JP2023037480A - Negative photosensitive composition, patterning method and method for producing hollow package - Google Patents

Abstract

To provide a photosensitive composition that can form a pattern (side wall) having high adhesion to a wire layer after a moisture resistance test at high temperature, a patterning method using the same and a method for producing a hollow package .SOLUTION: A negative photosensitive composition contains an epoxy group-containing compound, a cationic polymerization initiator, and a compound represented by the general formula (c1). In the general formula (c1), n is an integer of 4 or greater. REP is an epoxy group-containing group. R1, R2 and R3 independently represent an alkyl group, an aryl group or an alkoxy group. R1, R2 and R3 may be different or two or more of them may be the same, where at least one of R1, R2 and R3 is an alkoxy group.SELECTED DRAWING: None

Description

The present invention relates to a negative photosensitive composition, a pattern forming method, and a hollow package manufacturing method.

In recent years, development of minute electronic devices such as surface acoustic wave (SAW) filters has been advanced. A package in which such an electronic device is sealed has a hollow structure for ensuring propagation of surface acoustic waves and movability of movable members of the electronic device.
The package having a hollow structure (hollow package) is formed by using a photosensitive composition to prepare a hollow structure in which a wiring substrate on which electrodes are formed is kept hollow, followed by molding.

The hollow structure can be produced as follows.
After a photosensitive composition is coated on the wiring substrate so as to surround the electrodes, exposure through a photomask, post-exposure baking (PEB), and development are performed to form sidewalls that will serve as spacers.
Next, from a dry film resist in which a base film, a photosensitive composition layer and a cover film are laminated in this order, the cover film is peeled off and laminated on the side wall to form a top plate portion, and a photomask is formed again. Exposure, PEB, and development are performed through , and an unnecessary portion is removed to produce a top plate portion, thereby producing a hollow structure.

Patent Literature 1 discloses a hollow package including a supporting substrate, a piezoelectric thin film, electrodes, a wiring layer, an insulating layer, a spacer layer (side wall), and a cover member (top plate portion). .
In the hollow package disclosed in Patent Document 1, a piezoelectric thin film is provided on a support substrate. An insulating layer is formed on the support substrate so as to surround the piezoelectric thin film. The wiring layer overlaps a part of the insulating layer, is electrically connected to the electrode, and is also connected to the external electrode. The spacer layer (side wall) has a frame shape in plan view and is formed along the outer periphery of the support substrate. The spacer layer (sidewall) overlaps the insulating layer, and part of the spacer layer (sidewall) covers part of the wiring layer. That is, part of the wiring layer is interposed between the insulating layer and the spacer layer (side wall). The cover member (top plate portion) is arranged on the spacer layer (side wall).
As a material for the spacer layer, synthetic resin such as epoxy resin is mentioned.
It is said that the wiring layer can be formed of metal materials such as aluminum, copper, and platinum.

JP 2019-103127 A

Electronic components are required to have high reliability. In response to such demands, it is necessary for electronic parts to have, for example, moisture resistance. Specifically, it is necessary that the side wall and the wiring layer have high adhesion even after a high-temperature moisture resistance test such as a pressure cooker test (PCT).
However, with conventional photosensitive compositions, the adhesion between the side wall and the wiring layer is insufficient after a humidity resistance test at high temperatures.
The conditions for the moisture resistance test under high temperature are, for example, a temperature of 105 to 160° C., a relative humidity of 75 to 100%, and an exposure time of 24 hours or more and 408 hours or less.

The present invention has been made in view of the above circumstances, and provides a photosensitive composition capable of forming a sidewall (pattern) having high adhesion to a wiring layer after a moisture resistance test at high temperature, and a pattern forming method using the same. and to provide a method for manufacturing a hollow package.

In order to solve the above problems, the present invention employs the following configurations.

That is, the first aspect of the present invention contains an epoxy group-containing compound (A), a cationic polymerization initiator (I), and a compound (C1) represented by the following general formula (c1). A negative-acting photosensitive composition, characterized in that:

［式中、ｎは、４以上の整数である。Ｒ^ＥＰは、エポキシ基含有基である。Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、アルキル基、アリール基又はアルコキシ基である。Ｒ^１、Ｒ^２及びＲ^３は、相互に異なっていてもよいし、二つ以上が同一であってもよい。但し、Ｒ^１、Ｒ^２及びＲ^３のうち、少なくとも一つはアルコキシ基である。］

[In the formula, n is an integer of 4 or more. ^REP is an epoxy group-containing group. R ¹ , R ² and R ³ are each independently an alkyl group, an aryl group or an alkoxy group. R ¹ , R ² and R ³ may be different from each other, or two or more of them may be the same. However, at least one of R ¹ , R ² and R ³ is an alkoxy group. ]

A second aspect of the present invention comprises a step of forming a photosensitive film on a substrate having aluminum wiring using the negative photosensitive composition according to the first aspect, and a step of exposing the photosensitive film. and developing the exposed photosensitive film with a developer containing an organic solvent to form a negative pattern.

A third aspect of the present invention is a method for manufacturing a hollow package having a hollow structure for accommodating the aluminum wiring on a substrate having the aluminum wiring, the method comprising the pattern forming method according to the second aspect. forming a side wall of the hollow structure on the substrate having the aluminum wiring using the A method for manufacturing a hollow package, comprising:

According to the present invention, a negative photosensitive composition capable of forming a side wall (pattern) having high adhesion to a wiring layer after a moisture resistance test at high temperature, a pattern forming method using the same, and a method for manufacturing a hollow package are provided. can provide.
According to the negative photosensitive composition, the pattern forming method, and the hollow package manufacturing method of the present invention, the adhesion between the substrate having the aluminum wiring and the side wall is high, especially after the moisture resistance test, and the reliability of the electronic component is improved. can be improved.

It is a mimetic diagram explaining one embodiment of a manufacturing method of a hollow package.

In the present specification and claims, the term "aliphatic" is a concept relative to aromatics, meaning groups having no aromaticity, compounds having no aromaticity, etc. Define.
"Alkyl group" includes linear, branched and cyclic monovalent saturated hydrocarbon groups unless otherwise specified. The same applies to the alkyl group in the alkoxy group.
Unless otherwise specified, the "alkylene group" includes straight-chain, branched-chain and cyclic divalent saturated hydrocarbon groups.
A "halogenated alkyl group" is a group in which some or all of the hydrogen atoms of an alkyl group are substituted with halogen atoms, and the halogen atoms include fluorine, chlorine, bromine and iodine atoms.
A "fluorinated alkyl group" refers to a group in which some or all of the hydrogen atoms in an alkyl group have been substituted with fluorine atoms.
A "structural unit" means a monomer unit (monomeric unit) that constitutes a polymer compound (resin, polymer, copolymer).
When describing "optionally having a substituent", when replacing a hydrogen atom (-H) with a monovalent group, and when replacing a methylene group (-CH ₂ -) with a divalent group and both.
“Exposure” is a concept that includes irradiation of radiation in general.

(Negative photosensitive composition)
The negative photosensitive composition of the present embodiment (hereinafter sometimes simply referred to as "photosensitive composition") comprises an epoxy group-containing compound (A) (hereinafter also referred to as "(A) component") and a cationic polymerization initiator (I) (hereinafter also referred to as "(I) component") and a compound represented by general formula (c1) (hereinafter this compound is also referred to as "(C1) component").
When a photosensitive film is formed using such a photosensitive composition and the photosensitive film is selectively exposed to light, the cationic moiety of component (I) is decomposed in the exposed areas of the photosensitive film. Acid is generated, and the action of the acid causes ring-opening polymerization of the epoxy groups in the component (A), reducing the solubility of the component (A) in a developer containing an organic solvent. In the unexposed area of the film, since the solubility of the component (A) in the developer containing an organic solvent does not change, the developer containing an organic solvent is used between the exposed area and the unexposed area of the photosensitive film. There is a difference in solubility for Therefore, when the photosensitive film is developed with a developer containing an organic solvent, the unexposed portion is dissolved and removed to form a negative pattern.

<Epoxy group-containing compound (A)>
In the photosensitive composition of the present embodiment, the epoxy group-containing compound (component (A)) includes a compound having sufficient epoxy groups in one molecule to form a negative pattern by exposure.
The (A) component used in the photosensitive composition of the present embodiment includes a novolac epoxy resin (hereinafter also referred to as "(A1) component"), a bisphenol epoxy resin (hereinafter also referred to as "(A2) component"), Examples include aliphatic epoxy resins and acrylic resins.
The component (A) may be used alone or in combination of two or more.
However, the component (A) shall exclude those corresponding to silane coupling agents.

≪Novolac type epoxy resin≫
As the novolac type epoxy resin (component (A1)), epoxy resins represented by the following general formula (anv0) are suitable.

［式中、Ｒ^ｐ１及びＲ^ｐ２は、それぞれ独立に、水素原子又は炭素原子数１～５のアルキル基である。複数のＲ^ｐ１は、互いに同一であってもよく異なっていてもよい。複数のＲ^ｐ２は、互いに同一であってもよく異なっていてもよい。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いてもよい。］

[In the formula, R ^p1 and R ^p2 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A plurality of R ^p1 may be the same or different from each other. A plurality of R ^p2 may be the same or different from each other. n ₁ is an integer from 1 to 5; ^REP is an epoxy group-containing group. Multiple ^REPs may be the same or different. ]

In the formula (anv0), the alkyl group having 1 to 5 carbon atoms of R ^p1 and R ^p2 is, for example, a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms. Linear or branched alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. . A cyclobutyl group, a cyclopentyl group, etc. are mentioned as a cyclic alkyl group.
Among them, R ^p1 and R ^p2 are preferably a hydrogen atom or a linear or branched alkyl group, more preferably a hydrogen atom or a linear alkyl group, and particularly preferably a hydrogen atom or a methyl group.
In formula (anv0), a plurality of R ^p1 may be the same or different. A plurality of R ^p2 may be the same or different from each other.

