JP2022043914A - Negative type photosensitive composition, pattern formation method and hollow structure manufacturing method - Google Patents

Abstract

To provide a negative type photosensitive composition which reduces stress inside a cured film and can enhance mold resistance, a pattern formation method and a hollow structure manufacturing method.SOLUTION: A negative type photosensitive composition contains an epoxy group-containing compound and a cation polymerization initiator, in which the epoxy group-containing compound contains component (A1): an epoxy resin having an epoxy equivalent of 300 g/eq. or more and component (A2): a specific novolak type epoxy resin having an epoxy equivalent smaller than the component (A1), a content of the component (A1) is 60-90 mass% with respect to the total mass (100 mass%) of the epoxy group-containing compound, and a content of the component (A2) is 10-40 mass% with respect to the total mass (100 mass%) of the epoxy group-containing compound.SELECTED DRAWING: None

Description

The present invention relates to a negative photosensitive composition, a pattern forming method, and a method for producing a hollow structure.

In recent years, with the miniaturization and high density of electronic components, there is an increasing demand for photosensitive compositions used for electronic components having a hollow sealing structure, such as surface acoustic wave (SAW) filters. In forming the hollow sealing structure of the electronic component, it is necessary to reduce the thickness and strength of the cured film obtained by curing the photosensitive composition.

The photosensitive composition is also used as a spacer (wall material) between the semiconductor wafer and the transparent substrate. For example, a negative photosensitive composition is used to form a photosensitive resin film on the surface of a semiconductor wafer or the like, and the photosensitive resin film is selectively exposed to radiation such as light or an electron beam to perform development processing. After applying the pattern to form a pattern, it is pressure-bonded to a transparent substrate (for example, a glass substrate) to form a spacer. In this photosensitive resin film, a film having a thickness required for a spacer is formed by a photolithography method, and high-resolution patterning is possible with a good shape and no residue. It is necessary that it is possible and that it adheres to a transparent substrate.

In response to the above requirements, a method of reducing the stress of the photosensitive resin film is known as a means used for improving the adhesion between the photosensitive resin film and the transparent substrate.
For example, with respect to the photosensitive material forming the photosensitive resin film, it has been proposed to use a solid bisphenol F type epoxy resin having a large epoxy equivalent in order to reduce the stress of the photosensitive resin film (Patent Documents). 1).

International Publication No. 2015/190476

However, in the conventional photosensitive material, the stress inside the cured film is high, and it cannot be said that the adhesion of the cured film to the substrate can be sufficiently ensured. On the other hand, if the stress inside the cured film is lowered in order to improve the adhesion of the cured film to the substrate, there is a problem that the mold resistance in the subsequent mold test cannot be guaranteed.

The present invention has been made in view of the above circumstances, and is a negative photosensitive composition in which the stress inside the cured film can be suppressed to a low level and the mold resistance can be enhanced, and a pattern forming method and a hollow structure using the negative photosensitive composition. Provides a method of manufacturing a body.

In order to solve the above problems, the present invention has adopted the following configuration.
The first aspect of the present invention is a negative photosensitive composition containing an epoxy group-containing compound (A) and a cationic polymerization initiator (I), wherein the epoxy group-containing compound (A) is (A1). Ingredients: Epoxy equivalent is 300 g / eq. The above epoxy resin and the component (A2): an epoxy resin represented by the following general formula (A2-1) whose epoxy equivalent is smaller than the component (A1) are included, and the content of the component (A1) is The content of the component (A2) is 60 to 90% by mass with respect to the total mass (100% by mass) of the epoxy group-containing compound (A), and the content of the component (A2) is the total mass (A) of the epoxy group-containing compound (A). It is a negative type photosensitive composition, characterized in that it is 10 to 40% by mass with respect to 100% by mass).

［式中、Ｒ^ｐ１及びＲ^ｐ２は、それぞれ独立に、水素原子又は炭素数１～５のアルキル基である。複数のＲ^ｐ１は、互いに同一でもよく異なってもよい。複数のＲ^ｐ２は、互いに同一でもよく異なってもよい。ｎ_１は、１～５の整数である。Ｒ^ＥＰは、エポキシ基含有基である。複数のＲ^ＥＰは、互いに同一であってもよく異なってもよい。］

[In the formula, R ^p1 and R ^p2 are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. The plurality of R ^p1s may be the same as or different from each other. The plurality of R ^p2s may be the same as or different from each other. n ₁ is an integer of 1 to 5. R ^EP is an epoxy group-containing group. The plurality of R ^EPs may be the same as or different from each other. ]

A second aspect of the present invention includes a step of forming a photosensitive resin film on a support and a step of exposing the photosensitive resin film using the negative photosensitive composition according to the first aspect. The pattern forming method is characterized by comprising a step of developing the photosensitive resin film after exposure with a developing solution containing an organic solvent to form a negative pattern.

A third aspect of the present invention is a method for manufacturing a hollow structure including a recess and a top plate portion that closes the opening surface of the recess, using the pattern forming method according to the second aspect. A step of preparing a substrate having a recess on the surface (0-i), a step of preparing a photosensitive resist film having a negative type photosensitive resin film (0-ii), and a step of preparing the photosensitive resist film. A step (i) of arranging the photosensitive resist film so that the surface of the resin film closes the opening surface of the recess in the substrate, and a step (ii) of exposing the photosensitive resin film after the step (i). ), The step (iii) of heat-treating the photosensitive resin film after the step (ii), and after the step (iii), the photosensitive resin film is developed to develop the opening surface of the recess. The roof pattern after the step (iv) of forming the roof pattern (iv) and the roof pattern after the step (iv) are further heat-treated to be cured, and the top plate portion is a cured product of the photosensitive resin film. It is a method for manufacturing a hollow structure, which comprises a step (v) for obtaining a hollow structure comprising the same.

According to the present invention, it is possible to provide a negative photosensitive composition in which the stress inside the cured film can be suppressed to a low level and the mold resistance can be enhanced, and a pattern forming method and a hollow structure manufacturing method using the negative photosensitive composition. can.
By applying the present invention, it is possible to improve the adhesion between the substrate and the material to be the wall and the mold resistance in the production of the hollow sealed structure in the electronic component.

In the present specification and claims, "aliphatic" is a concept relative to aromatics and means a group having no aromaticity, a compound having no aromaticity, or the like. Define.
Unless otherwise specified, the "alkyl group" shall include linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
Unless otherwise specified, the "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups.
The "alkyl halide group" is a group in which a part or all of the hydrogen atom of the alkyl group is substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
"Fluorinated alkyl group" refers to a group in which a part or all of the hydrogen atom of the alkyl group is substituted with a fluorine atom.
The “constituent unit” means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
When describing "may have a substituent", a case where a hydrogen atom (-H) is substituted with a monovalent group and a case where a methylene group ( _-CH2- ) is substituted with a divalent group. And both are included.
"Exposure" is a concept that includes general irradiation of radiation.

(Negative photosensitive composition)
The negative photosensitive composition of the present embodiment (hereinafter, may be simply referred to as “photosensitive composition”) contains an epoxy group-containing compound (A) and a cationic polymerization initiator (I). Hereinafter, each of these components is also referred to as a component (A) and a component (I), respectively.
When a photosensitive resin film is formed using such a photosensitive composition and the photosensitive resin film is selectively exposed, the cation portion of the component (I) is formed in the exposed portion of the photosensitive resin film. The acid is generated by decomposition, and the epoxy group in the component (A) undergoes ring-opening polymerization due to the action of the acid, and the solubility of the component (A) in the developing solution containing an organic solvent is reduced, while the solubility of the component (A) is reduced. In the unexposed portion of the photosensitive resin film, the solubility of the component (A) in the developing solution containing the organic solvent does not change, so that the organic solvent is used between the exposed portion and the unexposed portion of the photosensitive resin film. There is a difference in solubility in the developing solution containing. Therefore, when the photosensitive resin film is developed with a developing solution containing an organic solvent, the unexposed portion is dissolved and removed, and a negative pattern is formed.

<Epoxy group-containing compound (A)>
The epoxy group-containing compound (component (A)) used in the photosensitive composition of the present embodiment has a component (A1): epoxy equivalent of 300 g / eq. The above epoxy resin and the component (A2): an epoxy resin represented by the following general formula (A2-1) whose epoxy equivalent is smaller than that of the component (A1) are included.

［式中、Ｒ^ｐ１及びＲ^ｐ２は、それぞれ独立に、水素原子又は炭素数１～５のアルキル基である。複数のＲ^ｐ１は、互いに同一でもよく異なってもよい。複数のＲ^ｐ２は、互いに同一でもよく異なってもよい。ｎ_１は、１～５の整数である。Ｒ^ＥＰは、エポキシ基含有基である。複数のＲ^ＥＰは、互いに同一であってもよく異なってもよい。］

[In the formula, R ^p1 and R ^p2 are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. The plurality of R ^p1s may be the same as or different from each other. The plurality of R ^p2s may be the same as or different from each other. n ₁ is an integer of 1 to 5. R ^EP is an epoxy group-containing group. The plurality of R ^EPs may be the same as or different from each other. ]

≪ (A1) component ≫
The component (A1) has an epoxy equivalent of 300 g / eq. The above epoxy resin.
The epoxy equivalent of the component (A1) is 300 g / eq. The above is 350 to 1500 g / eq. Is preferable, and 400 to 1200 g / eq. Is more preferable.

Examples of the component (A1) include an epoxy resin having a structure represented by the following general formula (abp1).

［式中、Ｒ^ＥＰは、エポキシ基含有基であり、Ｒ^ａ３１、Ｒ^ａ３２はそれぞれ独立に、水素原子又は炭素数１～５のアルキル基であり、ｎａ^３１は１～５０の整数である。］

[In the ^formula , R ^EP is an epoxy group-containing group, Ra 31 and Ra ³² are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, and na ³¹ is an integer of 1 to 50. ]

In the above formula (abp1), R ^EP is an epoxy group-containing group.
The epoxy group-containing group of ^REP is not particularly limited, and is a group consisting only of an epoxy group; a group consisting only of an alicyclic epoxy group; an epoxy group or an alicyclic epoxy group and a divalent linking group. A group having and can be mentioned.
The alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure which is a 3-membered ring ether, and specifically, a group having an alicyclic group and an oxacyclopropane structure.
The alicyclic group which 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, a cyclooctyl group and the like. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group and the like. Further, 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, the epoxy group or the alicyclic epoxy group is via a divalent linking group bonded to an oxygen atom (—O—) in the formula. It is preferable that the groups are bonded.

Here, the divalent linking group is not particularly limited, but a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom and the like are preferable.

For divalent hydrocarbon groups that may have substituents:
The divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
The aliphatic hydrocarbon group in the divalent hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
More specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group having a ring in its structure, and the like.

