epoxy resin represented by the following chemical formula (A0-1). Product name: "YX7700" (epoxy equivalent: 273 g / eq, softening point: 66°C), manufactured by Mitsubishi Chemical Corporation.

[0243] [ka]

[0244] (A)-2: Novolac-type epoxy resin represented by the following chemical formula (A1-1), product name "jER-157S70", manufactured by Mitsubishi Chemical Corporation.

[0245] [ka]

[0246] (m02)-1: An aliphatic epoxy compound represented by the following chemical formula (m02-1). Product name: "CEL2021P", manufactured by Daicel Corporation.

[0247] [ka]

[0248] (m03)-1: Aliphatic epoxy compound represented by the following chemical formula (m03-1) (1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, Mw 1,900, Mn 660, Mw / Mn 2.9). Product name "EHPE-3150", manufactured by Daicel Corporation.

[0249] [ka] [In the formula, n represents an integer of 1 or more.]

[0250] (I)-1: A photoacid generator represented by the following chemical formula (I1-4). (I)-2: A photoacid generator represented by the following chemical formula (I1-1). (I)-3: A photoacid generator represented by the following chemical formula (I3-1-1).

[0251] [ka]

[0252] [ka]

[0253] [ka]

[0254] (X)-1: Glycidoxypropyltrimethoxysilane. Product name: "XIAMETER OFS-6040 Silane", manufactured by Dow Toray.

[0255] <Formation of hardened pattern> Using the photosensitive compositions of Examples 1 to 3 and Comparative Example 1, and the photosensitive composition A, attempts were made to form a cured pattern in the shape of a spirally wound coil.

[0256] The photosensitive composition of Example 1 was applied onto a substrate film using an applicator and dried in an oven at 70°C for 10 minutes to form a photosensitive film (11) having a thickness of 45 μm, thereby obtaining a photosensitive laminate film (11).

[0257] Except for changing the photosensitive composition of Example 1 to the photosensitive composition of Example 2, the coating and drying were carried out as described above to form a photosensitive film (12) having a thickness of 45 μm on the base film, thereby obtaining a photosensitive laminate film (12).

[0258] Except for changing the photosensitive composition of Example 1 to the photosensitive composition of Example 3, the coating and drying were carried out as described above to form a photosensitive film (13) having a thickness of 45 μm on the base film, thereby obtaining a photosensitive laminate film (13).

[0259] Except for changing the photosensitive composition of Example 1 to the photosensitive composition of Comparative Example 1, the coating and drying were carried out as described above to form a photosensitive film (21) having a thickness of 45 μm on a base film, thereby obtaining a photosensitive laminate film (21).

[0260] Except for changing the photosensitive composition of Example 1 to photosensitive composition A, the coating and drying were carried out as described above to form a photosensitive film A with a thickness of 65 μm on a base film, thereby obtaining a photosensitive laminate film A.

[0261] Example 1 Forming a first resist layer: The photosensitive film (11) formed on the base film of the laminate film (11) and a 5-inch silicon substrate (support) containing bismaleimide triazine resin were laminated under conditions of 45° C., 0.3 MPa, and 0.5 m / min so that the photosensitive film (11) and the support were adjacent to each other, thereby forming a first resist layer on the support.

[0262] forming a second resist layer; Next, the base film in contact with the photosensitive film (11) constituting the first resist layer was peeled off, and the exposed photosensitive film (11) and the photosensitive film A formed on the base film of the laminated film A were laminated under conditions of 45°C, 0.3 MPa, and 0.5 m / min to obtain a laminate (11-1) of the support, the first resist layer, and the second resist layer.

[0263] forming a third resist layer; Next, the base film in contact with the photosensitive film A constituting the second resist layer was peeled off, and the exposed photosensitive film A and the photosensitive film A formed on the base film of the laminate film A were laminated under conditions of 45°C, 0.3 MPa, and 0.5 m / min to obtain a laminate (11-1) and a laminate (11-2) of the third resist layer. The resulting laminate (11-2) was then subjected to baking treatment (PAB) at a temperature of 40° C. for 60 minutes.

[0264] Regarding the laminate (11-2) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: 45 μm thick photosensitive film (11) Second resist layer: Photosensitive film A with a thickness of 65 μm Third resist layer: Photosensitive film A with a thickness of 65 μm

[0265] A step of exposing the laminate: Next, the laminate (11-2) after the baking treatment (PAB) was irradiated with 800 mJ / cm 2 using an aligner (Canon, PLA-501F) through a mask having a spirally wound coil-shaped pattern. 2 (i-line integrated value) was exposed. In the exposure, the space width was set to 50 μm, and the line widths were set to 50 μm, 40 μm, 30 μm, 20 μm, and 10 μm. Then, post-exposure baking was performed in an oven at 62° C. for 45 minutes.

[0266] Developing process: Next, the laminate (11-2) after the exposure and baking was subjected to solvent development (dip, vertical) at 23° C. for 40 minutes using PGMEA as a developer, to obtain a resist pattern in the shape of a spirally wound coil. Then, a rinsing treatment was carried out with PGMEA for 5 minutes.

[0267] Steps for obtaining a hardened pattern: Next, the resist pattern after the rinsing treatment was subjected to a heat treatment in an oven at a temperature of 200°C for 60 minutes, thereby obtaining a spirally wound line and space cured pattern (space width: 50 μm, line widths: 50 μm, 40 μm, 30 μm, 20 μm, 10 μm) using the photosensitive composition of Example 1.