In the formula (anv0), _n1 is an integer of 1 to 5, preferably 2 or 3, more preferably 2.

In the formula (anv0), ^REP is an epoxy group-containing group.
The epoxy group-containing group of R ^EP is not particularly limited, and includes 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. and a group having
An alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure which is a three-membered ring ether, and specifically a group having an alicyclic group and an oxacyclopropane structure.
The alicyclic group that forms the basic skeleton of the alicyclic epoxy group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups. Moreover, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group etc. are mentioned as a polycyclic alicyclic group. Moreover, the hydrogen atoms 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 alicyclic epoxy group and a divalent linking group, the epoxy group or alicyclic epoxy It is preferred that the groups are attached.

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

Regarding the optionally substituted divalent hydrocarbon group:
Such a divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
The aliphatic hydrocarbon group in the divalent hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
More specifically, the aliphatic hydrocarbon group includes a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing 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 straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferable, and specifically, a methylene group [ _--CH.sub.2-- ], an ethylene group [--( _CH.sub.2 ) _.sub.2-- ], a trimethylene group [ -(CH ₂ ) ₃ -], tetramethylene group [-(CH ₂ ) ₄ -], pentamethylene group [-(CH ₂ ) ₅ -] and the like.
The branched chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, and most preferably 2 or 3 carbon atoms. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specifically, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) _2- , -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ - and other alkylmethylene groups;- CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C(CH ₂ Alkylethylene groups such as CH ₃ ) ₂ -CH ₂ -; alkyltrimethylene groups such as -CH(CH ₃ )CH ₂ CH ₂ - and -CH ₂ CH(CH ₃ )CH ₂ -; -CH(CH ₃ ) Examples include alkylalkylene groups such as alkyltetramethylene groups such as CH ₂ CH ₂ CH ₂ — and —CH ₂ CH(CH ₃ )CH ₂ CH ₂ —. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

The aliphatic hydrocarbon group containing a ring in the structure includes an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group that is linear or branched. Examples thereof include a group bonded to the end of a chain aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group intervenes in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include those mentioned above.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. 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 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 preferably has 7 to 12 carbon atoms. includes 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. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n+2) π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5-30, more preferably 5-20, still more preferably 6-15, and particularly preferably 6-12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; mentioned. The heteroatom in the aromatic heterocycle includes oxygen atom, sulfur atom, nitrogen atom and the like. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings.
Specific examples of aromatic hydrocarbon groups include groups obtained by removing two hydrogen atoms from the above aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); aromatic compounds containing two or more aromatic rings A group obtained by removing two hydrogen atoms from (e.g., biphenyl, fluorene, etc.); One of the hydrogen atoms of the group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl group or heteroaryl group) A group in which one is 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 hydrogen from an arylalkyl group such as a 2-naphthylethyl group) group from which one atom has been further removed), and the like. The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

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

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

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

For bivalent linking groups containing heteroatoms:
The heteroatom in the heteroatom-containing bivalent linking group is an atom other than a carbon atom and a hydrogen atom, such as an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom and the like.

Among the heteroatom-containing bivalent linking groups, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O)-, and -OC(=O). -O-; -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)- (H is substituted with an alkyl group, an acyl group, etc. group); -S-, -S(=O) ₂ -, -S(=O) ₂ -O-, general formula -Y ²¹ -O-Y ²² -, -Y ²¹ -O-, -Y ²¹ -C(=O)-O-, -C(=O)-O-Y ²¹ , -[Y ²¹ -C(=O)-O] _m″ -Y ²² - or - a group represented by Y ²¹ -OC(=O)-Y ²² - [wherein Y ²¹ and Y ²² are each independently a divalent hydrocarbon group optionally having a substituent; , O is an oxygen atom, and m″ is an integer from 0 to 3. ] and the like.
When the divalent linking group containing a heteroatom 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 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.
formulas -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 -O-C(=O)-Y ²² -, Y ²¹ and Y ²² each independently have a substituent and Examples of the divalent hydrocarbon group include the divalent hydrocarbon group optionally having substituent(s) mentioned in the above description of the divalent linking group ” and the like.
Y ²¹ is preferably a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, more preferably a straight-chain alkylene group having 1 to 5 carbon atoms, and a methylene group or an ethylene group. Especially preferred.
Y ²² is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group having 1 to 5 carbon atoms, more preferably a straight-chain 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 preferred, and 1 is particularly preferred. 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)-O-Y ²² - is particularly preferred, and among these, a group represented by the formula —(CH ₂ ) _a′ —C(═O)—O—(CH ₂ ) _b′ — is preferred, in which a′ is 1 to An integer of 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, 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 more preferred, and 1 is most preferred.

Among them, a glycidyl group is preferable as the epoxy group-containing group in ^REP .

Further, as the component (A1), a resin having a constitutional unit represented by the following general formula (anv1) is also suitable.

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

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

In the formula (anv1), the alkyl groups having 1 to 5 carbon atoms for R ^a22 and R ^a23 are the same as the alkyl groups having 1 to 5 carbon atoms for R ^p1 and R ^p2 in the formula (anv0). .
The halogen atoms of R ^a22 and R ^a23 are preferably chlorine atoms or bromine atoms.
In formula (anv1), R ^EP is the same as R ^EP in formula (anv0), and is preferably a glycidyl group.

Specific examples of the structural unit represented by the formula (anv1) are shown below.

The (A1) component may be a resin consisting only of the structural unit (anv1), or may be a resin having the structural unit (anv1) and other structural units.
Other structural units include, for example, structural units represented by the following general formulas (anv2) to (anv3).

［式中、Ｒ^ａ２４は、置換基を有してい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、炭素原子数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いてもよい炭化水素基である。］

[In the formula, R ^a24 is a hydrocarbon group optionally having a substituent. R ^a25 to R ^a26 and R ^a28 to R ^a30 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. R ^a27 is an epoxy group-containing group or a hydrocarbon group optionally having a substituent. ]

In the formula (anv2), R ^a24 is a hydrocarbon group which may have a substituent. The hydrocarbon group which may have a substituent includes 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 still more preferably 1 or 2 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, n-butyl group, 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, more preferably 3 to 5 carbon atoms. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group and a 2,2-dimethylbutyl group, with an isopropyl group being preferred.

When R ^a24 is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
As a monocyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples 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 preferably has 7 to 12 carbon atoms. adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

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

In formulas (anv2) and (anv3), R ^a25 to R ^a26 and R ^a28 to R ^a30 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.
The alkyl group having 1 to 5 carbon atoms and the halogen atom are the same as defined above for R ^a22 and R ^a23 respectively.

In the formula (anv3), R ^a27 is an epoxy group-containing group or a hydrocarbon group which may have a substituent. The epoxy group-containing group of R ^a27 is the same as R ^EP in the formula (anv0). The hydrocarbon group optionally having a substituent for R ^a27 is the same as R ^a24 in the formula (anv2).

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

When the component (A1) has other structural units in addition to the structural unit (anv1), the ratio of each structural unit in the component (A1) is not particularly limited, but it constitutes the component (A1). The total amount of constituent units having an epoxy group is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and even more preferably 30 to 70 mol%, based on the total amount of all constituent units.

Commercially available products of component (A1) include, for example, novolac type epoxy resins such as jER-152, jER-154, jER-157S70, and jER-157S65 (manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, and EPICLON N. -740, EPICLON N-770, EPICLON N-775, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695, EPICLON HP5000 (above, manufactured by DIC Corporation), EOCN-1020 (above, manufactured by Nippon Kayaku Co., Ltd.), 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 component (A1) is preferably 10 to 40 parts by mass, preferably 15 to 35 parts by mass, when the total parts by mass of component (A) is 100 parts by mass. It is more preferably 20 to 30 parts by mass.

≪Bisphenol type epoxy resin≫
The bisphenol-type epoxy resin (hereinafter also referred to as "(A2) component") may be any resin having a structural unit containing a bisphenol skeleton, and among these, a solid bisphenol-type epoxy resin is preferable.
A solid bisphenol type epoxy resin refers to a resin having a structural unit containing a bisphenol skeleton that is solid at 25°C.
The epoxy equivalent of component (A2) is, for example, 800 g/eq. 800 to 1200 g/eq. is more preferable, and 900 to 1100 g/eq. is more preferred.

As the (A2) component, epoxy resins represented by the following general formula (abp1) are suitable.

［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。Ｒ^ａ３１及びＲ^ａ３２は、それぞれ独立に、水素原子、炭素原子数１～５のアルキル基、又は炭素原子数１～５のフッ素化アルキル基である。ｎａ^３１は、１～５０の整数である。］

[In the formula, ^REP is an epoxy group-containing group. Multiple ^REPs may be the same or different. R ^a31 and R ^a32 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. na ³¹ is an integer of 1-50. ]

In formula (abp1), R ^EP is the same as R ^EP in formula (anv0), and is preferably a glycidyl group.
In the formula (abp1), the alkyl group having 1 to 5 carbon atoms in R ^a31 and R ^a32 is the same as the alkyl group having 1 to 5 carbon atoms in R ^p1 and R ^p2 in the formula (anv0). . Among them, each of R ^a31 and R ^a32 is preferably a hydrogen atom or a methyl group.
In the fluorinated alkyl group having 1 to 5 carbon atoms for R ^a31 and R ^a32 , part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms for R ^a31 and R ^a32 are substituted with fluorine atoms. groups.
In the formula (abp1), na ³¹ is an integer of 1-50, preferably an integer of 4-15, more preferably an integer of 5-8.