The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [-CH _2- ], an ethylene group [-(CH ₂ ) _2- ], a trimethylene group [ -(CH ₂ ) _3- ], tetramethylene group [-(CH ₂ ) _4- ], pentamethylene group [-(CH ₂ ) _5- ] and the like can be mentioned.
The branched-chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, further 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 specifically, -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, and -C (CH ₃ ). _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) ₂ -etc. Alkyl methylene groups;- CH (CH ₃ ) CH _2- , -CH (CH ₃ ) CH (CH ₃ )-, -C (CH ₃ ) ₂ CH _2- , -CH (CH ₂ CH ₃ ) CH _2- , -C (CH ₂ ) CH ₃ ) ₂ -CH ₂ -etc. Alkylethylene groups; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ -etc. Alkyltrimethylene groups; -CH (CH ₃ ) Examples thereof include an alkylalkylene group such as an alkyltetramethylene group such as CH ₂ CH ₂ CH _2- , −CH ₂ CH (CH ₃ ) CH ₂ CH _2- , and the like. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

As the aliphatic hydrocarbon group containing a ring in the structure, an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an alicyclic hydrocarbon ring) and an alicyclic hydrocarbon group are linear or branched. Examples thereof include a group bonded to the end of a chain-shaped aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like. Examples of the linear or branched aliphatic hydrocarbon group include the same groups as described above.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. 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 obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically. Examples thereof include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

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 a monocyclic type or a polycyclic type. 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; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, the aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); an aromatic compound containing two or more aromatic rings. A group from which two hydrogen atoms have been removed (for example, biphenyl, fluorene, etc.); one of the hydrogen atoms of the group (aryl group or heteroaryl group) from which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocyclic ring. Hydrogen from an aryl group in an arylalkyl group such as a group substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group). A group from which one atom is further removed) and the like can be mentioned. The carbon number of the alkylene group bonded to the aryl group or the heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

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

The alicyclic hydrocarbon group in the aliphatic hydrocarbon group containing a ring in the structure as a divalent hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group are preferable, and a methoxy group is preferable. Groups and ethoxy groups are most preferred.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
Examples of the halogenated alkyl group as the substituent include a group in which a part or all of the hydrogen atom of the alkyl group is substituted with the halogen atom.
In the alicyclic hydrocarbon group, a part of the carbon atom constituting the ring structure may be substituted with a substituent containing a heteroatom. As the substituent containing the heteroatom, —O—, —C (= O) —O—, —S—, —S (= O) _2- , —S (= O) ₂ -O— are preferable.

As 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, an alkyl halide group, a hydroxyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
Examples of the alkoxy group, the halogen atom and the alkyl halide group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the alicyclic hydrocarbon group.

About divalent linking groups containing heteroatoms:
The hetero atom in the divalent linking group including the hetero atom is an atom other than the carbon atom and the hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

Among the divalent linking groups containing a heteroatom, the preferred linking groups are -O-, -C (= O) -O-, -C (= O)-, and -OC (= O). -O-; -C (= O) -NH-, -NH-, -NH-C (= O) -O-, -NH-C (= NH)-(H is a substitution of an alkyl group, an acyl group, etc.) It may be substituted with a group.); -S-, -S (= O) _2- , -S (= O) ₂ -O-, general formula-Y ²¹ -OY ^22- , -Y ^21- O-, -Y ²¹ -C (= O) -O-, -C (= O) -O-Y ²¹ ,-[Y ²¹ -C (= O) -O] _{m "} -Y ²² -or -Y Group represented by ²¹ -OC (= O) -Y ^22- [In the formula, Y ²¹ and Y ²² are divalent hydrocarbon groups that may independently have substituents, and are O. Is an oxygen atom and m "is an integer of 0 to 3. ] And so on.
When the divalent linking group containing the hetero atom is -C (= O) -NH-, -NH-, -NH-C (= O) -O-, -NH-C (= NH)- The H may be substituted with a substituent such as an alkyl group or an acyl. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
Equations-Y ²¹ -O-Y 22-, -Y ^{21-O-, -Y 21 -} C (= O) -O-, -C ^{(= O) -O-Y 21-,-[Y 21 - C} (= O) -O] _{m "} -Y ²² -or -Y ²¹ -OC (= O) -Y ²² -In, Y ²¹ and Y ²² may have substituents independently of each other. It is a good divalent hydrocarbon group. The divalent hydrocarbon group is the "divalent hydrocarbon group which may have a substituent" mentioned in the above description as the divalent linking group. Similar things can be mentioned.
As ^Y21 , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or an ethylene group is particularly preferable. preferable.
As Y ²² , a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group or an alkyl methylene group is more preferable. 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.
In the group represented by the formula- [Y ²¹ -C (= O) -O] _{m "} -Y ^22- , m" is an integer of 0 to 3, preferably an integer of 0 to 2, and 0. Or 1 is more preferable, and 1 is particularly preferable. That is, the group represented by the formula- [Y ²¹ -C (= O) -O] _{m "} -Y ^22- is represented by the formula-Y ²¹ -C ⁽ = O) -OY 22-. A group is particularly preferable. Among them, a group represented by the formula- (CH ₂ ) _a' -C (= O) -O- (CH ₂ ) b'-is preferable. In the formula, _a'is 1 to 1 to. It is an integer of 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 and 1 to 8. Is preferred, an integer of 1 to 5 is more preferred, 1 or 2 is even more preferred, and 1 is most preferred.

Of these, the glycidyl group is preferable as the epoxy group-containing group in ^REP .

In the above formula (abp1), ^Ra31 and ^Ra32 are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.
The alkyl group having 1 to 5 carbon atoms of R ^a31 and Ra ³² is, for example, a linear, branched chain, or cyclic alkyl group having 1 to 5 carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like. Examples of the cyclic alkyl group include a cyclobutyl group and a cyclopentyl group.
Among them, as Ra ³¹ and Ra ³² , 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 further preferable.

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

Preferred (A1) components include, for example, an epoxy resin having a structure represented by the following general formula (a1-01) or the following general formula (a1-02).

［式中、Ｒ^ＥＰは、エポキシ基含有基であり、ｎａ^３１は４～５０の整数である。］

[In the formula, R ^EP is an epoxy group-containing group, and na ³¹ is an integer of 4 to 50. ]

［式中、Ｒ^ＥＰは、エポキシ基含有基であり、ｎａ^３１は４～５０の整数である。］

[In the formula, R ^EP is an epoxy group-containing group, and na ³¹ is an integer of 4 to 50. ]

In the formula (a1-01) and the formula (a1-02), the R ^EP is an epoxy group-containing group, and has the same description as the R ^EP in the formula (abp1). Of these, the glycidyl group is preferable as the epoxy group-containing group in ^REP .
In the formula (a1-01) and the formula (a1-02), na ³¹ is an integer of 4 to 50, preferably an integer of 4 to 15, and more preferably an integer of 5 to 8. be.

An epoxy resin having a structure represented by the above general formula (a1-01) is preferable because the stress inside the cured film can be easily suppressed to a lower level.
An epoxy resin having a structure represented by the above general formula (a1-02) is preferable because the mold resistance can be easily enhanced.

Commercially available products that can be used as the (A1) component are, for example, JER-4004, JER-4005, JER-4007, JER-4010 (all manufactured by Mitsubishi Chemical Corporation); Made) and the like.

As the component (A1), one type may be used alone, or two or more types may be used in combination.
In the photosensitive composition of the present embodiment, the content of the component (A1) is 60 to 90% by mass and 65 to 90% by mass with respect to the total mass (100% by mass) of the component (A). It is preferably 70 to 90% by mass, and more preferably 70 to 90% by mass.

≪ (A2) component ≫
The component (A2) is an epoxy resin represented by the following general formula (A2-1) whose epoxy equivalent is smaller than that of the component (A1). That is, a novolak type epoxy resin (Anv) is used as the component (A2).
The component (A2) may have an epoxy equivalent that is relatively smaller than the epoxy equivalent in the component (A1).

［式中、Ｒ^ｐ１及びＲ^ｐ２は、それぞれ独立に、水素原子又は炭素数１～５のアルキル基である。複数のＲ^ｐ１は、互いに同一でもよく異なってもよい。複数のＲ^ｐ２は、互いに同一でもよく異なってもよい。ｎ_１は、１～５の整数である。Ｒ^ＥＰは、エポキシ基含有基である。複数のＲ^ＥＰは、互いに同一であってもよく異なってもよい。］

[In the formula, R ^p1 and R ^p2 are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. The plurality of R ^p1s may be the same as or different from each other. The plurality of R ^p2s may be the same as or different from each other. n ₁ is an integer of 1 to 5. R ^EP is an epoxy group-containing group. The plurality of R ^EPs may be the same as or different from each other. ]

In the above formula (A2-1), the alkyl groups having 1 to 5 carbon atoms of R ^p1 and R ^p2 are, for example, linear, branched or cyclic alkyl groups having 1 to 5 carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like. Examples of the cyclic alkyl group include a cyclobutyl group and a cyclopentyl group.
Among them, as R ^p1 and R ^p2 , 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 further preferable.
In the formula (A2-1), the plurality of R ^p1s may be the same or different from each other. The plurality of R ^p2s may be the same as or different from each other.

In the formula (A2-1), n ₁ is an integer of 1 to 5, preferably 2 or 3, and more preferably 2.

In the formula (A2-1), R ^EP is an epoxy group-containing group, and has the same description as R ^EP in the above formula (abp1). Of these, the glycidyl group is preferable as the epoxy group-containing group in ^REP .

Commercially available products that can be used as the epoxy resin represented by the above general formula (A2-1) include, for example, JER-152, JER-154, JER-157S70, JER-157S65 (all manufactured by Mitsubishi Chemical Corporation) and the like. Can be mentioned.

As the component (A2), one type may be used alone, or two or more types may be used in combination.
In the photosensitive composition of the present embodiment, the content of the component (A2) is 10 to 40% by mass and 10 to 35% by mass with respect to the total mass (100% by mass) of the component (A). It is preferably 10 to 30% by mass, and more preferably 10 to 30% by mass.

When an epoxy resin having a structure represented by the general formula (a1-01) as a component (A1) and an epoxy resin represented by the general formula (A2-1) as a component (A2) are used in combination, the component (A1) is used. The content of the component (A1) (the epoxy resin having the structure represented by the general formula (a1-01)) is a wall to the substrate with respect to the total amount (100% by mass) of the component (A2) and the component (A2). From the viewpoint of achieving both adhesiveness and mold resistance of the material, it is 60 to 90% by mass, more preferably 60 to 80% by mass, further preferably 60 to 75% by mass, and 60 to 70%. The content of the component (A2) is particularly preferably 10 to 40% by mass, more preferably 20 to 40% by mass, still more preferably 25 to 40% by mass, and more preferably 25 to 40% by mass. It is more preferably 30 to 40% by mass.

When an epoxy resin having a structure represented by the general formula (a1-02) as a component (A1) and an epoxy resin represented by the general formula (A2-1) as a component (A2) are used in combination, the component (A1) is used. The content of the component (A1) (the epoxy resin having the structure represented by the general formula (a1-02)) is a wall to the substrate with respect to the total amount (100% by mass) of the component (A2) and the component (A2). From the viewpoint of achieving both adhesiveness and mold resistance of the material, it is 60 to 90% by mass, more preferably 65 to 90% by mass, further preferably 70 to 90% by mass, (A2). The content of the component is 10 to 40% by mass, more preferably 10 to 35% by mass, and even more preferably 10 to 30% by mass.

≪Other (A) component≫
In the photosensitive composition of the present embodiment, the component (A) is an epoxy group-containing compound other than the component (A1) and the component (A2) (hereinafter, this is also referred to as "component (A3)"). May include.

Examples of the component (A3) include a novolak type epoxy resin (Anv) having a structural unit represented by the following general formula (anv1).

［式中、Ｒ^ＥＰは、エポキシ基含有基であり、Ｒ^ａ２２、Ｒ^ａ２３は、それぞれ独立に水素原子、炭素数１～５のアルキル基又はハロゲン原子である。］

[In the formula, R ^EP is an epoxy group-containing group, and Ra ²² and Ra ²³ are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, or halogen atoms, respectively. ]

In the formula (anv1), the alkyl groups having 1 to 5 carbon atoms of R ^a22 and R ^a23 are the same as the alkyl groups having 1 to 5 carbon atoms of R ^p1 and R ^p2 in the formula (A2-1). The halogen atom of R ^a22 and R ^a23 is preferably a chlorine atom or a bromine atom.
In the formula (anv1), the R ^EP is the same as the R ^EP in the formula (abp1), and a glycidyl group is preferable.