[0268] Example 2 Step of forming first to third resist layers: A laminate (12-2) was obtained in the same manner as in Example 1, except that the laminate film (11) was changed to the laminate film (12). The laminate (12-2) had first to third resist layers laminated in this order on a 5-inch silicon substrate (support) containing a bismaleimide triazine resin.

[0269] Regarding the laminate (12-2) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: 45 μm thick photosensitive film (12) Second resist layer: Photosensitive film A with a thickness of 65 μm Third resist layer: Photosensitive film A with a thickness of 65 μm

[0270] A step of exposing a laminate to light, a step of developing the laminate, and a step of obtaining a hardened pattern: Next, the laminate (12-2) after baking (PAB) was subjected to the same operations as in Example 1, including the step of exposing the laminate, the step of developing, and the step of obtaining a cured pattern, to obtain a line-and-space cured pattern using the photosensitive composition of Example 2.

[0271] Example 3 Step of forming first to third resist layers: A laminate (13-2) was obtained in the same manner as in Example 1, except that the laminate film (11) was changed to the laminate film (13). The laminate (13-2) had first to third resist layers laminated in this order on a 5-inch silicon substrate (support) containing a bismaleimide triazine resin.

[0272] Regarding the laminate (13-2) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: 45 μm thick photosensitive film (13) Second resist layer: Photosensitive film A with a thickness of 65 μm Third resist layer: Photosensitive film A with a thickness of 65 μm

[0273] A step of exposing a laminate to light, a step of developing the laminate, and a step of obtaining a hardened pattern: Next, the laminate (13-2) after baking (PAB) was subjected to the steps of exposing the laminate, developing, and obtaining a cured pattern in the same manner as in Example 3, thereby obtaining a line-and-space cured pattern using the photosensitive composition of Example 3.

[0274] Comparative Example 1 Step of forming first to third resist layers: A laminate (21-2) was obtained in the same manner as in Example 1, except that the laminate film (11) was changed to the laminate film (21), in which the first to third resist layers were laminated in this order on a 5-inch silicon substrate (support) containing a bismaleimide triazine resin.

[0275] Regarding the laminate (21-2) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: 45 μm thick photosensitive film (21) Second resist layer: Photosensitive film A with a thickness of 65 μm Third resist layer: Photosensitive film A with a thickness of 65 μm

[0276] A step of exposing a laminate to light, a step of developing the laminate, and a step of obtaining a hardened pattern: Next, the laminate (21-2) after baking (PAB) was subjected to the steps of exposing the laminate, developing, and obtaining a cured pattern in the same manner as in Example 1, thereby obtaining a line-and-space cured pattern using the photosensitive composition of Comparative Example 1.

[0277] [Evaluation of cured pattern shape] The line-and-space cured patterns of each example formed by the above <Formation of Cured Pattern> were observed from above, and OM (optical microscope) images (magnification: 100x) were obtained. The OM images are shown in FIG.

[0278] The pattern shape was evaluated based on the following criteria, and the results are shown in FIG. Evaluation criteria A: The width between patterns was uniform and the pattern shape was good. B: The width between the cured patterns was not uniform. C: The cured pattern was peeled off from the substrate.

[0279] Among the laminates for which a good cured pattern was obtained, the narrowest line widths were as follows: Example 1: 20 μm Example 2: 20 μm Example 3: 20 μm Comparative example 1: 40μm

[0280] From the above, it was confirmed that the photosensitive compositions of the Examples were capable of forming cured patterns with finer line widths and more uniform intervals than the photosensitive compositions of the Comparative Examples.

Claims

1. Contains a polyfunctional aromatic epoxy compound and a photoacid generator, The polyfunctional aromatic epoxy compound is a photosensitive composition containing a novolac-type epoxy resin having a structural unit (a01) represented by the following general formula (a0-1) and a structural unit (a02) represented by the following general formula (a0-2): 【Chemistry 1】 [In the formula, R ０１ is an alkyl group having 1 to 5 carbon atoms. ０１ is an integer from 1 to 4. ０１ When R is 2 or more, multiple R ０１ may be the same or different from each other. R Ｅ０ is an epoxy group-containing group. ０２ and R ０３ are each independently an alkyl group having 1 to 5 carbon atoms or a halogen atom. ０２ and n ０３ are integers from 0 to 3. 0≦n ０２ +n ０３ ≦3. ０２ When R is 2 or more, multiple R ０２ may be the same or different. ０３ When R is 2 or more, multiple R ０３ may be the same or different.

2. 2. The photosensitive composition according to claim 1, wherein the content of the photoacid generator is 0.1 to 5 parts by mass based on 100 parts by mass of the polyfunctional aromatic epoxy compound.

3. forming a first resist layer on a support using a first photosensitive composition; forming a second resist layer on the first resist layer using a second photosensitive composition; A method for producing a laminate comprising the steps of: A method for producing a laminate, comprising using the photosensitive composition according to claim 1 or 2 as the first photosensitive composition.

4. The method of claim 3 , wherein the support comprises a substrate comprising a bismaleimide triazine resin.

5. A step of exposing a laminate produced by the method for producing a laminate according to claim 3 to light; developing the exposed laminate to form a resist pattern; curing the resist pattern to obtain a cured pattern; The method for forming a hardened pattern comprises the steps of:

6. The method for forming a cured pattern according to claim 5 , wherein the cured pattern is a coil-shaped pattern wound in a spiral shape.

7. The method for forming a hardened pattern according to claim 6 , wherein the hardened pattern constitutes an insulating portion of an inductor.

8. A laminate of a first resist layer and a second resist layer, The laminate, wherein the first resist layer is a resist layer formed from the photosensitive composition according to claim 1 or 2.

Images