JP2023034044A - Method for manufacturing laminate, method for forming curing pattern, laminate and photosensitive composition - Google Patents

Abstract

To provide a method for manufacturing a laminate which can be formed into a resin cured film that enables a high aspect of a pattern and is less likely to be peeled from a support, and a photosensitive composition which is useful as a material forming the lowest layer of the laminate.SOLUTION: A method for manufacturing a laminate 10 includes the steps of forming a first resist layer 11 on a support 20 using a first photosensitive composition, and forming a second resist layer 12 on the first resist layer 11 using a second photosensitive composition, wherein a photosensitive composition having sensitivity higher than that of the second photosensitive composition is used as the first photosensitive composition. The first photosensitive composition contains a polyfunctional aromatic epoxy compound, an optical acid generator, and an alicyclic epoxy compound.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a method for producing a laminate, a method for forming a cured pattern, a laminate, and a photosensitive composition.

2. Description of the Related Art As an inductor, which is one of the passive elements of electric and electronic circuits, a wire-wound inductor having an insulating portion made of a cured resin film and a coil pattern made of a plated layer of copper or the like is used.
FIG. 5 is a partial cross-sectional view showing an example of a wire-wound inductor. A wire-wound inductor 200 shown in FIG. 5 comprises a coil-shaped hardening pattern 120 formed on a support 20 and a plating layer 30 filling a space in the hardening pattern 120 .
A wire-wound inductor is made by forming a resist layer on a support, selectively exposing the resist layer through a photomask, developing it, and then curing it to form a coil-shaped cured pattern (resin It is produced by forming a hardened film) and then plating between the insulating portions.

Conventionally, as a technique for manufacturing a wire-wound inductor, a first insulating layer, a spirally wound coil pattern formed on the first insulating layer, and a coil pattern formed on the first insulating layer and a method of manufacturing a coil component including an in-layer insulating pattern arranged along the coil pattern and a second insulating layer covering the coil pattern and the in-layer insulating pattern (Patent References 1 and 2).

JP 2020-136466 A JP 2020-136467 A

2. Description of the Related Art In recent years, electrical and electronic components have become multi-functional, and inductors are required to be small and maintain current capacity. In order to meet such demands, it is necessary to miniaturize the insulating portion that constitutes the inductor. However, with the miniaturization of the insulating portion, the aspect ratio of the cured pattern (cured resin film) forming the insulating portion increases, and the contact area between the cured resin film and the support decreases. On the other hand, in the conventional manufacturing method, the cured resin film is easily peeled off from the support, which may cause short circuit.

The present invention has been made in view of the above circumstances, and a laminate that can achieve a high aspect ratio of the pattern and can be a cured resin film that is difficult to peel off from the support, a method for producing the same, and the lowest layer of the laminate It is an object to provide a photosensitive composition useful as a material for forming a and a cured pattern.

The inventors of the present invention have found, through investigation, that a laminate of a first resist layer and a second resist layer is utilized when forming a coil-shaped cured pattern (resin cured film) that serves as an insulating portion of a wire-wound inductor. , the sensitivity of the first photosensitive composition which is the material of the first resist layer in contact with the support, the sensitivity of the second photosensitive composition which is the material of the second resist layer adjacent to the first resist layer By making the sensitivity higher than the sensitivity, the adhesion between the support and the first resist layer is enhanced, and peeling of the cured resin film from the support and collapse of the cured pattern are suppressed. Completed.
In order to solve the above problems, the present invention employs the following configurations.

That is, the first aspect of the present invention comprises the steps of forming a first resist layer on a support using a first photosensitive composition, and forming a second photosensitive composition on the first resist layer. and forming a second resist layer using a photosensitive composition, wherein the first photosensitive composition is compared with the second photosensitive composition. A method for producing a laminate, characterized by using a photosensitive composition having high sensitivity.

A second aspect of the present invention includes a step of exposing the laminate manufactured by the laminate manufacturing method according to the first aspect, and a step of developing the exposed laminate to form a resist pattern. and a step of curing the resist pattern to obtain a cured pattern.