A specific example of the structural unit represented by the above formula (anv1) is shown below.

The novolak type epoxy resin (Av) may be a resin composed of only the structural unit (anv1), or may be a resin having a structural unit (anv1) and another structural unit. Examples of other structural units include structural units represented by the following general formulas (anv2) to (anv3).

［式中、Ｒ^ａ２４は、置換基を有してもよい炭化水素基である。Ｒ^ａ２５～Ｒ^ａ２６、Ｒ^ａ２８～Ｒ^ａ３０は、それぞれ独立に水素原子、炭素数１～５のアルキル基又はハロゲン原子である。Ｒ^ａ２７は、エポキシ基含有基又は置換基を有してもよい炭化水素基である。］

[In the formula, ^Ra24 is a hydrocarbon group which may have a substituent. R ^a25 to ^Ra26 and R ^a28 to ^Ra30 are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, or halogen atoms, respectively. ^Ra27 is a hydrocarbon group which may have an epoxy group-containing group or a substituent. ]

In formula (anv2), ^Ra24 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 or 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 thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and the like. Among these, a methyl group, an ethyl group or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.

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

When ^Ra24 is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically. Examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

When the cyclic hydrocarbon group of ^Ra24 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 a monocyclic type or a polycyclic type. 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; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, the aromatic hydrocarbon group in ^Ra24 is a group (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle; and includes two or more aromatic rings. A group obtained by removing one hydrogen atom from an aromatic compound (for example, biphenyl, fluorene, etc.); a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or the aromatic heterocycle is substituted with an alkylene group (for example, a benzyl group, etc.). Examples thereof include an arylalkyl group such as a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, and a 2-naphthylethyl group). The carbon number of the alkylene group bonded to the aromatic hydrocarbon ring or the aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

In the formulas (anv2) and (anv3), ^Ra25 to ^Ra26 and ^Ra28 to ^Ra30 are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms or halogen atoms, and have 1 to 5 carbon atoms, respectively. The alkyl group and the halogen atom are the same as those of Ra ²² and Ra ²³ , respectively.

In formula (anv3), ^Ra27 is a hydrocarbon group which may have an epoxy group-containing group or a substituent. The epoxy group-containing group of Ra ²⁷ is the same as R ^EP in the above formula ( ^A2-1 ), and the hydrocarbon group which may have a substituent of Ra ²⁷ is the same as Ra 24.

Specific examples of the structural units represented by the above equations (anv2) to (anv3) are shown below.

When the novolak type epoxy resin (Anv) has other structural units in addition to the structural unit (anv1), the ratio of each structural unit in the resin (Anv) is not particularly limited, but the resin (Anv). ), The total of the constituent units having an epoxy group is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, still more preferably 30 to 70 mol%, based on the total of all the constituent units constituting the above.

Commercially available products that can be used as the above-exemplified novolak type epoxy resin (Anv) are, for example, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, and EPICLON N-690. , EPICLON N-695, EPICLON HP5000 (all manufactured by DIC Corporation); EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.); YDCN-704 (manufactured by Nittetsu Chemical & Materials Co., Ltd.) and the like.

Further, as the component (A3), a compound represented by the following chemical formula (A3-1) may be used in addition to the above-mentioned resin. Examples of commercially available products that can be used as the compound represented by the following chemical formula (A3-1) include TECHMORE VG-3101L (manufactured by Printec Co., Ltd.).

As the component (A3), a compound represented by the following chemical formula (A3-2) may be used in addition to the above-mentioned resin. 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) and the like.

The component (A3) includes, for example, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether; pentaerythritol tetraglycidyl ether, ditrimethylolpropane tetraglycidyl ether, diglycerin tetraglycidyl ether, erythritol tetraglycidyl ether; xylitol pentaglycidyl. Ether, dipentaerythritol pentaglycidyl ether, inositol pentaglycidyl ether; dipentaerythritol hexaglycidyl ether, sorbitol hexaglycidyl ether, inositol hexaglycidyl ether and the like can also be mentioned.

Further, examples of the component (A3) include an aliphatic epoxy resin and an acrylic resin (Aac).
Examples of the aliphatic epoxy resin and acrylic resin (Aac) include resins having epoxy group-containing units represented by the following general formulas (a1-1) to (a1-2).

［式中、Ｒは水素原子、炭素数１～５のアルキル基又は炭素数１～５のハロゲン化アルキル基である。Ｖａ^４１は、置換基を有していてもよい２価の炭化水素基である。ｎａ^４１は０～２の整数である。Ｒ^ａ４１、Ｒ^ａ４２はエポキシ基含有基である。ｎａ^４２は０又は１である。Ｗａ^４１は（ｎａ^４３＋１）価の脂肪族炭化水素基である。ｎａ^４３は１～３の整数である。］

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Va ⁴¹ is a divalent hydrocarbon group which may have a substituent. na ⁴¹ is an integer of 0 to 2. R ^a41 and R ^a42 are epoxy group-containing groups. na ⁴² is 0 or 1. Wa ⁴¹ is a (na ⁴³ +1) valent aliphatic hydrocarbon group. na ⁴³ is an integer of 1 to 3. ]

In the formula (a1-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms.
The alkyl group having 1 to 5 carbon atoms of R is preferably linear or branched, and specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl. Examples include a group, a pentyl group, an isopentyl group, a neopentyl group and the like.
The halogenated alkyl group having 1 to 5 carbon atoms of R is a group in which a part or all of hydrogen atoms of the alkyl group having 1 to 5 carbon atoms is substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is particularly preferable.
As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is most preferable from the viewpoint of industrial availability.

In the formula (a1-1), Va ⁴¹ is a divalent hydrocarbon group which may have a substituent and has a substituent described in REP in the formula ( ^abp1 ). Examples thereof include groups similar to divalent hydrocarbon groups which may be present.
Among the above, the hydrocarbon group of Va ⁴¹ is preferably an aliphatic hydrocarbon group, more preferably a linear or branched aliphatic hydrocarbon group, and further preferably a linear aliphatic hydrocarbon group. Linear alkylene groups are particularly preferred.

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

In the formulas (a1-1) and (a1-2), R ^a41 and R ^a42 are epoxy group-containing groups and are the same as R ^EP in the above formula (abp1).

In the formula (a1-2), the (na ⁴³ +1) valent aliphatic hydrocarbon group in Wa ⁴¹ means a hydrocarbon group having no aromaticity, and may be saturated or unsaturated. It is also good, usually preferably saturated. The aliphatic hydrocarbon group includes a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, or a linear or branched aliphatic hydrocarbon group. And a group combining an aliphatic hydrocarbon group containing a ring in the structure can be mentioned.

In the formula (a1-2), na ⁴³ is an integer of 1 to 3, preferably 1 or 2.

Specific examples of the structural units represented by the above formula (a1-1) or (a1-2) are shown below.

In the above formula, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.
R ^a51 represents a divalent hydrocarbon group having 1 to 8 carbon atoms. R ^a52 represents a divalent hydrocarbon group having 1 to 20 carbon atoms. R ^a53 represents a hydrogen atom or a methyl group. na ⁵¹ is an integer of 0 to 10.
R ^a51 , R ^a52 , and R ^a53 may be the same or different from each other.

Further, the acrylic resin (Aac) may have a structural unit derived from another polymerizable compound for the purpose of appropriately controlling physical and chemical properties.
Examples of such a polymerizable compound include known radically polymerizable compounds and anionic 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; 2-methacryloyloxyethyl succinic acid and 2-methacryloyloxy. Methacrylic acid derivatives having a carboxyl group and an ester bond such as ethylmaleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth). ) (Meta) acrylic acid alkyl esters such as acrylate; (meth) acrylate hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl (meth) acrylate, benzyl ( (Meta) Acrylic acid aryl esters such as acrylates; Dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α- Vinyl group-containing aromatic compounds such as methylhydroxystyrene and α-ethylhydroxystyrene; Vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile groups such as acrylonitrile and methacrylonitrile Containing polymerizable compounds; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide; and the like.

When the aliphatic epoxy resin and the acrylic resin (Aac) have other structural units, the content ratio of the epoxy group-containing unit in the resin is preferably 5 to 40 mol%, preferably 10 to 30 mol%. Is more preferable, and most preferably 15 to 25 mol%.

Further, as the aliphatic epoxy resin, a compound containing a partial structure represented by the following general formula (m1) (hereinafter, also referred to as “(m1) component”) is also preferably mentioned.

［式中、ｎ_２は、１～４の整数である。＊は結合手を示す。］

[In the formula, n ₂ is an integer of 1 to 4. * Indicates a bond. ]

In the formula (m1), n ₂ is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2.

Examples of the component (m1) include compounds in which a plurality of partial structures represented by the above general formula (m1) are bonded via a divalent linking group or a single bond. Among these, a compound in which a plurality of partial structures represented by the above general formula (m1) are bonded via a divalent linking group is preferable.
The divalent linking group here is not particularly limited, and examples thereof include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like. For the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom, the substituent described in REP (epoxy group-containing group) in the above formula ( ^abp1 ) is used. It is the same as the divalent hydrocarbon group which may have and the divalent linking group containing a hetero atom, and among them, the divalent linking group containing a hetero atom is preferable, and —Y ²¹ −C (= O). More preferably, a group represented by —O— and a group represented by —C (= O) —O—OY ²¹ −. As ^Y21 , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or an ethylene group is particularly preferable. preferable.

Further, as the aliphatic epoxy resin, a compound represented by the following general formula (m2) (hereinafter, also referred to as “(m2) component”) is also preferably mentioned.

［式中、Ｒ^ＥＰは、エポキシ基含有基である。複数のＲ^ＥＰは、互いに同一であってもよく異なっていてもよい。］

[In the formula, ^REP is an epoxy group-containing group. The plurality of R ^EPs may be the same as or different from each other. ]

In the formula (m2), the R ^EP is an epoxy group-containing group and is the same as the R ^EP in the above formula (abp1).

Commercially available products that can be used as the aliphatic epoxy resin include, for example, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (all manufactured by ADEKA Corporation); , Selokiside 8000, Selokiside 8010, EHPE-3150, EPOLEAD PB 3600, PB 4700 (all manufactured by Daicel Co., Ltd.); 850L (all manufactured by Nagase ChemteX Corporation); TEPIC-VL (manufactured by Nissan Chemical Industries, Ltd.) and the like can be mentioned.

When the (A3) component is used in combination with the photosensitive composition of the present embodiment, the content of the (A3) component shall be 30% by mass or less with respect to the total mass (100% by mass) of the (A) component. It is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, and particularly preferably 5 to 20% by mass.

The content of the component (A) in the photosensitive composition of the present embodiment may be adjusted according to the film thickness of the photosensitive resin film to be formed and the like.
For example, in the photosensitive composition of the present embodiment, the content of the component (A) is preferably 80% by mass or more, more preferably 90% by mass or more, based on the total mass (100% by mass) of the photosensitive composition. It is preferable, and more preferably 95% by mass or more.

<Cationic polymerization initiator (I)>
The cationic polymerization initiator (component (I)) is irradiated with ultraviolet rays, far ultraviolet rays, excimer laser light such as KrF and ArF, and active energy rays such as X-rays and electron beams to generate cations, and the cations are polymerized. It is a compound that can be an initiator.

The component (I) in the photosensitive composition of the present embodiment is not particularly limited, and for example, a compound represented by the following general formula (I1) (hereinafter referred to as “component (I1)”) and the following general formula (I2). ) (Hereinafter referred to as “(I2) component”), and examples thereof include a compound represented by the following general formula (I3-1) or (I3-2) (hereinafter referred to as “(I3) component”).
Among the above, since both the component (I1) and the component (I2) generate a relatively strong acid by exposure, when a pattern is formed by using a photosensitive composition containing the component (I). , Sufficient sensitivity is obtained and a good pattern is formed.