Commercial products that can be used as the (A2) component include, for example, jER-4005, jER-4007, jER-4010 (manufactured by Mitsubishi Chemical Corporation); jER-827, jER-828, jER-834, jER-1001 , jER-1002, jER-1003, jER-1055, jER-1007, jER-1009, jER-1010 (manufactured by Mitsubishi Chemical Corporation); EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (manufactured by DIC Corporation), etc. is 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 component (A2) is preferably 60 to 90 parts by mass, preferably 65 to 85 parts by mass, when the total parts by mass of component (A) is 100 parts by mass. It is more preferably 70 to 80 parts by mass.

When the (A1) component and the (A2) component are used together, the ratio of the (A1) component and the (A2) component is 1/9 or more as a mass ratio represented by the (A1) component/(A2) component. It is preferably 5/5 or less, more preferably 1/9 or more and less than 5/5, further preferably 2/8 or more and 4/6 or less, and 2/8 or more and 3/7 or less. is particularly preferred.
If the mass ratio is within the preferred range, the resolution is further improved, and a pattern (side wall) having high adhesion to the wiring layer is easily formed.

≪Aliphatic epoxy resin≫
Preferred examples of aliphatic epoxy resins include compounds represented by the following general formula (ta1) (hereinafter, this compound is also referred to as "(A3) component").

［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. Multiple ^REPs may be the same or different. ]

In formula (ta1), ^REP is an epoxy group-containing group and is the same as ^REP in formula (anv0).

Commercially available products that can be used as the component (A3) include, for example, TEPIC, TEPIC-VL, TEPIC-PAS, TEPIC-G, TEPIC-S, TEPIC-SP, TEPIC-SS, TEPIC-HP, TEPIC-L, TEPIC- TEPIC series such as FL and TEPIC-UC (manufactured by Nissan Chemical Industries, Ltd.);

As the component (A3), 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 component (A3) is preferably 0.1 to 10 parts by mass when the total parts by mass of component (A) is 100 parts by mass. 0.5 to 5 parts by mass, more preferably 1 to 3.5 parts by mass.

Examples of aliphatic epoxy resins also include compounds containing a partial structure represented by the following general formula (m1) (hereinafter also referred to as "component (m1)").

［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 formula (m1), _n2 is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2.

Component (m1) includes a compound in which a plurality of partial structures represented by the 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 general formula (m1) are bonded via a divalent linking group is preferable.
The divalent linking group here is not particularly limited, but preferably includes an optionally substituted divalent hydrocarbon group and a heteroatom-containing divalent linking group.
Here, the divalent hydrocarbon group optionally having a substituent and the divalent linking group containing a hetero atom are described in R ^EP (epoxy group-containing group) in the above formula (anv0). , a divalent hydrocarbon group which may have a substituent ^, and a divalent linking group containing a hetero atom. A group represented by C(=O)-O- and a group represented by -C(=O)-O-Y ²¹ - are more preferable. Y ²¹ is preferably a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, more preferably a straight-chain alkylene group having 1 to 5 carbon atoms, and a methylene group or an ethylene group. Especially preferred.

Commercial products that can be used as aliphatic epoxy resins include, for example, ADEKA RESIN EP-4080S, EP-4085S, and EP-4088S (manufactured by ADEKA Corporation); Celoxide 8000, Celoxide 8010, EHPE-3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (manufactured by Daicel Corporation); Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation) and the like.

≪Acrylic resin≫
Examples of acrylic resins include resins having epoxy group-containing units represented by general formulas (a1-1) and (a1-2) below.

［式中、Ｒは水素原子、炭素原子数１～５のアルキル基、又は炭素原子数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及びＲ^ａ４２はそれぞれ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 a halogenated alkyl group having 1 to 5 carbon atoms. Va ⁴¹ is a divalent hydrocarbon group optionally having a substituent. na ⁴¹ is an integer of 0-2. R ^a41 and R ^a42 are each 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 1-3. ]

In the above formula (a1-1), the alkyl group having 1 to 5 carbon atoms in R is preferably linear or branched, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like.
The halogenated alkyl group having 1 to 5 carbon atoms in R is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is particularly preferred.
R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group in view of industrial availability.

In the formula (a1-1), Va ⁴¹ is a divalent hydrocarbon group which may have a substituent, and has the substituent described in R ^EP in the formula (anv0). and the same divalent hydrocarbon groups as those which may be used.
Among the above, the hydrocarbon group of Va ⁴¹ is preferably an aliphatic hydrocarbon group, more preferably a linear or branched aliphatic hydrocarbon group, still more preferably a linear aliphatic hydrocarbon group, A straight-chain alkylene group is particularly preferred.

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

In formulas (a1-1) and (a1-2) above, R ^a41 and R ^a42 are epoxy group-containing groups and are the same as R ^EP in formula (anv0) above.

In the above 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. may be used, and is usually preferably saturated. As the aliphatic hydrocarbon group, 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 an aliphatic hydrocarbon group containing a ring in its structure.

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

Specific examples of structural units represented by formula (a1-1) or (a1-2) are shown below.
In the formula below, 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 from 0-10.
R ^a51 , R ^a52 and R ^a53 may be the same or different.

Furthermore, the acrylic resin may have structural units derived from other polymerizable compounds for the purpose of appropriately controlling physical and chemical properties.
Examples of such polymerizable compounds include known radically polymerizable compounds and anionically polymerizable compounds. Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethylsuccinic acid and 2-methacryloyloxy Methacrylic acid derivatives having a carboxyl group and an ester bond such as ethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) ) acrylates and other (meth) acrylic acid alkyl esters; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and other (meth) acrylic acid hydroxyalkyl esters; phenyl (meth) acrylate, benzyl ( (meth)acrylic acid aryl esters such as meth)acrylate; 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; and amide bond-containing polymerizable compounds such as acrylamide and methacrylamide.

When the above acrylic resin has other structural units, the content ratio of the epoxy group-containing unit in the resin is preferably 5 to 40 mol%, more preferably 10 to 30 mol%, and 15 to More preferably, it is 25 mol %.

As the epoxy group-containing compound, in addition to the resins described above, a compound represented by the following chemical formula (A4-1) and a compound represented by the following chemical formula (A4-2) may be used.
Commercially available products that can be used as the compound represented by the following chemical formula (A4-1) include, for example, TECHMORE VG-3101L (manufactured by Printec Co., Ltd.).
Commercially available products that can be used as the compound represented by the following chemical formula (A4-2) include, for example, Showfree (registered trademark) BATG (manufactured by Showa Denko KK).

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

In the photosensitive composition of the present embodiment, the (A) component preferably contains the (A1) component and the (A2) component, and among these, the composition containing the (A1) component and a solid bisphenol epoxy resin. More preferably, one containing an epoxy resin represented by the general formula (anv0) and an epoxy resin represented by the general formula (abp1) is even more preferable.

The polystyrene equivalent mass average molecular weight of component (A) is preferably 100 to 300,000, more preferably 200 to 200,000, and still more preferably 300 to 200,000. With such a weight-average molecular weight, peeling from a support (such as a substrate having a wiring layer) is less likely to occur, and the strength of the formed cured film is sufficiently increased.

The content of component (A) in the photosensitive composition of the embodiment may be adjusted according to the film thickness of the photosensitive film to be formed.

<Cationic polymerization initiator (I)>
In the photosensitive composition of the present embodiment, the cationic polymerization initiator (component (I)) is irradiated with active energy rays such as ultraviolet rays, far ultraviolet rays, excimer laser light such as KrF and ArF, X-rays, and electron beams. It is a compound that can generate cations through reaction, and the cations can serve as polymerization initiators.
The (I) component used in the photosensitive composition of the present embodiment includes an onium borate salt (hereinafter also referred to as "(I1) component"), and a cationic polymerization initiator other than the (I1) component (other cationic polymerization initiators). is mentioned.

≪Onium borate salt≫
An onium borate salt (component (I1)) generates a relatively strong acid upon exposure. Therefore, by forming a pattern using a photosensitive composition containing the component (I1), sufficient sensitivity can be obtained and a good pattern can be formed. In addition, the use of component (I1) has a low risk of toxicity and metal corrosion.
As the component (I1), for example, compounds represented by the following general formula (I1) are suitable.

［式中、Ｒ^ｂ０１～Ｒ^ｂ０４は、それぞれ独立に、置換基を有し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、ｑ価の有機カチオンである。］

[In the formula, R ^b01 to R ^b04 are each independently an optionally substituted aryl group or a fluorine atom. q is an integer of 1 or more, and Q ^q+ is a q-valent organic cation. ]

Anion portion In the above formula (I1), the aryl group in R ^b01 to R ^b04 preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, still more preferably 6 to 15 carbon atoms, and 6 to 12 carbon atoms. is particularly preferred. Specific examples include a naphthyl group, a phenyl group, an anthracenyl group, and the like, and a phenyl group is preferable because it is easily available.
The aryl groups in R ^b01 to R ^b04 may have a substituent. The substituents are not particularly limited, but are halogen atoms, hydroxyl groups, alkyl groups (preferably linear or branched alkyl groups, preferably having 1 to 5 carbon atoms), and halogenated alkyl groups. is preferred, a halogen atom or a halogenated alkyl group having 1 to 5 carbon atoms is more preferred, and a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms is particularly preferred. When the aryl group has a fluorine atom, the polarity of the anion portion is increased, which is preferable.
Among them, each of R ^b01 to R ^b04 in formula (I1) is preferably a fluorinated phenyl group, and particularly preferably a perfluorophenyl group.