A third aspect of the present invention is a laminate of a first resist layer and a second resist layer, wherein the first resist layer comprises a polyfunctional aromatic epoxy compound, a photoacid generator, It is a layer containing an alicyclic epoxy compound represented by the following general formula (m1), and the second resist layer is a layer containing a polyfunctional aromatic epoxy compound and a photoacid generator (provided that the (excluding those containing an alicyclic epoxy compound).

［式中、Ｒ^１～Ｒ^１８は、それぞれ独立に、水素原子、ハロゲン原子又は有機基である。Ｘは、２価の連結基又は単結合である。］

[In the formula, R ¹ to R ¹⁸ are each independently a hydrogen atom, a halogen atom or an organic group. X is a divalent linking group or a single bond. ]

A fourth aspect of the present invention is characterized by containing a polyfunctional aromatic epoxy compound, a photoacid generator, and an alicyclic epoxy compound represented by the following general formula (m1): It is a photosensitive composition for forming the layer in contact with the support.

［式中、Ｒ^１～Ｒ^１８は、それぞれ独立に、水素原子、ハロゲン原子又は有機基である。Ｘは、２価の連結基又は単結合である。］

[In the formula, R ¹ to R ¹⁸ are each independently a hydrogen atom, a halogen atom or an organic group. X is a divalent linking group or a single bond. ]

According to the present invention, a laminate that can achieve a high aspect ratio of a pattern and can be a cured resin film that is difficult to peel off from a support, a method for producing the same, and a photosensitive material useful as a material for forming the bottom layer of the laminate Compositions and cure patterns can be provided.

1 is a cross-sectional view showing one embodiment of a laminate 10 formed on a support 20; FIG. 4 is a schematic diagram for explaining a step (iv) of exposing the laminate 10 formed on the support 20. FIG. FIG. 10 is a schematic diagram for explaining a step (v) of developing the exposed laminate 10 to form a resist pattern 110. FIG. FIG. 4 is a schematic diagram for explaining a step (vi) of curing a resist pattern 110 to obtain a cured pattern 120 composed of a cured resin film 10c; 1 is a partial cross-sectional view showing an example of a wire-wound inductor; FIG.

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.

The present invention is characterized by a photosensitive material for forming the bottom layer of the cured pattern (the layer in contact with the support), which can constitute the insulating portion of the inductor, and known techniques can be used for the configuration of layers other than the bottom layer. Applicable.
1 to 4 are schematic diagrams for explaining an embodiment of a process for forming a cured pattern that constitutes an insulating portion in an inductor.
The process of forming a cured pattern will now be described with reference to the accompanying drawings.
In the drawings, in order to make each component easy to see, the component may be shown schematically, and depending on the component, the scale of the dimensions may be changed.

(Laminate manufacturing method)
A first aspect of the present invention comprises a step of forming a first resist layer on a support using a first photosensitive composition, and a second photosensitive composition on the first resist layer. and forming a second resist layer using a material. In such a laminate manufacturing method, a photosensitive composition having higher sensitivity than the second photosensitive composition is used as the first photosensitive composition.

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

The layered product 10 is produced by a step (i) of forming a first resist layer 11 on a support 20 using a first photosensitive composition, and a second photosensitive composition on the first resist layer 11 . Step (ii) of forming a second resist layer 12 using the composition, and step (iii) of forming a third resist layer 13 and a fourth resist layer 14 on the second resist layer 12 in this order. ), and can be manufactured by a manufacturing method having.
Each of steps (i) to (iii) will be described below. Details of the first photosensitive composition and the second photosensitive composition will be described later.

<Step (i)>
In step (i), a first resist layer 11 is formed on a support 20 using a first photosensitive composition. In this embodiment, the first photosensitive composition is a photosensitive composition having higher sensitivity than the second photosensitive composition used in step (ii) described below.
The method of forming the first resist layer 11 on the support 20 may be, for example, a method of applying the first photosensitive composition in a solution state onto the support and pre-baking (PAB) treatment. A method of laminating the film-shaped first photosensitive composition and a support may also be used.