≪ (I1) component ≫
The component (I1) is a compound represented by the following general formula (I1).

［式中、Ｒ^ｂ０１～Ｒ^ｂ０４は、それぞれ独立に、置換基を有していてもよいアリール基、又はフッ素原子である。ｑは１以上の整数であって、Ｑ^ｑ＋は、それぞれ独立に、ｑ価の有機カチオンである。］

[In the formula, R ^b01 to R ^b04 are aryl groups or fluorine atoms which may independently have a substituent. q is an integer of 1 or more, and Q ^{q +} is an independently q-valent organic cation. ]

-Anion portion In the above formula (I1), R ^b01 to R ^b04 are aryl groups or fluorine atoms which may independently have a substituent.
The aryl group in R ^b01 to R ^b04 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 thereof include a naphthyl group, a phenyl group, an anthrasenyl group and the like, and a phenyl group is preferable because it is easily available.
The aryl group in R ^b01 to R ^b04 may have a substituent. The substituent is not particularly limited, but is a halogen atom, a hydroxyl group, an alkyl group (preferably a linear or branched alkyl group, preferably 1 to 5 carbon atoms), and an alkyl halide group. Is preferable, a halogen atom or an alkyl halide group having 1 to 5 carbon atoms is more preferable, and a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms is particularly preferable. It is preferable that the aryl group has a fluorine atom because the polarity of the anion portion is increased.
Among them, as R ^b01 to R ^b04 of the formula (I1), a fluorinated phenyl group is preferable, and a perfluorophenyl group is particularly preferable.

Preferred specific examples of the anion moiety of the compound represented by the formula (I1) are tetrakis (pentafluorophenyl) borate ([B _{(C6 F 5) 4 ] -} ⁾ ; tetrakis [(trifluoromethyl) phenyl] borate. ([B (C ₆ H ₄ CF ₃ ) ₄ ] ^- ); Difluorobis (pentafluorophenyl) borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ^- ); Trifluoro (pentafluorophenyl) borate ([(C 6 F 5) 2 BF 2]-); C ₆ F ₅ ) BF ₃ ] ^- ); Tetrakiss (difluorophenyl) borate ([B (C ₆ H ₃ F ₂ ) ₄ ] ^- ) and the like.
Of these, tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ^- ) is particularly preferable.

-In the cation part equation (I1), q is an integer of 1 or more, and Q ^{q +} is an organic cation having a q valence independently.
Sulfonium cations and iodonium cations are preferably mentioned as the Q ^{q +} , and organic cations represented by the following general formulas (ca-1) to (ca-5) are particularly preferable.

［式中、Ｒ^２０１～Ｒ^２０７、およびＲ^２１１～Ｒ^２１２は、それぞれ独立に、置換基を有していてもよいアリール基、ヘテロアリール基、アルキル基またはアルケニル基を表す。Ｒ^２０１～Ｒ^２０３、Ｒ^２０６～Ｒ^２０７、Ｒ^２１１～Ｒ^２１２は、相互に結合して、式中のイオウ原子と共に環を形成してもよい。Ｒ^２０８～Ｒ^２０９は、それぞれ独立に、水素原子または炭素数１～５のアルキル基を表す。Ｒ^２１０は、置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、又は置換基を有していてもよい－ＳＯ_２－含有環式基である。Ｌ^２０１は、－Ｃ（＝Ｏ）－または－Ｃ（＝Ｏ）－Ｏ－を表す。Ｙ^２０１は、それぞれ独立に、アリーレン基、アルキレン基またはアルケニレン基を表す。ｘは、１または２である。Ｗ^２０１は、（ｘ＋１）価の連結基を表す。］

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

Examples of the aryl group in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² include an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable.
Examples of the heteroaryl group in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² include those in which a part of the carbon atom constituting the aryl group is replaced with a hetero atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Examples of the heteroaryl group include a group obtained by removing one hydrogen atom from 9H-thioxanthene; and examples of the substituted heteroaryl group include a group obtained by removing one hydrogen atom from 9H-thioxanthene-9-one.
The alkyl group in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
The alkenyl group in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² preferably has 2 to 10 carbon atoms.
Examples of the substituents that R ²⁰¹ to R ²⁰⁷ and R ²¹⁰ to R ²¹² may have include an alkyl group, a halogen atom, an alkyl halide group, a carbonyl group, a cyano group, an amino group, and an oxo group (=). Examples thereof include O), an aryl group, and a group represented by the following formulas (ca-r-1) to (ca-r-10), respectively.

［式中、Ｒ’^２０１は、それぞれ独立に、水素原子、置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基、又は置換基を有していてもよい鎖状のアルケニル基である。］

[In the formula, ^R'201 independently has a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. It is a chain alkenyl group that may be present. ]

In the above formulas (ca-r-1) to (ca-r-10), ^R'201 independently has a hydrogen atom and a cyclic group and a substituent which may have a substituent. It is a chain-like alkyl group which may be present, or a chain-like alkenyl group which may have a substituent.

Cyclic group which may have a substituent:
The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. Further, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

The aromatic hydrocarbon group in ^R'201 is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, still more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, the carbon number does not include the carbon number in the substituent.
Specifically, as the aromatic ring of the aromatic hydrocarbon group in ^R'201 , benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or a part of carbon atoms constituting these aromatic rings is substituted with a heteroatom. Examples thereof include aromatic heterocycles, or rings in which a part of hydrogen atoms constituting these aromatic rings or aromatic heterocycles is substituted with an oxo group or the like. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like.
Specifically, as the aromatic hydrocarbon group in ^R'201 , a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, an anthracenyl group, etc.), a hydrogen atom of the aromatic ring. A group in which one of the groups is substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.), A group obtained by removing one hydrogen atom from a ring in which a part of the hydrogen atom constituting the aromatic ring is substituted with an oxo group or the like (for example, anthraquinone), or an aromatic heterocycle (for example, 9H-thioxanthene or 9H-thioxanthene). A group obtained by removing one hydrogen atom from -9-on, etc.) can be mentioned. The carbon number of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

Examples of the cyclic aliphatic hydrocarbon group in ^R'201 include an aliphatic hydrocarbon group containing a ring in the structure.
As the aliphatic hydrocarbon group containing a ring in this structure, an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an alicyclic hydrocarbon ring) and an alicyclic hydrocarbon group are linear or branched. Examples thereof include a group bonded to the end of a chain-shaped aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a monocycloalkane is preferable. 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 obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 30 carbon atoms. Among them, the polycycloalkane is a polycycloalkane having a polycyclic skeleton of a crosslinked ring system such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecan; a fused ring system such as a cyclic group having a steroid skeleton. Polycycloalkanes having a polycyclic skeleton of are more preferred.

Among them, as the cyclic aliphatic hydrocarbon group in ^R'201 , a group in which one or more hydrogen atoms are removed from monocycloalkane or polycycloalkane is preferable, and a group in which one hydrogen atom is removed from polycycloalkane is preferable. More preferably, an adamantyl group and a norbornyl group are particularly preferable, and an adamantyl group is most preferable.

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, and 1 to 4 carbon atoms. Is more preferable, and 1 to 3 are most preferable.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [-CH _2- ], an ethylene group [-(CH ₂ ) _2- ], a trimethylene group [ -(CH ₂ ) _3- ], tetramethylene group [-(CH ₂ ) _4- ], pentamethylene group [-(CH ₂ ) _5- ] and the like can be mentioned.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, and -C (CH ₃ ). _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) ₂ -etc. Alkyl methylene groups;- CH (CH ₃ ) CH _2- , -CH (CH ₃ ) CH (CH ₃ )-, -C (CH ₃ ) ₂ CH _2- , -CH (CH ₂ CH ₃ ) CH _2- , -C (CH ₂ ) CH ₃ ) ₂ -CH ₂ -etc. Alkylethylene groups; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ -etc. Alkyltrimethylene groups; -CH (CH ₃ ) Examples thereof include an alkylalkylene group such as an alkyltetramethylene group such as CH ₂ CH ₂ CH _2- , −CH ₂ CH (CH ₃ ) CH ₂ CH _2- , and the like. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

Chain-like alkyl group which may have a substituent:
The chain-like alkyl group of ^R'201 may be either linear or branched.
The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specifically, for example, 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 and a tetradecyl group. Examples thereof include a 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-chain alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, for example, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, Examples thereof include 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group and 4-methylpentyl group.

Chain alkenyl group which may have a substituent:
The chain alkenyl group of ^R'201 may be either linear or branched, preferably having 2 to 10 carbon atoms, more preferably 2 to 5, and even more preferably 2 to 4. 3 is particularly preferable. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), a butynyl group and the like. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, a 2-methylpropenyl group and the like.
Among the above, as the chain alkenyl group, a linear alkenyl group is preferable, a vinyl group and a propenyl group are more preferable, and a vinyl group is particularly preferable.

Examples of the substituent in the cyclic group, chain-like alkyl group or alkenyl group of ^R'201 include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group and an oxo group. Examples thereof include a cyclic group, an alkylcarbonyl group and a thienylcarbonyl group in ^R'201 .

Among them, ^R'201 is preferably a cyclic group which may have a substituent and a chain alkyl group which may have a substituent.

When R ²⁰¹ to R ²⁰³ , R ²⁰⁶ to R ²⁰⁷ , and R ²¹¹ to R ²¹² are bonded to each other to form a ring together with the sulfur atom in the formula, heteroatoms such as sulfur atom, oxygen atom, and nitrogen atom, and heteroatoms such as sulfur atom and nitrogen atom are formed. Carbonyl group, -SO-, -SO _2- , -SO _3- , -COO-, -CONH- or _-N (RN)-(the _RN is an alkyl group having 1 to 5 carbon atoms), etc. It may be bonded via a functional group of. As the ring to be formed, one ring containing a sulfur atom in its ring skeleton, including the sulfur atom, is preferably a 3- to 10-membered ring, and particularly preferably a 5- to 7-membered ring. preferable. Specific examples of the formed ring include, for example, thiophene ring, thiazole ring, benzothiophene ring, thianthrene ring, benzothiophene ring, dibenzothiophene ring, 9H-thioxanthene ring, thioxanthone ring, thianthrene ring, phenoxatiin ring, tetrahydro. Examples thereof include a thiophenium ring and a tetrahydrothiopyranium ring.

In the above formula (ca-3), R ²⁰⁸ to R ²⁰⁹ independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. In the case of, they may be bonded to each other to form a ring.

In the above formula (ca-3), R ²¹⁰ is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an alkenyl group which may have a substituent. It is a _—SO2 -containing cyclic group which may have a substituent.
Examples of the aryl group in R ²¹⁰ include an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable.
The alkyl group in R ²¹⁰ is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
The alkenyl group in R ²¹⁰ preferably has 2 to 10 carbon atoms.

In the above formulas (ca-4) and (ca-5), Y ²⁰¹ independently represents an arylene group, an alkylene group or an alkenylene group, respectively.
Examples of the arylene group in Y ²⁰¹ include a group obtained by removing one hydrogen atom from the aryl group exemplified as the aromatic hydrocarbon group in ^R'201 .
Examples of the alkylene group and the alkaneylene group in Y ²⁰¹ include a chain-like alkyl group in ^R'201 and a group in which one hydrogen atom is removed from the group exemplified as the chain-like alkenyl group.