Preferred specific examples of the anion portion of the compound represented by the formula (I1) include tetrakis(pentafluorophenyl)borate ([B(C ₆ F ₅ ) ₄ ] ⁻ ); tetrakis[(trifluoromethyl)phenyl] Borate ([B(C ₆ H ₄ CF ₃ ) ₄ ] ⁻ ); difluorobis(pentafluorophenyl)borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ⁻ ); trifluoro(pentafluorophenyl)borate ([ (C ₆ F ₅ )BF ₃ ] ⁻ ); tetrakis(difluorophenyl)borate ([B(C ₆ H ₃ F ₂ ) ₄ ] ⁻ );
Among them, tetrakis(pentafluorophenyl)borate ([B(C ₆ F ₅ ) ₄ ] ⁻ ) is particularly preferred.

The cation portion In the formula (I1), Q ^q+ preferably includes a sulfonium cation and an iodonium cation, and organic cations represented by the following general formulas (ca-1) to (ca-5) are particularly preferred. 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原子数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、また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 optionally substituted aryl group, heteroaryl group, alkyl group or alkenyl group. R ²⁰¹ to R ²⁰³ , R ²⁰⁶ to R ²⁰⁷ and R ²¹¹ to R ²¹² may combine with 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 is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted —SO ₂ —containing cyclic group. L ²⁰¹ represents -C(=O)- or -C(=O)-O-. Each Y ²⁰¹ independently represents an arylene group, an alkylene group or an alkenylene group. x is 1 or 2; W ²⁰¹ represents a (x+1)-valent linking group. ]

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

［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, each R′ ²⁰¹ is independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted chain alkyl group, or a substituted is a chain alkenyl group that may be ]

In the above formulas (ca-r-1) to (ca-r-10), R' ²⁰¹ is each independently a hydrogen atom, an optionally substituted cyclic group, a substituent a chain alkyl group which may be substituted or a chain alkenyl group which may have a substituent.

Cyclic group optionally having 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 without aromaticity. Also, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

The aromatic hydrocarbon group for R' ²⁰¹ is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, still more preferably 5 to 20, particularly preferably 6 to 15, most preferably 6 to 10. . However, the number of carbon atoms does not include the number of carbon atoms in the substituent.
Specific examples of the aromatic ring of the aromatic hydrocarbon group for R′ ²⁰¹ include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or those in which some of the carbon atoms constituting the aromatic ring are substituted with heteroatoms. or rings in which some of the hydrogen atoms constituting these aromatic rings or aromatic heterocycles are substituted with oxo groups or the like. The heteroatom in the aromatic heterocycle includes oxygen atom, sulfur atom, nitrogen atom and the like.
Specific examples of the aromatic hydrocarbon group for R′ ²⁰¹ include 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.), and a hydrogen atom of the aromatic ring. one of which is substituted with an alkylene group (e.g., a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, an arylalkyl group such as a 2-naphthylethyl group, etc.), A group obtained by removing one hydrogen atom from a ring in which a portion of the hydrogen atoms constituting the aromatic ring is substituted with an oxo group (e.g., anthraquinone, etc.), an aromatic heterocyclic ring (e.g., 9H-thioxanthene, 9H-thioxanthene) -9-one, etc.) with one hydrogen atom removed. The alkylene group (the alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

The cyclic aliphatic hydrocarbon group for R' ²⁰¹ includes an aliphatic hydrocarbon group containing a ring in its structure.
The aliphatic hydrocarbon group containing a ring in this structure includes an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group that is linear or branched. Examples thereof include a group bonded to the end of a chain aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group intervenes in the middle of a linear or branched aliphatic hydrocarbon group.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples 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 preferably has 7 to 30 carbon atoms. Among them, the polycycloalkanes include polycycloalkanes having a bridged ring system polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; condensed ring systems such as cyclic groups having a steroid skeleton; Polycycloalkanes having a polycyclic skeleton of are more preferred.

Among them, the cyclic aliphatic hydrocarbon group for R′ ²⁰¹ is preferably a group obtained by removing one or more hydrogen atoms from monocycloalkane or polycycloalkane, and a group obtained by removing one hydrogen atom from polycycloalkane. More preferred are an adamantyl group and a norbornyl group, and most preferred is an adamantyl group.

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 is more preferred, and 1-3 are most preferred.
As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferable, and specifically, a methylene group [ _--CH.sub.2-- ], an ethylene group [--( _CH.sub.2 ) _.sub.2-- ], a trimethylene group [ -(CH ₂ ) ₃ -], tetramethylene group [-(CH ₂ ) ₄ -], pentamethylene group [-(CH ₂ ) ₅ -] and the like.
The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specifically, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) _2- , -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ - and other alkylmethylene 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 Alkylethylene groups such as CH ₃ ) ₂ -CH ₂ -; alkyltrimethylene groups such as -CH(CH ₃ )CH ₂ CH ₂ - and -CH ₂ CH(CH ₃ )CH ₂ -; -CH(CH ₃ ) Examples include alkylalkylene groups such as alkyltetramethylene groups such as CH ₂ CH ₂ CH ₂ — and —CH ₂ CH(CH ₃ )CH ₂ CH ₂ —. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

A chain alkyl group optionally having a substituent:
The chain alkyl group for R' ²⁰¹ may be 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, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, isohexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group and the like.
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, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group and the like.

A chain alkenyl group optionally having a substituent:
The chain alkenyl group for R' ²⁰¹ may be linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and still more preferably 2 to 4 carbon atoms. , 3 are particularly preferred. Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butynyl groups. Examples of branched alkenyl groups include 1-methylvinyl group, 2-methylvinyl group, 1-methylpropenyl group, 2-methylpropenyl group and the like.
Among the above, the chain alkenyl group is preferably a linear alkenyl group, more preferably a vinyl group or a propenyl group, and particularly preferably a vinyl group.

Examples of substituents on the cyclic group, chain 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, an oxo group, and the above A cyclic group, an alkylcarbonyl group, a thienylcarbonyl group and the like for R' ²⁰¹ can be mentioned.

Of these, R' ²⁰¹ is preferably an optionally substituted cyclic group or an optionally substituted chain alkyl group.

When R ²⁰¹ to R ²⁰³ , R ²⁰⁶ to R ²⁰⁷ and R ²¹¹ to R ²¹² are mutually bonded to form a ring together with the sulfur atom in the formula, heteroatoms such as a sulfur atom, an oxygen atom and a nitrogen atom, a carbonyl group, -SO-, -SO ₂ -, -SO ₃ -, -COO-, -CONH- or -N(R _N )- (the R _N is an alkyl group having 1 to 5 carbon atoms); You may couple|bond via functional groups, such as. As the ring to be formed, one ring containing a sulfur atom in the formula in its ring skeleton is preferably a 3- to 10-membered ring including a sulfur atom, particularly a 5- to 7-membered ring. preferable. Specific examples of the ring formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthrene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiine ring, and a tetrahydro A thiophenium ring, a tetrahydrothiopyranium ring, and the like are included.

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

In the formula (ca-3), R ²¹⁰ is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or It is a —SO ₂ —containing cyclic group optionally having a substituent.
The aryl group for R ²¹⁰ includes an unsubstituted aryl group having 6 to 20 carbon atoms, preferably a phenyl group or a naphthyl group.
The alkyl group for R ²¹⁰ is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
The alkenyl group for R ²¹⁰ preferably has 2 to 10 carbon atoms.

In the above formulas (ca-4) and (ca-5), each Y ²⁰¹ independently represents an arylene group, an alkylene group or an alkenylene group.
Examples of the arylene group for Y ²⁰¹ include groups obtained by removing one hydrogen atom from the aryl group exemplified as the aromatic hydrocarbon group for R′ ²⁰¹ .
Examples of the alkylene group and alkenylene group for Y ²⁰¹ include groups obtained by removing one hydrogen atom from the groups exemplified as the chain alkyl group and chain alkenyl group for R′ ²⁰¹ .

In the above formulas (ca-4) and (ca-5), x is 1 or 2.
W ²⁰¹ is a (x+1)-valent, ie divalent or trivalent linking group.
The divalent linking group in W ²⁰¹ is preferably a divalent hydrocarbon group which may have a substituent, and may have a substituent exemplified for R ^EP in the above formula (A1). Groups similar to divalent hydrocarbon groups are preferred. The divalent linking group in W ²⁰¹ may be linear, branched or cyclic, preferably cyclic. Among them, a group in which two carbonyl groups are combined at both ends of an arylene group, or a group consisting only of an arylene group is preferable. The arylene group includes a phenylene group, a naphthylene group and the like, and a phenylene group is particularly preferred.
The trivalent linking group for W ²⁰¹ includes a group obtained by removing one hydrogen atom from the divalent linking group for W ²⁰¹ , a group obtained by further bonding the divalent linking group to the divalent linking group, and the like. mentioned. The trivalent linking group for W ²⁰¹ is preferably a group in which two carbonyl groups are bonded to an arylene group.