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

When the first photosensitive composition in the form of a film is used, a laminated film (1) in which a photosensitive resin film is previously formed on a base film in the same manner as described above is laminated with the photosensitive resin film and the support 20. A first resist layer 11 (photosensitive resin film) is formed on the support 20 by laminating so that the .
The conditions for laminating the photosensitive resin film using the first photosensitive composition and the support 20 are, for example, a temperature of 30 to 100° C., a pressure of 0.1 to 0.5 MPa, and a processing speed of 0.2 to 0.2. 1.0 m/min is preferable.

The thickness of the first resist layer 11 (photosensitive resin film) is preferably 50 μm or less, more preferably 5 to 50 μm, still more preferably 10 to 40 μm.

As the base film constituting the laminate film (1), a known one can be used, and for example, a thermoplastic resin film or the like is used. The thermoplastic resin includes polyester such as polyethylene terephthalate. The thickness of the base film is preferably 2-150 μm.

As the support 20, a conventionally known one can be used.
More specifically, substrates for electronic components include silicon, silicon nitride, titanium, tantalum, lithium tantalate (LiTaO ₃ ), niobium, lithium niobate (LiNbO ₃ ), palladium, titanium tungsten, copper, chromium, and iron. , metal substrates such as aluminum, glass substrates, and the like.
Materials for the wiring pattern include, for example, copper, aluminum, nickel, and gold.
Further, the support 20 may be one in which an organic material film is provided on the substrate as described above. Examples of organic material films include organic antireflection coatings (organic BARC) and organic films such as lower layer organic films in multilayer resist methods.
Further, the support 20 may be a substrate as described above impregnated with a thermosetting resin (a substrate containing a thermosetting resin). A bismaleimide triazine resin etc. are mentioned as a thermosetting resin here.
From the viewpoints of heat resistance, electrical properties, ease of processing, cost, etc., the support 20 in the present embodiment preferably includes a substrate containing a thermosetting resin, and a substrate containing a bismaleimide triazine resin. is more preferably used.

<Step (ii)>
In step (ii), a second resist layer 12 is formed on the first resist layer 11 using a second photosensitive composition. In the present embodiment, a photosensitive composition having lower sensitivity than the first photosensitive composition is used for the second photosensitive composition.
A method of forming the second resist layer 12 on the first resist layer 11 includes a method of laminating the second photosensitive composition in the form of a film and the first resist layer 11. .
Using the second photosensitive composition in the form of a film, a laminated film (2) in which a photosensitive resin film is formed in advance on a base film in the same manner as described above, is prepared using the second photosensitive composition. A second resist layer 12 is formed on the first resist layer 11 by laminating the photosensitive resin film and the first resist layer 11 so that they are adjacent to each other.
The conditions for laminating the photosensitive resin film using the second photosensitive composition and the first resist layer 11 are, for example, a temperature of 30 to 100° C., a pressure of 0.1 to 0.5 MPa, and a processing speed. It is preferable to set it to 0.2 to 1.0 m/min.

The thickness of the second resist layer 12 (photosensitive resin film) is preferably 80 μm or less, more preferably 40 to 80 μm, still more preferably 50 to 70 μm.

As the base film constituting the laminate film (2), a known one can be used, and for example, a thermoplastic resin film or the like is used. The thermoplastic resin includes polyester such as polyethylene terephthalate. The thickness of the base film is preferably 2-150 μm.

<Step (iii)>
In step (iii), a third resist layer 13 and a fourth resist layer 14 are formed in this order on the second resist layer 12 .
As the third photosensitive composition and the fourth photosensitive composition, the same composition as the second photosensitive composition used in the step (ii) can be used.
As the operation in step (iii), first, the second resist layer 12 and a film-shaped third photosensitive composition are laminated, and a third resist is formed on the second resist layer 12. A layer 13 is formed. Next, the third resist layer 13 and a film-shaped fourth photosensitive composition are laminated to form a fourth resist layer 14 on the third resist layer 13 .