In the above formula (ca-4) and formula (ca-5), x is 1 or 2.
W ²⁰¹ is a (x + 1) valence, i.e., a divalent or trivalent linking group.
As the divalent linking group in W ²⁰¹ , a divalent hydrocarbon group which may have a substituent is preferable, and a substituent exemplified by REP in the above formula ( ^abp1 ) may be possessed. Groups similar to divalent hydrocarbon groups are preferred. The divalent linking group in W ²⁰¹ may be linear, branched or cyclic, and is preferably cyclic. Of these, a group in which two carbonyl groups are combined at both ends of the arylene group or a group consisting of only an arylene group is preferable. Examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is particularly preferable.
Examples of the trivalent linking group in W ²⁰¹ include a group obtained by removing one hydrogen atom from the divalent linking group in W ²⁰¹ , and a group in which the divalent linking group is further bonded to the divalent linking group. Can be mentioned. As the trivalent linking group in W ²⁰¹ , a group in which two carbonyl groups are bonded to an arylene group is preferable.

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

［式中、Ｒ”^２０１は、水素原子又は置換基である。該置換基としては、前記Ｒ^２０１～Ｒ^２０７、およびＲ^２１０～Ｒ^２１２が有していてもよい置換基として挙げたものと同様である。］

[In the formula, R " ²⁰¹ is a hydrogen atom or a substituent. As the substituent, those listed as the substituents that the R ²⁰¹ to R ²⁰⁷ and the R ²¹⁰ to R ²¹² may have. The same is true.]

Further, as the cation represented by the above formula (ca-1), the cations represented by the following general formulas (ca-1-25) to (ca-1-35) are also preferable.

［式中、Ｒ’^２１１はアルキル基である。Ｒ^ｈａｌは、水素原子又はハロゲン原子である。］

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

Further, as the cation represented by the above formula (ca-1), the cations represented by the following chemical formulas (ca-1-36) to (ca-1-47) are also preferable.

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

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

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

Further, as the cation represented by the above formula (ca-5), the cations represented by the following general formulas (ca-5-1) to (ca-5-3) are also preferable.

［式中、Ｒ’^２１２はアルキル基又は水素原子である。Ｒ’^２１１はアルキル基である。］

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

Among the above, the cation portion [(Q ^{q +} ) _{1 / q} ] is preferably a cation represented by the general formula (ca-1), and is represented by the formulas (ca-1-1) to (ca-1-47), respectively. The represented cations are more preferred, and the cations represented by the formulas (ca-1-29), formula (ca-1-35), and formula (ca-1-47) are even more preferred.

≪ (I2) component ≫
The component (I2) is a compound represented by the following general formula (I2).

［式中、Ｒ^ｂ０５は、置換基を有していてもよいフッ素化アルキル基、又はフッ素原子である。複数のＲ^ｂ０５は、互いに同一であってもよく異なっていてもよい。ｑは１以上の整数であって、Ｑ^ｑ＋は、それぞれ独立に、ｑ価の有機カチオンである。］

[In the formula, R ^b05 is a fluorinated alkyl group or a fluorine atom which may have a substituent. The plurality of R ^b05s may be the same as or different from each other. q is an integer of 1 or more, and Q ^{q +} is an independently q-valent organic cation. ]

-Anion portion In the above formula (I2), R ^b05 is a fluorinated alkyl group or a fluorine atom which may have a substituent. The plurality of R ^b05s may be the same as or different from each other.
The fluorinated alkyl group in R ^b05 preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms. Specifically, in the alkyl group having 1 to 5 carbon atoms, a group in which a part or all of a hydrogen atom is replaced with a fluorine atom can be mentioned.
Among them, as R ^b05 , 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, a trifluoromethyl group or a pentafluoro is preferable. Ethyl groups are more preferred.

The anion portion of the compound represented by the formula (I2) is preferably represented by the following general formula (b0-2a).

［式中、Ｒ^ｂｆ０５は、置換基を有していてもよいフッ素化アルキル基である。ｎｂ^１は、１～５の整数である。］

[In the formula, R ^bf05 is a fluorinated alkyl group which may have a substituent. nb ¹ is an integer of 1 to 5. ]

In the formula (b0-2a), the fluorinated alkyl group which may have a substituent in R ^bf05 is the same as the fluorinated alkyl group which may have a substituent described in R ^b05 . be.
Among them, as R ^bf05 , a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, a perfluoroalkyl group having 1 to 5 carbon atoms is more preferable, and a trifluoromethyl group or a pentafluoroethyl group is further preferable.
In the 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.

-In the cation part equation (I2), q is an integer of 1 or more, and Q ^{q +} is an organic cation having a q valence independently.
As the Q ^{q +} , the same as the above formula (I1) can be mentioned, and among them, the cation represented by the general formula (ca-1) is preferable, and the formulas (ca-1-1) to (ca-1) are preferable. The cations represented by −47) are more preferable, and the cations represented by the formulas (ca-1-35) and (ca-1-47) are even more preferable.

≪ (I3) component ≫
The component (I3) is a compound represented by the following general formula (I3-1) or (I3-2).

［式中、Ｒ^ｂ１１～Ｒ^ｂ１２は、ハロゲン原子以外の置換基を有していてもよい環式基、ハロゲン原子以外の置換基を有していてもよい鎖状のアルキル基、又はハロゲン原子以外の置換基を有していてもよい鎖状のアルケニル基である。ｍは１以上の整数であって、Ｍ^ｍ＋はそれぞれ独立にｍ価の有機カチオンである。］

[In the formula, R ^b11 to R ^b12 are 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 halogen atom. It is a chain alkenyl group which may have a substituent other than the above. m is an integer of 1 or more, and M ^{m +} is an independently m-valent organic cation. ]

{(I3-1) component}
-In the anion part formula (I3-1), R ^b12 is a cyclic group which may have a substituent other than a halogen atom, and a chain alkyl group which may have a substituent other than a halogen atom. , Or a chain alkenyl group that may have a substituent other than a halogen atom, among the cyclic group, chain alkyl group, and chain alkenyl group described above in ^R'201 . , Those having no substituent or those having a substituent other than the halogen atom.
The 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-like alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. As the aliphatic cyclic group, a group obtained by removing one or more hydrogen atoms from adamantan, norbornane, isobornane, tricyclodecane, tetracyclododecan, etc. (may have a substituent other than a halogen atom); It is more preferable that the group is obtained by removing one or more hydrogen atoms from the above.
The hydrocarbon group of R ^b12 may have a substituent other than the halogen atom, and the substituent may be a hydrocarbon group (aromatic hydrocarbon group, aliphatic group) in R ^b11 of the above formula (I3-2). Examples thereof include substituents other than the halogen atom which the cyclic group (cyclic group, chain alkyl group) may have.
The term "may have a substituent other than a halogen atom" as used herein means not only excluding the case of having a substituent consisting of only a halogen atom but also the case of having a substituent containing at least one halogen atom. (For example, when the substituent is a fluorinated alkyl group, etc.) is excluded.

A preferable specific example of the anion portion of the component (I3-1) is shown below.

-Cation part In formula (I3-1), M ^{m +} is an m-valent organic cation.
As the organic cation of M ^{m +} , the same cations as those represented by the above general formulas (ca-1) to (ca-5) are preferably mentioned, and among these, the above general formula (ca-1) is used. The cation represented by is more preferable. Among these, at least one of R ²⁰¹ , R ²⁰² , and R ²⁰³ in the above general formula (ca-1) may have a substituent and may have an organic group having 16 or more carbon atoms (aryl group, heteroaryl). A sulfonium cation (group, alkyl group or alkenyl group) is particularly preferable because it improves resolution and roughness characteristics.
The substituents that the organic group may have are the same as above, and are an alkyl group, a halogen atom, an alkyl halide group, a carbonyl group, a cyano group, an amino group, an oxo group (= O), and an aryl. Groups and groups represented by the above formulas (ca-r-1) to (ca-r-10) can be mentioned.
The organic group (aryl group, heteroaryl group, alkyl group or ^alkenyl group) preferably has 16 to 25 carbon atoms, more preferably 16 to 20 carbon atoms, and particularly preferably 16 to 18 carbon atoms. Examples of the organic cations of the above formulas (ca-1-25), (ca-1-26), (ca-1-28) to (ca-1-36), (ca-1-38), and the like. Preferred are cations represented by (ca-1-46) and (ca-1-47), respectively, and among them, cations represented by the above formula (ca-1-29) are particularly preferable.

{(I3-2) component}
-In the anion part formula (I3-2), R ^b11 is a cyclic group which may have a substituent other than a halogen atom, and a chain alkyl group which may have a substituent other than a halogen atom. , Or a chain alkenyl group that may have a substituent other than a halogen atom, among the cyclic group, chain alkyl group, and chain alkenyl group described above in ^R'201 . , Those having no substituent or those having a substituent other than the halogen atom.

Among these, as R ^b11 , 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 halogen. A chain alkyl group which may have a substituent other than an atom is preferable. Examples of the substituent that these groups may have include 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, an alkylene group may be used as a substituent. In this case, the substituents are shown in the following general formulas (y-al-1) to (y-al-7), respectively. The linking group to be added is preferable.

［式中、Ｖ’^１０１は単結合または炭素数１～５のアルキレン基であり、Ｖ’^１０２は炭素数１～３０の２価の飽和炭化水素基である。］

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

The divalent saturated hydrocarbon group in ^V'102 is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and an alkylene group having 1 to 5 carbon atoms. Is more preferable.

The alkylene group in ^V'101 and ^V'102 may be a linear alkylene group or a branched chain alkylene group, and a linear alkylene group is preferable.
Specific examples of the alkylene group in ^V'101 and ^V'102 are methylene groups [-CH ₂ -];-CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, -C (CH ₃ ). _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) ₂ -etc. Alkyl methylene groups; ethylene Group [-CH ₂ CH _2- ]; -CH (CH ₃ ) CH _2- , -CH (CH ₃ ) CH (CH ₃ )-, -C (CH ₃ ) ₂ CH _2- , -CH (CH ₂ CH) ₃ ) Alkylethylene groups such as CH _2- ; trimethylene group (n-propylene group) [-CH ₂ CH ₂ CH _2- ]; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) Alkyltrimethylene groups such as CH _2- ; Tetramethylene groups [-CH ₂ CH ₂ CH ₂ CH _2- ]; -CH (CH ₃ ) CH ₂ CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ Alkyltetramethylene groups such as CH _2- ; pentamethylene groups [-CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ] and the like can be mentioned.
Further, a part of the methylene group in the alkylene group in ^V'101 or ^V'102 may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic ring-type group is obtained by further removing one hydrogen atom from the cyclic aliphatic hydrocarbon group of ^R'201 (monocyclic alicyclic hydrocarbon group, polycyclic alicyclic hydrocarbon group). A divalent group is preferable, and a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group is more preferable.

As the aromatic hydrocarbon group, a phenyl group or a naphthyl group is more preferable.
The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
The chain-like alkyl group preferably has 1 to 10 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like. Linear alkyl groups such as nonyl group and decyl group; 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl Examples thereof include branched alkyl groups such as a group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

As R ^b11 , a cyclic group which may have a substituent other than a halogen atom is preferable.
A preferable specific example of the anion portion of the component (I3-2) is shown below.

-Cation part In the formula (I3-2), M ^{m +} is an organic cation having an m valence, which is the same as M ^{m +} in the formula (I3-1).

Further, the component (I) is a cationic polymerization initiator that generates an acid having a pKa (acid dissociation constant) of -5 or less by exposure because of the high elasticity of the resin film and the tendency to form a fine structure without residue. It is preferable to have. High sensitivity to exposure can be obtained by using a cationic polymerization initiator that generates an acid having a pKa of -6 or less, more preferably -8 or less. (I) The lower limit of pKa of the acid generated by the component is preferably -15 or more. By using such a cationic polymerization initiator that generates a suitable pKa acid, high sensitivity can be easily achieved.
Here, "pKa (acid dissociation constant)" refers to a substance generally used as an index indicating the acid strength of the target substance. In addition, pKa in this specification is a value under the temperature condition of 25 degreeC. Further, the pKa value can be measured and obtained by a known method. Further, calculated values using known software such as "ACD / Labs" (trade name, manufactured by Advanced Chemistry Development) can also be used.