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

［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。］

[Wherein, ^{R ″ 201} is ^a hydrogen atom or a substituent ^. is.]

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

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

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

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

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

As the cation represented by the formula (ca-5), cations represented by the following general formulas (ca-5-1) to (ca-5-3) are also 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 moiety [(Q ^q+ ) _1/q ] is preferably a cation represented by the general formula (ca-1), and each of the formulas (ca-1-1) to (ca-1-48) The cation represented by the formula (ca-1-25) is more preferable, the cation represented by the formula (ca-1-29), the cation represented by the formula (ca-1-35), A cation represented by formula (ca-1-47) and a cation represented by formula (ca-1-48) are more preferable.

Specific examples of preferred component (I1) are given below.

≪Other cationic polymerization initiators≫
Examples of cationic polymerization initiators other than the component (I1) include compounds represented by the following general formula (I2-1) or (I2-2) (hereinafter referred to as "(I2) component"); Examples thereof include compounds represented by I3-1) or (I3-2) (hereinafter referred to as “component (I3)”).

(I2) About the component:
The component (I2) is a compound represented by the following general formula (I2-1) or (I2-2).
Since the component (I2) generates a relatively strong acid upon exposure, when a pattern is formed using the photosensitive composition containing the component (I), sufficient sensitivity can be obtained and a good pattern can be obtained. It is formed.

［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、ｑ価の有機カチオンである。］

[In the formula, R ^b05 is an optionally substituted fluorinated alkyl group or a fluorine atom. A plurality of R ^b05 may be the same or different. q is an integer of 1 or more, and Q ^q+ is a q-valent organic cation. ]

［式中、Ｒ^ｂ０６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^ｂ０６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、ｑ価の有機カチオンである。］

[In the formula, R ^b06 is an optionally substituted fluorinated alkyl group or a fluorine atom. A plurality of R ^b06 may be the same or different. q is an integer of 1 or more, and Q ^q+ is a q-valent organic cation. ]

Anion Moiety In the above formula (I2-1), R ^b05 is an optionally substituted fluorinated alkyl group or a fluorine atom. A plurality of R ^b05 may be the same or different.
The fluorinated alkyl group for 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. Specific examples include alkyl groups having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are substituted with fluorine atoms.
Among them, R ^b05 is preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, a fluorine atom, a trifluoromethyl group or pentafluoro Ethyl groups are more preferred.

The anion portion of the compound represented by formula (I2-1) is preferably represented by general formula (b0-2a) below.

［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, ^Rbf05 is a fluorinated alkyl group which may have a substituent. nb ¹ is an integer from 1 to 5; ]

In formula (b0-2a), the optionally substituted fluorinated alkyl group for R ^bf05 is the same as the optionally substituted fluorinated alkyl group for R ^b05 . be.
In formula (b0-2a), nb ¹ is preferably an integer of 1 to 4, more preferably an integer of 2 to 4, and most preferably 3.

In formula (I2-2) above, R ^b06 is an optionally substituted fluorinated alkyl group or a fluorine atom. A plurality of R ^b06 may be the same or different.
The fluorinated alkyl group for R ^b06 preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms. Specific examples include alkyl groups having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are substituted with fluorine atoms.
Among them, R ^b06 is preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and still more preferably a fluorine atom.

Cation Moiety In formulas (I2-1) and (I2-2), q is an integer of 1 or more, and Q ^q+ is a q-valent organic cation.
Examples of Q ^q+ include those similar to Q ^q+ in the above formula (I1). Among them, the cation represented by general formula (ca-1) is preferable, and the Cations represented by (ca-1-48) are more preferable, respectively, a cation represented by formula (ca-1-25), a cation represented by formula (ca-1-29), a cation represented by formula (ca-1 -35) and the cation represented by the formula (ca-1-47) are more preferred.

Specific examples of suitable (I2) component are given below.

(I3) About the component:
The (I3) component 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。］

[Wherein, R ^b11 to R ^b12 are a cyclic group optionally having a substituent other than a halogen atom, a chain alkyl group optionally having a substituent other than a halogen atom, or a halogen atom It is a chain alkenyl group optionally having a substituent other than . m is an integer of 1 or more, and each M ^m+ is independently an m-valent organic cation. ]

{(I3-1) component}
Anion portion In formula (I3-1), R ^b12 is a cyclic group optionally having a substituent other than a halogen atom, a chain alkyl group optionally having a substituent other than a halogen atom , or a chain alkenyl group which may have a substituent other than a halogen atom, and which is a cyclic group, a chain alkyl group, and a chain alkenyl group in the description of R' ²⁰¹ described above. , those having no substituents or those having substituents other than halogen atoms.
R ^b12 is preferably a chain alkyl group optionally having a substituent other than a halogen atom or an aliphatic cyclic group optionally having a substituent other than a halogen atom.
The chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 3 to 10 carbon atoms. Aliphatic cyclic groups include groups obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. (which may have substituents other than halogen atoms); camphor It is more preferable to be a group obtained by removing one or more hydrogen atoms from etc.
The hydrocarbon group of R ^b12 may have a substituent other than a halogen atom ^, and examples of the substituent include the hydrocarbon group (aromatic hydrocarbon group, aliphatic tricyclic group, chain alkyl group) may have the same substituents other than the halogen atom.
Here, "may have a substituent other than a halogen atom" not only excludes the case of having a substituent consisting only of 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.).

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

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

{(I3-2) component}
Anion portion In formula (I3-2), R ^b11 is a cyclic group optionally having a substituent other than a halogen atom, a chain alkyl group optionally having a substituent other than a halogen atom , or a chain alkenyl group which may have a substituent other than a halogen atom, and which is a cyclic group, a chain alkyl group, and a chain alkenyl group in the description of R' ²⁰¹ described above. , those having no substituents or those having substituents other than halogen atoms.

Among these, R ^b11 is an aromatic hydrocarbon group optionally having a substituent other than a halogen atom, an aliphatic cyclic group optionally having a substituent other than a halogen atom, or a halogen A chain alkyl group which may have substituents other than atoms is preferred. Substituents these groups may have include hydroxyl groups, oxo groups, alkyl groups, aryl groups, lactone-containing cyclic groups, ether bonds, ester bonds, and combinations thereof.
When it contains an ether bond or an ester bond as a substituent, it may be via an alkylene group, and the substituent in this case is represented by the following general formulas (y-al-1) to (y-al-7), respectively. is preferred.
In the following general formulas (y-al-1) to (y-al-7), R ^b11 in the above formula (I3-2) is bound to the following general formulas (y-al-1) to It is V' ¹⁰¹ in (y-al-7).

［式中、Ｖ’^１０１は、単結合または炭素原子数１～５のアルキレン基である。Ｖ’^１０２は、炭素原子数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. V' ¹⁰² is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms. ]

The divalent saturated hydrocarbon group for 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 1 to 5 carbon atoms. is more preferably an alkylene group of

The alkylene group for V' ¹⁰¹ and V' ¹⁰² may be a straight-chain alkylene group or a branched alkylene group, and a straight-chain alkylene group is preferred.
Specific examples of the alkylene group for V' ¹⁰¹ and V' ¹⁰² include a methylene group [-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 - and other alkylmethylene groups; ethylene groups [-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 group [-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.
Further, part of the methylene groups 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 cyclic group is obtained by removing one hydrogen atom from the cyclic aliphatic hydrocarbon group (monocyclic alicyclic hydrocarbon group, polycyclic alicyclic hydrocarbon group) of R′ ²⁰¹ . A divalent group is preferred, and a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group is more preferred.

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

R ^b11 is preferably a cyclic group optionally having a substituent other than a halogen atom.
Preferred specific examples of the anion portion of component (I3-2) are shown below.

Cation Moiety In formula (I3-2), M ^m+ is an m-valent organic cation, which is the same as M ^m+ in formula (I3-1).

In addition, the component (I) is a cationic polymerization initiator that generates an acid with a pKa (acid dissociation constant) of −5 or less by exposure, in order to increase the elasticity of the resin film and to easily form a fine structure without residue. Preferably. By using a cationic polymerization initiator that generates an acid having a pKa of preferably −6 or less, more preferably −8 or less, high sensitivity to exposure can be obtained. The lower limit of the pKa of the acid generated by component (I) is preferably -15 or higher. By using a cationic polymerization initiator that generates an acid with such a suitable pKa, it becomes easier to achieve high sensitivity.
Here, "pKa (acid dissociation constant)" is generally used as an indicator of acid strength of a target substance. In addition, pKa in this specification is a value in 25 degreeC temperature conditions. Also, the pKa value can be obtained by measuring by a known method. Also, calculated values using known software such as "ACD/Labs" (trade name, manufactured by Advanced Chemistry Development) can be used.

Specific examples of suitable (I3) component are given below.

As the component (I), one type may be used alone, or two or more types may be used in combination.
In the photosensitive composition of the present embodiment, component (I) is preferably at least one selected from the group consisting of component (I1), component (I2) and component (I3).

In the photosensitive composition of the present embodiment, the content of component (I) is preferably 0.05 to 5 parts by mass when the total parts by mass of component (A) is 100 parts by mass. 0.1 to 3 parts by mass, more preferably 0.15 to 3 parts by mass, and particularly preferably 0.2 to 1 part by mass.
When the content of component (I) is at least the lower limit of the preferred range, sufficient sensitivity is obtained, and the lithography properties of the resist pattern are further improved. In addition, the strength of the cured resin film is further enhanced. On the other hand, when it is equal to or less than the upper limit of the preferred range, the sensitivity is moderately controlled, and a resist pattern with a good shape can be easily obtained.