The lamination conditions for forming the third resist layer 13 and the lamination conditions for forming the fourth resist layer 14 are the same as the conditions for forming the second resist layer 12 .
The thickness of the third resist layer 13 (photosensitive resin film) is preferably 80 μm or less, more preferably 40 to 80 μm, still more preferably 50 to 70 μm.
The thickness of the fourth resist layer 14 (photosensitive resin film) is preferably 80 μm or less, more preferably 40 to 80 μm, still more preferably 50 to 70 μm.

Next, the first to fourth resist layers laminated on the support 20 are subjected to baking (post-apply bake (PAB)) treatment, for example, at a temperature of 30 to 50° C. for 20 to 60 minutes, if necessary. Apply.
As described above, the laminate 10 in which the first resist layer 11, the second resist layer 12, the third resist layer 13, and the fourth resist layer 14 are laminated in this order is formed on the support 20. can be manufactured.

About laminate 10:
The laminated body 10 manufactured by the manufacturing method having the steps (i), (ii), and (iii) described above is a laminate of four resist layers.
In FIG. 1, the height of the laminate 10 from the surface of the support 20, that is, the total thickness of the four resist layers is, for example, 60 to 260 μm.

<Photosensitive composition>
In the method for producing a laminate according to the present embodiment, a photosensitive composition having higher sensitivity than the second photosensitive composition is used as the first photosensitive composition.

"A photosensitive composition having higher sensitivity than the second photosensitive composition" means that when a resist pattern is formed under the same conditions using each photosensitive composition, a predetermined shape as a target is obtained. A photosensitive composition in which the optimum exposure dose Eop (mJ/cm ² ) for forming a resist pattern is smaller than the optimum exposure dose Eop when the second photosensitive composition is used.

For example, when attempting to form a line-and-space pattern (LS pattern) with a target size of 20 μm line width/50 μm space width, a photosensitive resin film having a thickness of 25 μm is irradiated with ghi rays and heated at 90° C. for 5 minutes. The difference between the optimum exposure amount Eop (1) of the first photosensitive composition and the optimum exposure amount Eop (2) of the second photosensitive composition (Eop (2) -Eop(1)) is preferably 10 (mJ/cm ² ) or more, more preferably 30 (mJ/cm ² ) or more, still more preferably 50 to 100 (mJ/cm ² ).
If the difference (Eop(2)-Eop(1)) is equal to or greater than the lower limit of the preferred range, the adhesion between the support and the first resist layer is strengthened, and a laminate that is difficult to peel off from the support is produced. easier to be

As the photosensitive compositions having different sensitivities when forming a resist pattern, it is possible to use a combination of compositions having different radiation absorption in exposure, or a combination of compositions having different polymerization rates of resin components. is preferred.

Hereinafter, an example of a combination of compositions in which the polymerization rate of the resin component is different, that is, a photosensitive composition (R1) as the first photosensitive composition and a photosensitive composition (R2) as the second photosensitive composition ) will be explained.
The photosensitive composition (R1) and the photosensitive composition (R2) differ in whether they contain an alicyclic epoxy compound represented by general formula (m1).

<<Photosensitive composition (R1)>>
As an embodiment of the first photosensitive composition, a photosensitive composition containing a polyfunctional aromatic epoxy compound, a photoacid generator, and an alicyclic epoxy compound represented by the following general formula (m1): (R1).
Since this photosensitive composition (R1) contains the alicyclic epoxy compound represented by the general formula (m1), the polymerization rate of the resin component is increased, and the sensitivity is increased when forming a resist pattern. planned.

The photosensitive composition (R1), which is one embodiment of the first photosensitive composition, comprises a polyfunctional aromatic epoxy compound (hereinafter also referred to as “(A) component”) and a photoacid generator (hereinafter “(I ) component”) and an alicyclic epoxy compound represented by the following general formula (m1) (hereinafter also referred to as “(m1) component”).
When a photosensitive resin film (resist layer) is formed using such a photosensitive composition (R1), and the photosensitive resin film is selectively exposed to light, ( Acid is generated from component I), and the action of the acid causes ring-opening polymerization of epoxy groups in component (A), reducing the solubility of the photosensitive resin film in a developer containing an organic solvent. , in the unexposed area of the photosensitive resin film, since the solubility of the photosensitive resin film in a developer containing an organic solvent does not change, between the exposed area and the unexposed area of the photosensitive resin film, There is a difference in solubility in developers containing organic solvents. Therefore, when the photosensitive resin film is developed with a developer containing an organic solvent, the unexposed portion is dissolved and removed to form a negative pattern.