Specific examples of the suitable component (I) are given below.

As the component (I), one type may be used alone, or two or more types may be used in combination.
The component (I) preferably contains at least one selected from the group consisting of the component (I1), the component (I2) and the component (I3), and is selected from the group consisting of the component (I1) and the component (I3). It is more preferable to contain one or more kinds, and it is further preferable to contain the component (I1) and the component (I3) in combination.

The content of the component (I) is preferably 0.3 to 5 parts by mass, more preferably 0.5 to 4 parts by mass, and 1 to 3 parts by mass with respect to 100 parts by mass of the component (A). It is more preferably 5.5 parts by mass.
When the content of the component (I) is at least the lower limit of the above-mentioned preferable range, sufficient sensitivity is obtained and the lithography characteristics of the pattern are further improved. In addition, the strength of the cured film is further increased. On the other hand, when it is not more than the upper limit of the above-mentioned preferable range, the sensitivity is appropriately controlled, and it becomes easy to obtain a pattern having a good shape.

<Arbitrary ingredient>
The photosensitive composition of the present embodiment may contain other components, if necessary, in addition to the above-mentioned components (A) and (I).
To the photosensitive composition of the embodiment, optionally, an additive for improving the performance of a miscible additive such as a metal oxide (M), a silane coupling agent, a sensitizer component, a solvent, and a film. A resin, a dissolution inhibitor, a basic compound, a plasticizer, a stabilizer, a colorant, an antihalation agent and the like can be appropriately added and contained.

≪Metal oxide (M) ≫
In the photosensitive composition of the present embodiment, in addition to the component (A) and the component (I), a cured film having increased strength can be easily obtained. ) Ingredients ”) may be contained. Further, by having the component (M) together, a high-resolution pattern can be formed with a good shape.
Examples of the component (M) include oxides of metals such as silicon (metal silicon), titanium, zirconium, and hafnium. Among these, an oxide of silicon is preferable, and among these, silica is particularly preferable.

Further, the shape of the component (M) is preferably particulate.
As the particle-like (M) component, those having a volume average particle diameter of 5 to 40 nm are preferable, those having a volume average particle diameter of 5 to 30 nm are more preferable, and those having a volume average particle diameter of 5 to 30 nm are more preferable. A particle group having a particle size of 10 to 20 nm is more preferable.
When the volume average particle size of the component (M) is at least the lower limit of the above-mentioned preferable range, the strength of the cured film is likely to be increased. On the other hand, when it is not more than the upper limit of the above-mentioned preferable range, residue is less likely to be generated in the formation of the pattern, and a pattern having a higher resolution is more likely to be formed. In addition, the transparency of the resin film is enhanced.
The particle size of the component (M) may be appropriately selected according to the exposure light source. Generally, it is said that the influence of light scattering is almost negligible for particles having a particle diameter of 1/10 or less with respect to the wavelength of light. Therefore, for example, when a fine structure is formed by photolithography with i-line (365 nm), the (M) component is a particle group having a primary particle diameter (volume average value) of 10 to 20 nm (particularly preferably a silica particle group). ) Is preferably used.

As the component (M), one type may be used alone, or two or more types may be used in combination.
When the component (M) is contained, the content is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the component (A).
When the content of the component (M) is at least the lower limit of the above-mentioned preferable range, the strength of the cured film is further increased. On the other hand, when it is not more than the upper limit of the above preferable range, the transparency of the resin film is further enhanced.

≪Silane coupling agent≫
The photosensitive composition of the present embodiment may further contain an adhesive aid in order to improve the adhesiveness with the substrate. As the adhesive aid, a silane coupling agent is preferable.
Examples of the silane coupling agent include a silane coupling agent having a reactive substituent such as a carboxy group, a methacryloyl group, an isocyanate group, and an epoxy group. Specific examples include trimethoxysilyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl). Ethyltrimethoxysilane and the like can be mentioned.
One type of silane coupling agent may be used alone, or two or more types may be used in combination.
When the silane coupling agent is contained, the content is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass with respect to 100 parts by mass of the component (A). It is more preferably 0.5 to 10 parts by mass.
When the content of the silane coupling agent is in the above-mentioned preferable range, the strength of the cured film is further increased. In addition, the adhesiveness between the cured film and the substrate is further strengthened.

≪Sensitizer ingredient≫
The photosensitive composition of the present embodiment may further contain a sensitizer component.
The sensitizer component is not particularly limited as long as it can absorb energy from exposure and transfer 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, acetphen-based photosensitizers, and 1,5-dihydroxynaphthalene. Naphthalene-based photosensitizers such as, phenol-based photosensitizers, anthracene-based photosensitizers such as 9-ethoxyanthracene, and known photosensitizers such as biacetyl, eosin, rosebengal, pyrene, phenothiazine, and antron. Can be used.
As the sensitizer component, one type may be used alone, or two or more types may be used in combination.
When the sensitizer component is contained, the content is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the component (A). It is more preferably 0.5 to 5 parts by mass.
When the content of the sensitizer component is in the above-mentioned preferable range, the sensitivity and the resolvability are further enhanced.

≪Solvent≫
The photosensitive composition of the present embodiment may further contain a solvent (hereinafter, may be referred to as "component (S)").
Examples of the component (S) include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone and 2-heptanone; ethylene glycol and diethylene glycol. , Polyvalent alcohols such as propylene glycol, dipropylene glycol; 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol. A compound having an ester bond such as monoacetate, a monomethyl ether such as the polyhydric alcohol or the compound having the ester bond, a monoalkyl ether such as monoethyl ether, monopropyl ether, or monobutyl ether, or an ether bond such as monophenyl ether. Derivatives of polyhydric alcohols such as compounds having [Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferable]; cyclic ethers such as dioxane, methyl lactate, and lactic acid. Esters such as ethyl (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, diphenyl ether, di Examples thereof include aromatic organic solvents such as benzyl ether, phenetol, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, simene and mesityrene, and dimethylsulfoxide (DMSO).
As the component (S), one type may be used alone, or two or more types may be used as a mixed solvent.

The amount to be used when the component (S) is contained is not particularly limited, and is appropriately set according to the coating film thickness at a concentration at which the photosensitive composition can be applied to a substrate or the like without dripping.
For example, the component (S) can be used so that the solid content concentration is 50% by mass or more, and the component (S) can be used so that the solid content concentration is 60% by mass or more.
Further, an embodiment in which the component (S) is substantially not contained (that is, an embodiment in which the solid content concentration is 100% by mass) can also be adopted.

In the negative photosensitive composition of the present embodiment described above, the component (A1): epoxy equivalent is 300 g / eq with respect to the total mass (100% by mass) of the epoxy group-containing compound (A). The above epoxy resin 60 to 90% by mass and the component (A2): the epoxy resin having an epoxy equivalent smaller than the component (A1) 10 to 40% by mass represented by the general formula (A2-1) are combined. I am using it.

By applying such a negative photosensitive composition containing specific epoxy group-containing compounds having different epoxy equivalents, the stress inside the cured film formed by the synergistic action between the specific epoxy group-containing compounds is increased. Since it can be kept low, it is possible to improve the adhesion between the substrate and the material to be the wall. In addition, the hollow structure produced by using the negative photosensitive composition of the present embodiment is less likely to cause a failure and has high reliability.
Further, by applying a negative photosensitive composition having a specific epoxy group-containing compound having a different epoxy equivalent, the heat of the cured film formed by the synergistic action between the specific epoxy group-containing compounds is obtained. The time elastic modulus is increased, and the mold resistance can be improved.

In the negative photosensitive composition of the present embodiment, the stress in the cured product is preferably 20 MPa or less, more preferably 18 MPa or less, and more preferably 16 MPa or less, from the viewpoint of adhesion of the cured film to the substrate. It is more preferably present, and particularly preferably 14 MPa or less.

The stress in the cured product can be measured using a residual stress measuring device.

In the negative photosensitive composition of the present embodiment, the elastic modulus E * at 150 ° C. of the cured product is preferably 40 MPa or more, more preferably 42 MPa or more, from the viewpoint of mold resistance. It is more preferably 45 MPa or more, and particularly preferably 50 MPa or more.

The thermal elastic modulus E * at 150 ° C. of the cured product is a measured value at a temperature of 150 ° C. when the viscoelasticity of the cured film is measured at a frequency of 1 MHz.

Further, according to the negative photosensitive composition of the present embodiment, in the production of the hollow sealing structure, a film having a thickness required for the spacer can be formed, and the shape is good, there is no residue, and the resolution is high. Patterning is possible.

Further, the negative photosensitive composition of the present embodiment can be similarly patterned even when a film is formed of a thick film, and good properties can be obtained. Therefore, the negative photosensitive composition of the present embodiment is also useful for a photosensitive dry film resist.

(Pattern formation method)
The pattern forming method of the present embodiment includes a step of forming a photosensitive resin film on a support (hereinafter referred to as "film forming step") using the negative photosensitive composition of the above-described embodiment and the photosensitive. A step of exposing the resin film (hereinafter referred to as "exposure step") and a step of developing the photosensitive resin film after exposure with a developing solution containing an organic solvent to form a negative pattern (hereinafter referred to as "development step"). ), And has.
The pattern forming method of the present embodiment can be performed as follows, for example.

[Film formation process]
First, the negative photosensitive composition of the above-described embodiment is applied onto the support by a known method such as a spin coating method, a roll coating method, a screen printing method, and a bake (post-apply bake (PAB)) treatment. For 2 to 60 minutes under temperature conditions of, for example, 50 to 150 ° C. to form a photosensitive resin film.

The support is not particularly limited, and conventionally known ones can be used, and examples thereof include a substrate for electronic components and a support having a predetermined wiring pattern formed therein. More specifically, it is made of metal such as silicon, silicon nitride, titanium, tantalum, lithium tantalate (LiTaO ₃ ), niobium, lithium niobate (LiNbO ₃ ), palladium, titanium tungsten, copper, chromium, iron and aluminum. Examples include a substrate and a glass substrate. As the material of the wiring pattern, for example, copper, aluminum, nickel, gold and the like can be used.

In the pattern forming method of the present embodiment, it is preferable to use, for example, a lithium tantalate substrate (LiTaO ₃ substrate) or a lithium niobate substrate (LiNbO ₃ substrate) for SAW devices mounted on a communication terminal as a support.

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

[Exposure process]
Next, the formed photosensitive resin film is exposed to the formed photosensitive resin film through a mask (mask pattern) in which a predetermined pattern is formed, or by direct irradiation of an electron beam without a mask pattern, using a known exposure device. Selective exposure by drawing or the like.
After the selective exposure, if necessary, a baking (post-exposure baking (PEB)) treatment is performed, for example, at a temperature condition of 80 to 150 ° C. for 40 to 1200 seconds, preferably 40 to 1000 seconds, more preferably. Apply for 60-900 seconds.

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

The exposure method of the photosensitive resin film may be a normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or an immersion exposure (Liquid Immersion Lithology).

The photosensitive resin film after the exposure step has high transparency, and for example, the haze value when irradiated with i-line (wavelength 365 nm) is preferably 3% or less, more preferably 1.0 to 2.7%. ..
As described above, the photosensitive resin film formed by using the negative photosensitive composition of the above-described embodiment has high transparency. Therefore, during exposure in pattern formation, light transmission is increased, and a negative pattern having good lithography characteristics can be easily obtained.
The haze value of the photosensitive resin film after such an exposure step is measured by using a method according to JIS K 7136 (2000).