<Compound (C1) Represented by General Formula (c1)>
The photosensitive composition of the present embodiment contains a compound represented by the following general formula (c1) (component (C1)) in addition to the components (A) and (I). The (C1) component acts as a silane coupling agent in pattern formation. That is, it contributes to the improvement of adhesion between the support (substrate having a wiring layer, etc.) and the pattern (side wall).

［式中、ｎは、４以上の整数である。Ｒ^ＥＰは、エポキシ基含有基である。Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、アルキル基、アリール基又はアルコキシ基である。Ｒ^１、Ｒ^２及びＲ^３は、相互に異なっていてもよいし、二つ以上が同一であってもよい。但し、Ｒ^１、Ｒ^２及びＲ^３のうち、少なくとも一つはアルコキシ基である。］

[In the formula, n is an integer of 4 or more. ^REP is an epoxy group-containing group. R ¹ , R ² and R ³ are each independently an alkyl group, an aryl group or an alkoxy group. R ¹ , R ² and R ³ may be different from each other, or two or more of them may be the same. However, at least one of R ¹ , R ² and R ³ is an alkoxy group. ]

In the formula (c1), n is an integer of 4 or more, preferably an integer of 4 or more and 12 or less, more preferably an integer of 5 or more and 12 or less, and still more preferably an integer of 6 or more and 12 or less. It is preferably an integer of 6 or more and 10 or less.

In formula (c1), ^REP is an epoxy group-containing group.
The epoxy group-containing group of R ^EP is not particularly limited, and includes 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. and a group having
An alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure which is a three-membered ring ether, and specifically a group having an alicyclic group and an oxacyclopropane structure.
The alicyclic group that forms the basic skeleton of the alicyclic epoxy group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups. Moreover, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group etc. are mentioned as a polycyclic alicyclic group. Moreover, the hydrogen atoms 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 alicyclic epoxy group and a divalent linking group, the epoxy group or alicyclic epoxy It is preferred that the groups are attached.
The divalent linking group here includes the divalent linking group (optionally substituted divalent hydrocarbon ^group , hetero atom and divalent linking groups including).
Among them, a glycidyl group is preferable as the epoxy group-containing group in ^REP .

In formula (c1), R ¹ , R ² and R ³ are each independently an alkyl group, an aryl group or an alkoxy group.
The alkyl groups for R ¹ , R ² and R ³ may be linear, branched or cyclic. Linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n -decyl group and the like. Branched alkyl groups include isopropyl, isobutyl, tert-butyl, sec-butyl, isopentyl, neopentyl, isohexyl, isoheptyl, isooctyl, tert-octyl, isononyl, and isodecyl groups. etc. A cyclopentyl group, a cyclohexyl group, etc. are mentioned as a cyclic alkyl group. Among these, straight-chain alkyl groups are preferred, straight-chain alkyl groups having 1 to 6 carbon atoms are preferred, and straight-chain alkyl groups having 1 to 3 carbon atoms are more preferred.
The aryl group for R ¹ , R ² and R ³ includes phenyl group, tolyl group, xylyl group, naphthyl group and the like.
Alkoxy groups for R ¹ , R ² and R ³ include methoxy, ethoxy, n-propoxy, isopropoxy and the like.
In formula (c1), each of R ¹ , R ² and R ³ is preferably an alkoxy group.

R ¹ , R ² and R ³ may be different from each other, or two or more of them may be the same. However, at least one of R ¹ , R ² and R ³ is an alkoxy group. Among them, all of R ¹ , R ² and R ³ are preferably alkoxy groups.

Some or all of the hydrogen atoms in the alkyl group, aryl group or alkoxy group for R ¹ , R ² and R ³ may be substituted with other substituents. Specific examples of this substituent include an alkyl group having 1 to 3 carbon atoms; an alkoxy group having 1 to 3 carbon atoms; a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.); an aromatic hydrocarbon group such as a phenyl group. a cyano group, an amino group, an ester group, an ether group, a carbonyl group, an acyl group, a sulfide group and the like; The substitution position of these substituents is not particularly limited, and the number of substituents is also not limited.

Preferred (C1) components are exemplified below.

As the component (C1), 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 component (C1) is preferably 0.05 to 3 parts by mass when the total parts by mass of component (A) is 100 parts by mass. 0.1 to 3 parts by mass, more preferably 0.25 to 3 parts by mass, and particularly preferably 0.5 to 2.5 parts by mass.
When the content of the component (C1) is at least the lower limit of the preferred range, the adhesion between the support (substrate having a wiring layer, etc.) and the pattern (side wall) is more likely to be enhanced. On the other hand, if it is equal to or less than the upper limit of the above preferable range, it becomes difficult for the component (C1) to undergo a change over time due to condensation.

<Optional component>
The photosensitive composition of the present embodiment may optionally contain other components (optional components) in addition to the components (A), (I) and (C1) described above.
The photosensitive compositions of embodiments optionally contain miscible additives such as metal oxides (M), sensitizer components, solvents, additional resins to improve film performance, dissolution inhibitors, , a basic compound, a plasticizer, a stabilizer, a coloring agent, an antihalation agent, and the like can be added as appropriate.

<<Metal oxide (M)>>
The photosensitive composition of the present embodiment, in addition to the (A) component, (I) component and (C1) component, since it is easy to obtain a cured film with increased strength, further metal oxide (M) (hereinafter also referred to as “(M) component”). By using the component (M) together, a pattern with a good shape and high resolution can be formed.
Examples of the component (M) include oxides of metals such as silicon (metallic silicon), titanium, zirconium and hafnium. Among these, oxides of silicon are preferred, and among these, it is particularly preferred to use silica.
The shape of component (M) is preferably particulate. Such particulate component (M) preferably comprises a particle group having a volume average particle diameter of 5 to 40 nm, more preferably comprising a particle group having a volume average particle diameter of 5 to 30 nm. More preferably, it consists of a group of particles with a diameter of 10 to 20 nm.

<<Sensitizer component>>
The photosensitive composition of this embodiment may further contain a sensitizer component.
The sensitizer component is not particularly limited as long as it can absorb energy from exposure and transmit the energy to other substances.
Specific examples of sensitizer components include benzophenone-based photosensitizers such as benzophenone and p,p'-tetramethyldiaminobenzophenone, carbazole-based photosensitizers, acetophene-based photosensitizers, and 1,5-dihydroxynaphthalene. naphthalene-based photosensitizers, phenol-based photosensitizers, anthracene-based photosensitizers such as 9-ethoxyanthracene, biacetyl, eosin, rose bengal, pyrene, phenothiazine, and known photosensitizers such as anthrone. can be used.

≪Solvent≫
The photosensitive composition of the present embodiment may further contain a solvent (hereinafter sometimes referred to as "(S) component").
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. , 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 Compounds having an ester bond such as monoacetate, monoalkyl ethers such as monomethyl ethers, monoethyl ethers, monopropyl ethers and monobutyl ethers of the polyhydric alcohols or compounds having an ester bond, or ether bonds such as monophenyl ethers [Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred]; cyclic ethers such as dioxane, methyl lactate, lactic acid Esters such as ethyl (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, di Aromatic organic solvents such as benzyl ether, phenetol, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene and mesitylene, dimethylsulfoxide (DMSO) and the like.

The (S) component may be used singly or as a mixed solvent of two or more.

When the component (S) is included, the amount used is not particularly limited, and is appropriately set according to the coating film thickness at a concentration at which the photosensitive composition can be coated onto a substrate or the like without dripping.
For example, the (S) component can be used so that the solid content concentration is 50% by mass or more, or the (S) component can be used so that the solid content concentration is 60% by mass or more.
Moreover, the aspect (namely, the aspect whose solid content concentration is 100 mass %) which does not contain (S) component substantially can be employ|adopted.

The negative photosensitive composition of the present embodiment described above contains an epoxy group-containing compound (A), a cationic polymerization initiator (I), and a compound (C1) represented by general formula (c1). It is. In the component (C1) employed in the present embodiment, the linking group between R ^EP —O— and —Si(R ¹ )(R ² )(R ³ ) is an alkanediyl having 4 or more carbon atoms. A long-chain hydrocarbon group having a larger number of carbon atoms than the conventional one (alkanediyl group having 3 carbon atoms) is selected. Since the component (C1) is contained, the negative photosensitive composition of the present embodiment can form sidewalls (patterns) with high adhesion to the wiring layer after a moisture resistance test at high temperature.
By using the negative photosensitive composition of the present embodiment, the adhesion between the substrate having the aluminum wiring and the side wall can be enhanced, particularly after the moisture resistance test, and the reliability of the electronic component can be improved. .

(Pattern formation method)
The pattern forming method of the present embodiment includes a step of forming a photosensitive film on a substrate having aluminum wiring using the negative photosensitive composition (photosensitive composition) of the above-described embodiment (hereinafter referred to as “film forming step ”), a step of exposing the photosensitive film (hereinafter referred to as “exposure step”), and developing the exposed photosensitive film with a developer containing an organic solvent to form a negative pattern. and a step (hereinafter referred to as “development step”).
The pattern forming method of this embodiment can be performed, for example, as follows.