Regarding the polyfunctional aromatic epoxy compound (component (A)):
Component (A) includes a compound having sufficient epoxy groups in one molecule to form a negative pattern by exposure.
The component (A) used in the photosensitive composition (R1) of the present embodiment includes novolac epoxy resins and bisphenol epoxy resins.

≪Novolac type epoxy resin≫
As the novolak-type epoxy resin (hereinafter also referred to as "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 (R1) of the present embodiment, the content of component (A1) may be 50% by mass or more, or 70% by mass or more, relative to the total mass (% by mass) of component (A). It may be 90% by mass or more, or may be 100% 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.

As the component (A2), one type may be used alone, or two or more types may be used in combination.
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.

In addition, polyfunctional aromatic epoxy compounds other than the above components (A1) and (A2) include compounds represented by the following chemical formula (A3-1) and chemical formulas (A3-2) below, in addition to those described above. You may use the compound represented by each.
Examples of commercial products that can be used as the compound represented by the following chemical formula (A3-1) include TECHMORE VG-3101L (manufactured by Printec Co., Ltd.).
Commercially available products that can be used as the compound represented by the following chemical formula (A3-2) include, for example, Showfree (registered trademark) BATG (manufactured by Showa Denko KK).

Examples of polyfunctional aromatic epoxy compounds other than those mentioned above include trimethylolpropane triglycidyl ether, glycerin triglycidyl ether; pentaerythritol tetraglycidyl ether, ditrimethylolpropane tetraglycidyl ether, diglycerin tetraglycidyl ether, and 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 (R1) of the present embodiment, as the component (A), one containing the component (A1) is preferably used.
The polystyrene equivalent weight 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, separation between the support and the first resist layer is less likely to occur.

The content of component (A) in the photosensitive composition (R1) of the embodiment may be adjusted according to the thickness of the first resist layer to be formed.

About the photoacid generator (component (I)):
In the photosensitive composition (R1) of the embodiment, the 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, electron beams, and the like to convert cations. It is preferable to use a photocationic polymerization initiator that is generated and whose cation can serve as a polymerization initiator.
The (I) component used in the photosensitive composition (R1) of the present embodiment includes an onium borate salt (hereinafter also referred to as “(I1) component”), a photocationic polymerization initiator other than the (I1) component (other light cationic polymerization initiator).

≪Onium borate salt≫
An onium borate salt (component (I1)) generates a relatively strong acid upon exposure. Therefore, by forming a pattern using the photosensitive composition (R1) 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 Photocationic Polymerization Initiators≫
Examples of photocationic 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"); Compounds represented by (I3-1) or (I3-2) (hereinafter referred to as "component (I3)") can be mentioned.

(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 photocationic 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. is preferably By using a photocationic 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 more. By using a photocationic 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 (R1) of the present embodiment, the component (I) is preferably at least one selected from the group consisting of the component (I1), the component (I2) and the component (I3). Those containing the component (I3), those containing the components (I2) and (I3) are more preferable, those containing the components (I1) and (I3), represented by the general formula (I2-1) and a compound represented by the general formula (I3-1), a compound represented by the general formula (I2-1) and a compound represented by the general formula (I2-1) are more preferable. and a compound represented by general formula (I3-1) is particularly preferred.

In the photosensitive composition (R1) of the present embodiment, the content of component (I) is 0.1 to 5 parts by mass when the total parts by mass of component (A) is 100 parts by mass. It is preferably from 0.15 to 3 parts by mass, and even more preferably from 0.2 to 1 part by mass.
When the content of component (I1) is at least the lower limit of the preferred range, sufficient sensitivity can be 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.