[Development process]
Next, the photosensitive resin film after the exposure is developed with a developing solution (organic developer) containing an organic solvent. After development, a rinsing treatment is preferably performed. Baking processing (post-baking) may be performed if necessary.

The organic solvent contained in the organic developer may be any one that can dissolve the component (A) (component (A) before exposure), and can be appropriately selected from known organic solvents. Specific examples thereof include ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, polar solvents such as ether solvents, hydrocarbon solvents and the like.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone and methylethylketone. , Methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, γ-butyrolactone, methylamylketone (2-heptanone) and the like. Among these, methylamylketone (2-heptanone) is preferable as the ketone solvent.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxy acetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether acetate, and the like. 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 mono Ethyl 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, propylene 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 formic acid, ethyl formic acid, formic acid Butyl, propyl silicate, 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-ethoxy Examples thereof include propionate and propyl-3-methoxypropionate. Among these, butyl acetate or PGMEA is preferable as the ester solvent.

Examples of the nitrile-based solvent include acetonitrile, propionitril, valeronitrile, butyronitril and the like.

A known additive can be added to the organic developer, if necessary. Examples of the additive include a surfactant. The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and / or silicon-based surfactant can be used.
As the surfactant, a nonionic surfactant is preferable, and a nonionic fluorine-based surfactant or a nonionic silicon-based surfactant is more preferable.
When the surfactant is blended, the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and 0.01 to 0.% With respect to the total amount of the organic developer. 5% by mass is more preferable.

The developing process can be carried out by a known developing method. For example, a method of immersing a support in a developing solution for a certain period of time (dip method), or a method in which a developing solution is raised on the surface of a support by surface tension for a certain period of time. A method of standing still (paddle method), a method of spraying the developer on the surface of the support (spray method), a method of applying the developer on the support rotating at a constant speed while scanning the developer dispensing nozzle at a constant speed. Examples include a method of continuously producing (dynamic dispense method).

The rinsing treatment (cleaning treatment) using the rinsing liquid can be carried out by a known rinsing method. Examples of the rinsing treatment method include a method of continuously spraying the rinsing liquid on a support rotating at a constant speed (rotary coating method), a method of immersing the support in the rinsing liquid for a certain period of time (dip method), and the like. Examples thereof include a method of spraying a rinse liquid on the surface of the support (spray method).
For the rinsing treatment, it is preferable to use a rinsing liquid containing an organic solvent.

A pattern can be formed by the film forming step, the exposure step and the developing step described above.

In the pattern forming method of the above-described embodiment, since the negative photosensitive composition according to the first aspect described above is used, the stress inside the cured film is suppressed to a low level, and the elastic modulus is high, so that the mold can be molded. It is possible to form a pattern with increased resistance.
The pattern forming method of such an embodiment is a useful method for producing a side wall (Wall) of a hollow structure. By applying such a pattern forming method, it is possible to manufacture a hollow structure having excellent heat cycle test, less likely to cause failure, and high reliability.
In addition, according to the pattern forming method of the embodiment, high sensitivity can be achieved, residues can be reduced, and a pattern having a good shape can be formed.

(Hardened film)
The cured film of the present embodiment is a cured negative-type photosensitive composition of the above-mentioned embodiment.

From the viewpoint of adhesion to the substrate, the cured film of the present embodiment preferably has a stress of 20 MPa or less, more preferably 4 MPa or more and 20 MPa or less, and further preferably 7 MPa or more and 20 MPa or less. It is preferable, and it is particularly preferable that it is 10 MPa or more and 20 MPa or less.

From the viewpoint of mold resistance, the cured film of the present embodiment preferably has a thermal elastic modulus E * at 150 ° C. of 40 MPa or more, more preferably 40 MPa or more and 100 MPa or less, and 40 MPa or more and 95 MPa. It is more preferably 40 MPa or more and 90 MPa or less, and particularly preferably 90 MPa or less.

How to manufacture a cured film:
The method for producing a cured film of the present embodiment includes the step (i) of forming a photosensitive resin film on a support using the negative photosensitive composition of the above-described embodiment and the curing of the photosensitive resin film. It has a step (ii) of obtaining a cured film.
The operation of the step (i) can be performed in the same manner as the above-mentioned [film forming step]. The baking treatment can be performed, for example, under the temperature condition of 80 to 150 ° C. for 40 to 600 seconds.
The curing treatment in the step (ii) can be performed under the conditions of, for example, a temperature of 100 to 250 ° C. and 0.5 to 2 hours.

The method for producing the cured film of the embodiment may include other steps in addition to the step (i) and the step (ii). For example, the above-mentioned [exposure step] may be provided between the step (i) and the step (ii), and the photosensitive resin film formed in the step (i) is selectively exposed. If necessary, the photosensitive resin film (pre-cured film) subjected to the bake (PEB) treatment can be cured to obtain a cured film.
According to the method for producing a cured film of the above-described embodiment, it is possible to improve the adhesion to the support and the mold resistance, and further, it is easy to obtain a cured film that faithfully reproduces the mask pattern. Can be manufactured.

(Manufacturing method of hollow structure)
The method for manufacturing a hollow structure of the present embodiment is a method for manufacturing a hollow structure including a recess and a top plate portion that closes the opening surface of the recess, and is the following step (0-i) and step. It has (0-iii), a step (i), a step (ii), a step (iii), a step (iv), and a step (v).

Step (0-i): A step of preparing a substrate having a recess on the surface using the above-mentioned pattern forming method Step (0-ii): Preparing a photosensitive resist film having a negative type photosensitive resin film. Step Step (i): Step of arranging the photosensitive resist film so that the surface of the photosensitive resin film of the photosensitive resist film closes the opening surface of the recess in the substrate Step (ii): The step (i). ) Later, a step of exposing the photosensitive resin film Step (iii): A step of heat-treating the photosensitive resin film after the step (iii) Step (iv): After the step (iii), the above Step of developing a photosensitive resin film to form a roof pattern that closes the opening surface of the recess Step (v): The roof pattern after the step (iv) is further cured by heat treatment. , A step of obtaining a hollow structure in which the top plate portion is made of a cured body of the photosensitive resin film.

[Step (0-i)]
In the step (0-i) in the present embodiment, a substrate having a recess on the surface is prepared by using the pattern forming method described above. Specifically, a negative pattern that becomes a side wall (Wall) of the hollow structure is formed on the substrate.
The width (horizontal dimension to the support) and height (vertical dimension to the support) of the side wall (Wall) are determined by the type of electronic device housed in the recess. It can be appropriately set according to the size of the (cavity).
The width of the side wall (Wall) is preferably, for example, 10 to 100 μm.
The bottom surface of the space that becomes the cavity in the hollow structure may be, for example, a square shape having a length of 500 μm and a width of 150 μm.

[Step (0-ii)]
In the step (0-ii) in the present embodiment, a photosensitive resist film having a negative type photosensitive resin film is prepared.

≪About photosensitive resist film≫
The photosensitive resist film in the present embodiment has, for example, a negative type photosensitive resin film containing the above-mentioned epoxy group-containing resin (component (A)) and cationic polymerization initiator (component (I)).
The description of the components constituting the photosensitive resist film is the same as described above.

When a photosensitive resin film is formed using such a photosensitive resist film and the photosensitive resin film is selectively exposed, acid is generated from the component (I) in the exposed portion of the photosensitive resin film. Then, due to the action of the acid, the epoxy group in the component (A) undergoes ring-opening polymerization, and the solubility of the component (A) in the developing solution containing an organic solvent is reduced, while the photosensitive resin film is formed. Since the solubility of the component (A) in the developing solution containing the organic solvent does not change in the unexposed portion, the developing solution containing the organic solvent is used between the exposed portion and the unexposed portion of the photosensitive resin film. There is a difference in solubility against. That is, the photosensitive resin film is a negative type. Therefore, when the photosensitive resin film is developed with a developing solution containing an organic solvent, the unexposed portion is dissolved and removed, and a negative pattern is formed.

Here, the negative-type photosensitive resin film of the photosensitive resist film is typically composed of a B-stage (semi-cured) resin material.
Examples of the photosensitive resist film include a laminated film in which a photosensitive resin film is laminated on a base film.

The photosensitive resist film is obtained by applying a negative photosensitive resin composition in which the components (A) and (I) are dissolved in a solvent on a base film and drying the mixture to form a photosensitive resin film. Can be manufactured.
The negative photosensitive resin composition may be applied onto the base film by an appropriate method using an applicator, a blade coater, a lip coater, a comma coater, a film coater, or the like.
The thickness of the photosensitive resin film is preferably 100 μm or less, more preferably 5 to 50 μm.

As the base film, a known one can be used, and for example, a thermoplastic resin film or the like is used. Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate. The thickness of the base film is preferably 2 to 150 μm.

The following steps (i) to (v) are performed using the substrate having a recess on the surface prepared in the above step (0-i) and the photosensitive resist film prepared in the above step (0-ii). ..

[Step (i)]
In the step (i), the photosensitive resist film is arranged so that the surface of the photosensitive resin film of the photosensitive resist film closes the opening surface of the recess in the substrate.
The photosensitive resist film is arranged so as to face the substrate via the side wall. Then, a hollow closed space (cavity) surrounded by the substrate, the side wall, and the photosensitive resin film is formed.

[Step (ii)]
In the step (ii), the photosensitive resin film is exposed.
For example, the photosensitive resin film is selectively exposed through a photomask on which a predetermined pattern is formed by using a known exposure device.

The wavelength used for exposure is not particularly limited, and radiation, for example, ultraviolet rays having a wavelength of 300 to 500 nm, i-line (wavelength 365 nm), or visible light is selectively irradiated (exposed). As the radiation source of these radiations, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser and the like can be used.

[Step (iii)]
In the step (iii), the photosensitive resin film after exposure is subjected to heat treatment, so-called post-exposure baking (PEB) treatment.
The PEB treatment is performed, for example, under a temperature condition of 80 to 150 ° C. for 40 to 600 seconds, preferably 60 to 300 seconds.
By the heat treatment in the step (iii), the photosensitive resin film after exposure becomes an exposed portion in which the epoxy group in the component (A) is ring-opened and polymerized, and an unexposed portion in which there is no change.

[Step (iv)]
In the step (iv), the photosensitive resin film after the PEB treatment is developed to form a negative pattern.
The development here can be performed in the same manner as in the above-mentioned [development step]. After development, a rinsing treatment is preferably performed.
By the development in the step (iv), the unexposed portion is melted and removed, and an afterimage remains as a negative pattern as a top plate portion (roof that closes the opening surface of the recess).

[Step (v)]
In the step (v), the negative pattern (exposed portion) after development is further cured by heat treatment (cure operation), and the top plate portion is a hollow structure made of a cured body of a photosensitive resin film. To get.

According to the method for manufacturing a hollow structure of the present embodiment, both the adhesion to the support and the mold resistance can be improved, the deformation of the top plate portion due to the curing operation is suppressed, and the deformation of the top plate portion is suppressed. , It is possible to stably manufacture a hollow structure having higher strength.
The hollow structure manufactured by the method for manufacturing a hollow structure of the present embodiment includes a recess and a top plate portion that closes the opening surface of the recess. The hollow structure can be suitably used for a hollow package used in SAW filters, MEMS, various sensors and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

<Preparation of negative photosensitive composition>
(Examples 1 to 4, comparative examples 1 to 5)
Each component shown in Table 1 was mixed and dissolved in 3-methoxybutyl acetate, filtered using a PTFE filter (pore diameter 1 μm, manufactured by PALL), and the negative photosensitive composition (solid content 80) of each example was obtained. ~ 85% by mass solution; viscosity 1.0 Pa · s at 23 ° C.) was prepared respectively.