[Film forming step]
First, on a substrate having aluminum wiring, the photosensitive composition of the above-described embodiment is applied by a known method such as a spin coating method, a roll coating method, or a screen printing method, and baked (post-apply bake (PAB)). The treatment is performed for 2 to 60 minutes at a temperature of, for example, 50 to 150° C. to form a photosensitive film.
The film forming step can also be performed by preparing a film of the photosensitive composition of the above-described embodiment in advance and disposing this film on a substrate having aluminum wiring.

_The substrate is not particularly limited, _and conventionally known substrates can be used. Substrates made of metals such as titanium tungsten, copper, chromium, and iron, and glass substrates can be used.
In this embodiment, aluminum wiring is used for the wiring pattern.
"Aluminum wiring" includes not only wiring made of aluminum alloys, but also wiring made of alloys of aluminum and other metals. It is preferable to use an aluminum alloy, an aluminum-copper alloy, or the like as an alloy constituting wiring that can be used as an aluminum wiring.
For example, as a substrate having aluminum wiring, a substrate on which an aluminum layer (Al layer) is formed by a sputtering method is used. The film thickness of the Al layer is, for example, 50 to 300 nm.

Although the film thickness of the photosensitive film formed from the photosensitive composition is not particularly limited, it is preferably about 10 to 100 μm.

[Exposure process]
Next, the formed photosensitive film is subjected to selective exposure such as exposure through a mask having a predetermined pattern formed thereon (mask pattern) or exposure without a mask pattern using a known exposure apparatus. conduct.
After performing the selective exposure, baking (post-exposure baking (PEB)) treatment is optionally 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 such as ultraviolet rays with a wavelength of 300 to 500 nm, i-rays (wavelength of 365 nm), or visible light is selectively irradiated (exposed). Low-pressure mercury lamps, high-pressure mercury lamps, extra-high pressure mercury lamps, metal halide lamps, argon gas lasers, and the like can be used as sources of these radiations.
Radiation here means ultraviolet rays, visible rays, deep ultraviolet rays, X-rays, electron beams, and the like. The dose of radiation varies depending on the type and blending amount of each component in the composition, the film thickness of the coating film, etc., but is 100 to 2000 mJ/cm ² in the case of using an ultra-high pressure mercury lamp, for example.

The method of exposing the photosensitive film may be normal exposure (dry exposure) carried out in air or an inert gas such as nitrogen, or may be liquid immersion lithography.

[Development process]
Next, the exposed photosensitive film is developed with a developer containing an organic solvent (organic developer). After development, a rinse treatment is preferably performed. Baking (post-baking) may be performed as necessary.

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

Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, and methyl ethyl ketone. , methyl isobutyl ketone, acetylacetone, acetonyl acetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, methyl amyl ketone (2-heptanone) and the like. Among these, methyl amyl ketone (2-heptanone) is preferable as the ketone solvent.

Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether acetate, Ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol 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 formate, ethyl formate, formic acid Butyl, propyl formate, 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 propionate, propyl-3-methoxypropionate and the like. Among these, butyl acetate or PGMEA is preferable as the ester solvent.

Nitrile solvents include, for example, acetonitrile, propionitrile, valeronitrile, butyronitrile and the like.

Known additives can be added to the organic developer as needed. Examples of such additives include surfactants. Although the surfactant is not particularly limited, for example, ionic or nonionic fluorine-based and/or silicon-based surfactants 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 a surfactant is blended, its blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and 0.01 to 0.5% by mass, relative to the total amount of the organic developer. 5% by mass is more preferred.

The development treatment can be carried out by a known development method, for example, a method of immersing the substrate in the developer for a certain period of time (dip method), or a method of raising the developer on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time. method (paddle method), method of spraying the developer onto the surface of the substrate (spray method), and method of continuously spraying the developer while scanning the developer spray nozzle at a constant speed onto the substrate rotating at a constant speed ( dynamic dispensing method) and the like.

Rinsing treatment (cleaning treatment) using a rinse liquid can be performed by a known rinsing method. Examples of the rinsing method include a method of continuously applying the rinse solution onto the substrate rotating at a constant speed (rotation coating method), a method of immersing the substrate in the rinse solution for a certain period of time (dip method), and a method of immersing the substrate in the rinse solution. and a method of spraying a rinse solution (spray method).
For the rinsing treatment, it is preferable to use a rinsing liquid containing an organic solvent.

Through the series of operations of the film forming process, the exposure process and the developing process described above, a negative pattern to be the side wall can be formed on the substrate having the aluminum wiring.

The pattern forming method of the present embodiment described above includes a film forming step of forming a photosensitive film on a substrate having aluminum wiring using the negative photosensitive composition (photosensitive composition) of the embodiment described above. , an exposure step, and a development step. In such a pattern forming method, since the photosensitive composition of the above-described embodiment is used, a negative pattern that becomes a sidewall having high adhesion to a substrate having aluminum wiring after a moisture resistance test at high temperature is formed. can.

(Manufacturing method of hollow package)
This embodiment is
A method for manufacturing a hollow package comprising a hollow structure housing aluminum wiring on a substrate having aluminum wiring, comprising:
forming sidewalls of the hollow structure on the substrate having the aluminum wiring using the pattern forming method of the above-described embodiment;
a step of forming a top plate portion on the side wall to fabricate the hollow structure housing the aluminum wiring;
including.
The manufacturing method of the hollow package of this embodiment can be performed, for example, as follows.

FIG. 1 is a schematic diagram illustrating an embodiment of a hollow package manufacturing method.
In the manufacturing method of the hollow package of the present embodiment, the top plate portion is formed on the negative pattern (side wall 20) formed on the substrate 10 having the aluminum wiring (not shown) by the pattern forming method of the above-described embodiment. A hollow structure 100 is formed to accommodate the aluminum wiring.
The hollow package manufacturing method of the present embodiment includes the following steps (0), (i), (ii), (iii), (iv), and (v). .

Step (0): A step of preparing a substrate 10 having aluminum wiring on which sidewalls 20 (negative pattern) are formed by the pattern forming method of the above-described embodiment, and a photosensitive resist film 30F having a photosensitive film 30. Step (i): A step of arranging a photosensitive resist film 30F so as to close the opening surface of the recess 15 formed by the side wall 20 and the substrate 10 Step (ii): After the step (i), the photosensitive film 30 Step (iii): A step of heat-treating the photosensitive film 30 after the step (ii) Step (iv): After the step (iii), the photosensitive film 30 is developed to expose the sidewall Step (v): forming a negative pattern (exposed portion 30A) that closes the opening surface of the recess 15 formed by 20 and the substrate 10; A step of further curing by heat treatment to obtain the hollow structural body 100 in which the exposed portion 30A serving as the top plate portion is composed of the cured body 40 of the photosensitive film 30.

[Step (0)]
In the step (0) of the present embodiment, the substrate 10 on which the side wall 20 (negative pattern) is formed by the pattern forming method of the embodiment described above and a photosensitive resist film 30F having a photosensitive film are prepared.
In FIG. 1, substrate 10 having aluminum wiring (not shown) and sidewalls 20 formed on substrate 10 constitute substrate 10 having recesses 15 on its surface.

<<About the photosensitive resist film 30F>>
The photosensitive resist film 30F in this embodiment has, for example, a negative photosensitive film 30 containing an epoxy group-containing compound (component (A)) and a cationic polymerization initiator (component (I)). The photosensitive film 30 can be formed from the negative photosensitive composition described above.
The photosensitive film 30 forming the exposure portion 30A that serves as the top plate portion may be made of the same material as the photosensitive material forming the side wall 20, or may be made of a different material.

When the photosensitive film 30 is formed using the photosensitive resist film 30F and selectively exposed to light, acid is generated from the component (I) in the exposed portion 30A of the photosensitive film 30. , 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 a developer containing an organic solvent is reduced, while the photosensitive film 30 is unexposed. In the portion 30B, since the solubility of the component (A) in the developer containing the organic solvent does not change, between the exposed portion 30A and the unexposed portion 30B of the photosensitive film 30, the developer containing the organic solvent There is a difference in solubility for That is, the photosensitive film 30 is of negative type. Therefore, when the photosensitive film 30 is developed with a developer containing an organic solvent, the unexposed portion 30B is dissolved and removed to form a negative pattern.

Here, the negative photosensitive film 30 included in the photosensitive resist film 30F is typically made of a B-stage (semi-cured state) resin material.
Examples of the photosensitive resist film 30F include a laminate film in which the photosensitive film 30 is laminated on a base film. As the photosensitive resist film 30F in this embodiment, it is preferable to use a laminate film in which the photosensitive film 30 is laminated on a base film.

The photosensitive resist film 30F is manufactured by coating a base film with a negative photosensitive composition in which components (A) and (I) are dissolved in a solvent and drying to form a photosensitive film 30. can.
The application of the negative photosensitive composition onto the substrate film may be carried out using an applicator, blade coater, lip coater, comma coater, film coater, or the like, using an appropriate method.
The thickness of the photosensitive film 30 is preferably 100 μm or less, more preferably 5 to 50 μm.

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

Using the substrate 10 having the side walls 20 on the surface and the photosensitive resist film 30F prepared in the above step (0), the following steps (i) to (v )I do.