Regarding the alicyclic epoxy compound represented by the general formula (m1) (component (m1)):

［式中、Ｒ^１～Ｒ^１８は、それぞれ独立に、水素原子、ハロゲン原子又は有機基である。Ｘは、２価の連結基又は単結合である。］

[In the formula, R ¹ to R ¹⁸ are each independently a hydrogen atom, a halogen atom or an organic group. X is a divalent linking group or a single bond. ]

In formula (m1), the halogen atoms for R ¹ to R ¹⁸ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

In the above formula (m1), the organic group for R ¹ to R ¹⁸ includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a hydrocarbon group containing a group in which two or more of these are bonded. A hydrogen group and the like can be mentioned.

Regarding the organic groups for R ¹ to R ¹⁸ , examples of the aliphatic hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and the like. be done.
Among the alkyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 10 carbon atoms are preferred, and alkyl groups having 1 to 4 carbon atoms are particularly preferred.
Among alkenyl groups having 2 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms are preferred, and alkenyl groups having 2 to 4 carbon atoms are particularly preferred.
Among the alkynyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 10 carbon atoms are preferred, and alkynyl groups having 2 to 4 carbon atoms are particularly preferred.

Regarding the organic groups for R ¹ to R ¹⁸ , the alicyclic hydrocarbon group includes, for example, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, and a bridged ring having 4 to 15 carbon atoms. Formula hydrocarbon group, etc. are mentioned.
Examples of the cycloalkyl group having 3 to 12 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclododecyl group and the like.
The cycloalkenyl group having 3 to 12 carbon atoms includes, for example, a cyclohexenyl group.
Examples of the bridged cyclic hydrocarbon group having 4 to 15 carbon atoms include a bicycloheptanyl group and a bicycloheptenyl group.

Regarding the organic groups for R ¹ to R ¹⁸ , examples of the aromatic hydrocarbon group include aryl groups having 6 to 14 carbon atoms.
Among the aryl groups having 6 to 14 carbon atoms, aryl groups having 6 to 10 carbon atoms are preferred, such as phenyl group and naphthyl group.

Regarding the organic groups for R ¹ to R ¹⁸ , the above-mentioned “group in which two or more of these are bonded” includes, for example, C 3-12 cycloalkyl-substituted C 1-20 alkyl such as cyclohexylmethyl group group; alkyl-substituted cycloalkyl group having 3 to 12 carbon atoms having 1 to 20 carbon atoms such as methylcyclohexyl group; aralkyl group having 7 to 18 carbon atoms such as benzyl group and phenethyl group (particularly preferably aralkyl group); C6-C14 aryl-substituted C2-C20 alkenyl group such as cinnamyl group; C1-C20 alkyl-substituted C6-C14 aryl group such as tolyl group; styryl group, etc. and an alkenyl-substituted aryl group having 6 to 14 carbon atoms having 2 to 20 carbon atoms.

The organic group for R ¹ to R ¹⁸ may contain a heteroatom, and examples thereof include a hydrocarbon group containing an oxygen atom or a halogen atom, or an optionally substituted alkoxy group.
The hydrocarbon group containing an oxygen atom or a halogen atom includes a group in which at least one hydrogen atom in the above hydrocarbon group is substituted with a group having an oxygen atom or a halogen atom.

The group having an oxygen atom includes, for example, a hydroxy group; a hydroperoxy group; an alkoxy group having 1 to 10 carbon atoms (methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, isobutyloxy group, etc.); carbon Alkenyloxy group having 2 to 10 carbon atoms (such as allyloxy group); selected from the group consisting of alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, halogen atom and alkoxy group having 1 to 10 carbon atoms optionally substituted aryloxy groups having 6 to 14 carbon atoms (e.g., tolyloxy group, naphthyloxy group, etc.); aralkyloxy groups having 7 to 18 carbon atoms (benzyloxy group, phenethyloxy group, etc.); C1-C10 acyloxy group (acetyloxy group, propionyloxy group, (meth)acryloyloxy group, benzoyloxy group, etc.); C1-C10 alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group) group, butoxycarbonyl group, etc.); having a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a halogen atom and an alkoxy group having 1 to 10 carbon atoms; aryloxycarbonyl group having 6 to 14 carbon atoms (eg, phenoxycarbonyl group, tolyloxycarbonyl group, naphthyloxycarbonyl group, etc.); aralkyloxycarbonyl group having 7 to 18 carbon atoms (benzyloxycarbonyl group, etc.); epoxy group-containing groups such as glycidyloxy; oxetanyl group-containing groups such as ethyloxetanyloxy; acyl groups having 1 to 10 carbon atoms (acetyl, propionyl, benzoyl, etc.); isocyanate; sulfo; carbamoyl an oxo group; or a group in which two or more of these are bonded via a single bond or an alkylene group having 1 to 10 carbon atoms.