In Table 1, each abbreviation has the following meaning. The numerical value in [] is the blending amount (part by mass; solid content conversion) of each component.
(A1) -1: Epoxy group-containing resin represented by the following general formula (A1-1). Product name "EPICLON1055", made by DIC. Epoxy equivalent 470 g / eq. ..
(A1) -2: Epoxy group-containing resin represented by the following general formula (A1-2). Product name "jER-4005P", manufactured by Mitsubishi Chemical Corporation. Epoxy equivalent 1070 g / eq. ..

(A2) -1: A compound represented by the following chemical formula (A2-1). Product name "jER-157S70", manufactured by Mitsubishi Chemical Corporation. Epoxy equivalent 210 g / eq. ..

(I) -1: Cationic polymerization initiator represented by the following chemical formula (I1-1). Product name "CPI-310B", manufactured by Sun Appro Co., Ltd.
(I) -2: Cationic polymerization initiator represented by the following chemical formula (I3-1-1). Product name "HS-1CS", manufactured by Sun Appro Co., Ltd.

<Evaluation (1)>
A cured film was formed using the negative photosensitive composition of each example, and the stress and the thermal elastic modulus shown below were evaluated.

[Stress evaluation]
The "warp amount" of a 6-inch silicon wafer having a thickness of 625 μm ± 25 μm was measured in advance using a residual stress measuring device (manufactured by Tencor Co., Ltd., model name FLX-2320).
The negative photosensitive composition of each example obtained above was uniformly applied onto the 6-inch silicon wafer using an applicator, and baked (PAB) was performed at a heating temperature of 115 ° C. for 5 minutes. A photosensitive resin film (thickness 15 μm) was formed.
Next, the photosensitive resin film was exposed to an irradiation amount (ghi broadband) of 200 mJ / cm ² .
Next, the photosensitive resin film after exposure was heated after exposure for 5 minutes on a hot plate at 90 ° C. to obtain a pre-cured film.
Then, the obtained pre-cured film was heated at 200 ° C. for 1 hour in a nitrogen atmosphere to be cured to obtain a desired cured film.

The amount of warpage of the 6-inch silicon wafer formed by the cured film was measured using the residual stress measuring device, and the stress [MPa] generated between the silicon wafer and the cured film was evaluated. The evaluation results are shown in Table 2.
In the stress evaluation, those evaluated as "◯" had a stress of 20 MPa or less, and those evaluated as "x" had a stress of more than 20 MPa.

[Evaluation of thermal elastic modulus]
The negative photosensitive compositions of each example obtained above were uniformly applied onto a 6-inch silicon wafer using an applicator, and subjected to bake treatment (PAB) at a heating temperature of 115 ° C. for 5 minutes for photosensitivity. A sex resin film (thickness 15 μm) was formed.
Next, the photosensitive resin film was exposed to an irradiation amount (ghi broadband) of 200 mJ / cm ² .
Next, the photosensitive resin film after exposure was heated after exposure for 5 minutes on a hot plate at 90 ° C. to obtain a pre-cured film.
Next, paddle development was performed at 23 ° C. for 120 seconds using propylene glycol monomethyl ether acetate (PGMEA) as a developing solution, and after shaking off and drying, the mixture was heated at 200 ° C. for 1 hour under a nitrogen atmosphere to cure. A quadrangular cured film having a size of 5 mm × 10 mm was obtained.
The strength of the obtained cured film was evaluated using the thermal elastic modulus as an index. The thermal elastic modulus was measured as follows. The measurement results are shown in Table 2.

The obtained cured film was peeled off from the silicon wafer, and the thermal elastic modulus (E * / MPa) of the cured film at 150 ° C. was measured by the following evaluation device and measurement conditions.
-Evaluation device: Reogel E-4000 (manufactured by UBM)
-Measurement conditions: tensile mode, frequency 1 MHz, distance between chucks 10 mm
In the evaluation of the thermal elastic modulus, those evaluated as "○" had a thermal elastic modulus of 40 MPa or more, and those evaluated as "x" had a thermal elastic modulus of less than 40 MPa. It is a thing.

<Evaluation (2)>
In addition, a hollow structure was prepared using the negative photosensitive composition of each example, and the reliability and mold resistance shown below were evaluated.

≪Manufacturing of hollow structure≫
As a roof material to be a top plate portion, a photosensitive resist film having a negative type photosensitive resin film formed by the photosensitive resin composition TMMF SP1030HQ3 was prepared.
A lithium tantalate substrate was used as the substrate.

The negative photosensitive composition of each example obtained above was uniformly applied onto the lithium tantalate substrate using an applicator, and baked (PAB) was performed at a heating temperature of 115 ° C. for 5 minutes. A photosensitive resin film (thickness 15 μm) was formed.
Next, the photosensitive resin film was exposed to an irradiation amount (ghi broadband) of 200 mJ / cm ² .
Next, the photosensitive resin film after exposure was heated after exposure for 5 minutes on a hot plate at 90 ° C. to obtain a pre-cured film.
Next, using PGMEA as a developer, paddle development was performed at 23 ° C. for 120 seconds, and after shaking off and drying, the mixture was heated at 200 ° C. for 1 hour under a nitrogen atmosphere to cure.
As described above, a wall-mounted substrate was obtained in which a concave pattern having a width of 50 μm and a side wall (Wall) made of a cured film was formed around a quadrangle of 500 μm in length × 150 μm in width on a lithium tantalate substrate.

Next, the photosensitive resist film was arranged (laminated) so as to close the opening surface of the recess in the wall-mounted substrate.

Then, using a Canon PLA-501 ghi line aligner, the photosensitive resist film was exposed to 200 mJ / cm ² (i-line equivalent) via a predetermined mask pattern.

Next, the photosensitive resist film after the exposure was heated in an oven at a temperature of 90 ° C. for 5 minutes after the exposure.

Next, the photosensitive resist film after exposure and heating is paddle-developed at 23 ° C. for 120 seconds using PGMEA as a developing solution to develop a top plate portion (roof that closes the opening surface of the recess). ) Was formed.

The roof pattern was further cured by heat treatment at a temperature of 200 ° C. for 60 minutes in an oven to produce a hollow structure (cavity size: length 500 μm × width 150 μm × height 45 μm).

[Evaluation of reliability]
The hollow structure produced by using the negative photosensitive composition of each example was allowed to stand in a constant temperature bath. The temperature in the constant temperature bath in which the hollow structure was placed was raised from room temperature to 125 ° C. and held at 125 ° C. for 15 minutes, then cooled to −55 ° C. and held at −55 ° C. for 15 minutes. After that, a heat cycle test was carried out in which the cycle of returning to room temperature was repeated 200 times.
The hollow structure after the completion of the 200-cycle heat cycle test was observed, and the presence or absence of peeling between the substrate and the hollow structure was evaluated with a microscope for reliability. Those in which no peeling occurred between the substrate and the hollow structure were evaluated as "◯", and those in which peeling did occur were evaluated as "x". The evaluation results are shown in Table 2.

[Evaluation of mold resistance]
The hollow structure produced by using the negative photosensitive composition of each example was subjected to compression molding using an epoxy resin molding compound material. Compression molding was performed using CPM-1080 (manufactured by TOWA) as a molding device under the conditions of a pressure of 6 MPa, a temperature of 130 ° C., and a time of 10 minutes. After that, the hollow structure was further heat-treated (cure operation) at 160 ° C. for 120 minutes.
The cross-sectional shape of the hollow structure after the curing operation was observed by SEM, and the one in which the wall material was not deformed was evaluated as "◯", and the one in which the wall material was deformed was evaluated as "x". The evaluation results are shown in Table 2.

From the results shown in Table 2, according to the negative photosensitive compositions of Examples 1 to 4 to which the present invention was applied, the stress inside the cured film was suppressed to a low level and the elastic modulus during heat was increased. You can check it.
By using the negative photosensitive compositions of Examples 1 to 4, it is possible to improve the adhesion to the substrate and the like and the mold resistance in the production of the hollow sealed structure in the electronic component. ..
In addition, it can be confirmed that the hollow structure produced by the negative photosensitive compositions of Examples 1 to 4 has good results of the heat cycle test, is less likely to cause a failure, and is highly reliable. ..

On the other hand, in the negative photosensitive compositions of Comparative Example 1 and Comparative Example 4, since the component (A) is composed of the component (A1), the thermal elastic modulus evaluation does not satisfy 150 ° C. and 40 MPa, and the mold resistance is high. The evaluation was "x".
In the negative photosensitive compositions of Comparative Example 2 and Comparative Example 5, the stress evaluation was “x” because the component (A1) and the component (A2) were composed of the same amount of parts by mass.
In the negative photosensitive composition of Comparative Example 3, since the component (A) was composed of the component (A2), the stress evaluation was “x”.

Claims (7)

A negative photosensitive composition containing an epoxy group-containing compound (A) and a cationic polymerization initiator (I).
The epoxy group-containing compound (A) is
(A1) Ingredient: Epoxy equivalent is 300 g / eq. With the above epoxy resin,
Component (A2): An epoxy resin represented by the following general formula (A2-1) whose epoxy equivalent is smaller than that of component (A1).
Including
The content of the component (A1) is 60 to 90% by mass with respect to the total mass (100% by mass) of the epoxy group-containing compound (A).
A negative photosensitive composition in which the content of the component (A2) is 10 to 40% by mass with respect to the total mass (100% by mass) of the epoxy group-containing compound (A).

[In the formula, R ^p1 and R ^p2 are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. The plurality of R ^p1s may be the same as or different from each other. The plurality of R ^p2s may be the same as or different from each other. n ₁ is an integer of 1 to 5. R ^EP is an epoxy group-containing group. The plurality of R ^EPs may be the same as or different from each other. ] The negative according to claim 1, wherein the content of the cationic polymerization initiator (I) is 0.3 to 5.0 parts by mass with respect to 100 parts by mass of the total mass of the epoxy group-containing compound (A). Mold photosensitive composition. The negative photosensitive composition according to claim 1 or 2, wherein the stress in the cured product is 20 MPa or less. The negative photosensitive composition according to any one of claims 1 to 3, wherein the cured product has a thermal elastic modulus at 150 ° C. of 40 MPa or more. A step of forming a photosensitive resin film on a support, a step of exposing the photosensitive resin film, and the exposure of the negative type photosensitive composition according to any one of claims 1 to 4. A pattern forming method comprising a step of developing a subsequent photosensitive resin film with a developing solution containing an organic solvent to form a negative pattern. The pattern forming method according to claim 5, wherein the support is a lithium tantalate substrate or a lithium niobate substrate. It is a method of manufacturing a hollow structure including a recess and a top plate portion that closes the opening surface of the recess.
A step (0-i) of preparing a substrate having a recess on the surface by using the pattern forming method according to claim 5 or 6.
The step of preparing a photosensitive resist film having a negative type photosensitive resin film (0-ii), and
The step (i) of arranging the photosensitive resist film so that the surface of the photosensitive resin film of the photosensitive resist film closes the opening surface of the recess in the substrate.
After the step (i), the step of exposing the photosensitive resin film (ii) and
The step (iii) of heat-treating the photosensitive resin film after the step (iii),
After the step (iii), the step (iv) of developing the photosensitive resin film to form a roof pattern that closes the opening surface of the recess.
The step (v) of obtaining a hollow structure in which the top plate portion is made of a cured body of the photosensitive resin film by further performing a heat treatment on the roof pattern after the step (iv). A method for manufacturing a hollow structure.