[Step (i)]
In step (i), the photosensitive resist film 30F is arranged so that the surface of the photosensitive film 30 constituting the photosensitive resist film 30F closes the opening of the recess 15 formed by the side wall 20 and the substrate 10. . After that, the base film is peeled off from the photosensitive film 30 constituting the photosensitive resist film 30F.
In FIG. 1, the photosensitive film 30 constituting the photosensitive resist film 30F is arranged so as to face the substrate 10 with the sidewall 20 interposed therebetween. A hollow closed space (cavity) surrounded by the substrate 10, the side wall 20, and the photosensitive film 30 is formed.

[Step (ii)]
In step (ii), the photosensitive film 30 is exposed.
For example, the photosensitive film 30 is selectively exposed through a photomask 60 on which a predetermined pattern is formed using a known exposure device.

The wavelength used for exposure is not particularly limited, and radiation such as ultraviolet rays with a wavelength of 300 to 500 nm, i-ray (wavelength of 365 nm), or visible light is selectively irradiated (exposed). Low-pressure mercury lamps, high-pressure mercury lamps, extra-high pressure mercury lamps, metal halide lamps, argon gas lasers, and the like can be used as sources of these radiations.

[Step (iii)]
In step (iii), the exposed photosensitive film 30 is subjected to a heat treatment, a so-called post-exposure bake (PEB) treatment.
The PEB treatment is performed, for example, at a temperature of 80 to 150° C. for 40 to 600 seconds, preferably 60 to 300 seconds.
By the heat treatment in step (iii), the exposed photosensitive film 30 becomes an exposed portion 30A in which the epoxy groups in the component (A) are ring-opening polymerized and an unexposed portion 30B that remains unchanged.

[Step (iv)]
In step (iv), the photosensitive film 30 (exposed portion 30A, unexposed portion 30B) after PEB processing is developed to form a negative pattern (exposed portion 30A).
The development here can be performed in the same manner as the [development step] in the pattern forming method of the embodiment described above. After development, a rinse treatment is preferably performed.
The development in step (iv) dissolves and removes the unexposed portion 30B, leaving an afterimage of the exposed portion 30A that will become the top plate portion (roof covering the opening surface of the recess 15) as a negative pattern.

[Step (v)]
In step (v), the negative pattern (exposed portion 30A) after development is further cured by heat treatment (curing operation), and the top plate portion is formed of the cured body 40 of the photosensitive film 30. A structure 100 is obtained.
The heat treatment (curing operation) is performed, for example, at a temperature of 150 to 250° C. for 30 minutes or more and 120 minutes or less, preferably 45 minutes or more and 90 minutes or less.
In FIG. 1, the cured body 40 is formed by curing and integrating the photosensitive material forming the side wall 20 and the photosensitive film 30 respectively.
Through the series of operations of steps (i) to (v) described above, the hollow structure 100 accommodating the aluminum wiring can be produced.

The manufacturing method of the hollow package of the present embodiment described above includes the steps of forming sidewalls of the hollow structure on a substrate having aluminum wiring using the pattern forming method of the embodiment described above, and and forming a top plate portion to fabricate the hollow structure that accommodates the aluminum wiring. Since the photosensitive composition of the embodiment described above is used in such a hollow package manufacturing method, the adhesion between the side wall and the substrate having the aluminum wiring is enhanced.
A hollow structure 100 shown in FIG. 1 comprises a substrate 10 having aluminum wiring and a cured body 40 . According to this embodiment, the bonding strength between the substrate 10 and the cured body 40 can be increased. Therefore, especially after the moisture resistance test, the adhesion between the substrate having the aluminum wiring and the side wall can be enhanced, and the reliability of the electronic component can be improved.

[Other processes]
Regarding the method for manufacturing a hollow package, in the above-described embodiment, the method for manufacturing a hollow package including step (0) and steps (i) to (v) was described, but it is not limited to this, and the above step is optional. After (v), a step of sealing the hollow structure with a sealing material may be further included.

As the sealing material, for example, a resin composition can be used. The resin used for the sealing material is not particularly limited as long as it can at least either seal or insulate the hollow structure. Examples thereof include epoxy-based resins and silicone-based resins.
The sealing material may contain other components such as a filler in addition to the resin.

A method of sealing the hollow structure with the sealing material is not particularly limited, and a method of supplying a heat-melted sealing material onto the hollow structure so as to cover the hollow structure and performing compression molding can be used. Thereby, a hollow package having a sealing material layer provided on the hollow structure is produced.
The sealing material layer has a function of protecting the MEMS, wiring parts, etc. in the hollow structure from the external environment.

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

<Preparation of negative photosensitive composition>
(Example 1, Comparative Examples 1 to 4)
Each component shown in Table 1 was mixed and dissolved in 3-methoxybutyl acetate, filtered using a PTFE filter (pore size 1 μm, manufactured by PALL), and the negative photosensitive composition (solid content 70 mass % solution) were prepared respectively.

In Table 1, each abbreviation has the following meaning. The numbers in [ ] are the blending amounts of each component (parts by mass; converted to solid content).
(A)-1: A novolak-type epoxy resin represented by the following chemical formula (A1-1). Trade name "jER-157S70", manufactured by Mitsubishi Chemical Corporation.

(A)-2: A solid bisphenol type epoxy resin represented by the following chemical formula (A2-1). Trade name "EPICLON1055", manufactured by DIC Corporation.

(I)-1: A cationic polymerization initiator represented by the following chemical formula (I1-5).

(C)-1: A compound represented by the following chemical formula (C1-1).
(C)-2: A compound represented by the following chemical formula (C2-1).
(C)-3: A compound represented by the following chemical formula (C2-2).
(C)-4: A compound represented by the following chemical formula (C2-3).

<Pattern formation>
A support was used in which an aluminum layer (Al layer) having a thickness of 200 nm was formed on a silicon wafer by a sputtering method.
Film formation process:
The negative photosensitive composition of each example was applied to the Al layer side of the support using a spin coater (manufactured by Mikasa Co., Ltd., MS-B150), and then on a hot plate at a temperature of 115 ° C. for 5 minutes. A photosensitive film having a thickness of 20 μm was formed by pre-baking (PAB) treatment and drying.

Exposure process:
Next, using an aligner (manufactured by Canon Inc., PLA-501), the photosensitive film is irradiated with ghi rays at a dose of 200 mJ/cm ² through a mask having a square pattern of 100 μm×100 μm. bottom.
Next, the exposed photosensitive film was subjected to post-exposure heating on a hot plate at 90° C. for 5 minutes.

Development process:
Next, the photosensitive film after exposure and heating is subjected to puddle development at 23° C. for 90 seconds using propylene glycol monomethyl ether acetate (PGMEA) as a developer to form a square negative pattern of 100 μm×100 μm. tried to form.

As a result, when the negative photosensitive compositions of Example 1 and Comparative Examples 1, 2 and 4 were used, a negative pattern was formed on the support.
When the negative photosensitive composition of Comparative Example 3 was used, pattern formation was impossible due to insufficient sensitivity.

Curing process:
Next, the negative pattern was further cured by heat treatment (200° C., 1 hour, under nitrogen atmosphere) in a baking furnace to obtain a cured body.

<Evaluation>
A pressure cooker test (PCT) was performed on the obtained cured body. Specifically, using a PCT apparatus (EHS-221MD, manufactured by Espec Co., Ltd.), the cured body was subjected to treatment under conditions of a temperature of 121° C. and a relative humidity of 100% for 96 hours.

[Evaluation of Adhesion between Al Layer and Hardened Body on Support]
A bond tester Condor Sigma manufactured by XYZTEC was used to measure the breaking load (N) between a cured body obtained by curing a negative pattern of 100 μm×100 μm and an aluminum layer (Al layer) on the support. Table 2 shows the measurement results.

From the results shown in Table 2, the negative photosensitive composition of Example 1 has better adhesion to the wiring layer after the moisture resistance test at high temperature than the negative photosensitive compositions of Comparative Examples 1, 2 and 4. It was confirmed that a pattern (side wall) with high resilience could be formed.

Reference Signs List 10 Substrate 15 Recess 20 Side Wall 30 Photosensitive Film 30F Photosensitive Resist Film 40 Curing Body 60 Photomask 100 Hollow Structure

Claims (5)

an epoxy group-containing compound (A);
a cationic polymerization initiator (I);
a compound (C1) represented by the following general formula (c1);
A negative photosensitive composition containing

[In the formula, n is an integer of 4 or more. ^REP is an epoxy group-containing group. R ¹ , R ² and R ³ are each independently an alkyl group, an aryl group or an alkoxy group. R ¹ , R ² and R ³ may be different from each other, or two or more of them may be the same. However, at least one of R ¹ , R ² and R ³ is an alkoxy group. ] 2. The negative photosensitive composition according to claim 1, wherein the content of said compound (C1) is 0.05 to 3 parts by mass with respect to 100 parts by mass of said epoxy group-containing compound (A). A step of forming a photosensitive film using the negative photosensitive composition according to claim 1 or 2 on a substrate having aluminum wiring;
exposing the photosensitive film;
a step of developing the exposed photosensitive film with a developer containing an organic solvent to form a negative pattern;
A method of forming a pattern, comprising: A method for manufacturing a hollow package comprising a hollow structure housing aluminum wiring on a substrate having aluminum wiring, comprising:
forming sidewalls of the hollow structure on the substrate having the aluminum wiring using the patterning method of claim 3;
a step of forming a top plate portion on the side wall to fabricate the hollow structure housing the aluminum wiring;
A method of making a hollow package, comprising: 5. The method of manufacturing a hollow package according to claim 4, further comprising the step of sealing said hollow structure with a sealing material after said step of fabricating said hollow structure.

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