A halogen atom in the hydrocarbon group containing a halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

The alkoxy group for R ¹ to R ¹⁸ includes alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, isopropyloxy, butoxy, and isobutyloxy. be done.

Regarding the organic groups represented by R ¹ to R ¹⁸ , examples of substituents that the alkoxy group may have include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), hydroxy group, and 1 carbon atom. -10 alkoxy group, C2-10 alkenyloxy group, C6-14 aryloxy group, C1-10 acyloxy group, mercapto group, C1-10 alkylthio group, C2 ~10 alkenylthio group, arylthio group having 6 to 14 carbon atoms, aralkylthio group having 7 to 18 carbon atoms, carboxy group, alkoxycarbonyl group having 1 to 10 carbon atoms, aryloxycarbonyl group having 6 to 14 carbon atoms, C7-18 aralkyloxycarbonyl group, amino group, mono- or di-C1-10 alkylamino group, C1-10 acylamino group, epoxy group-containing group, oxetanyl group-containing group, C1- 10 acyl groups, oxo groups, or groups in which two or more of these are bonded via a single bond or an alkylene group having 1 to 10 carbon atoms.

Among the above, R ¹ to R ¹⁸ in the formula (m1) are preferably hydrogen atoms, and particularly preferably all of R ¹ to R ¹⁸ are hydrogen atoms.

In the formula (m1), the divalent linking group in X includes, for example, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, an amide group, or a group in which a plurality of these are linked. be done.
Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms (preferably a linear or branched alkylene group having 1 to 3 carbon atoms). a cycloalkylene group having 3 to 12 carbon atoms; a cycloalkylidene group having 3 to 12 carbon atoms (preferably a cycloalkylene group having 3 to 6 carbon atoms or a cycloalkylidene group having 3 to 6 carbon atoms);
The linear or branched alkylene group having 1 to 3 carbon atoms includes methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, trimethylene group and the like.
The cycloalkylene group having 3 to 12 carbon atoms includes a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group, a 1,2-cyclohexylene group and a 1,3-cyclohexylene group. , 1,4-cyclohexylene group, cyclohexylidene group and the like.

Among the above, X in the formula (m1) is preferably a single bond.

Preferred (m1) components include 3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexane carboxylate, (3,4,3′,4′-diepoxy)bicyclohexyl, bis(3,4-epoxy cyclohexylmethyl)ether, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexan-1-yl)ethane, 2,2-bis(3,4-epoxycyclohexan-1-yl)propane, 1 , 2-bis(3,4-epoxycyclohexan-1-yl)ethane and the like.

As the component (m1), one type may be used alone, or two or more types may be used in combination.
In the photosensitive composition (R1) of the present embodiment, the content of component (m1) is 0.5 to 20 parts by mass when the total parts by mass of component (A) is 100 parts by mass. It is preferably from 1 to 15 parts by mass, and even more preferably from 2 to 10 parts by mass.
When the content of the component (m1) is at least the lower limit of the above preferred range, the sensitivity is increased when forming the resist pattern, and the support and the photosensitive resin film (first resist layer) It becomes easier to increase the adhesion with. On the other hand, when it is equal to or less than the upper limit of the preferred range, film formation is facilitated.

About optional ingredients:
The photosensitive composition (R1) of the present embodiment may optionally contain other components (optional components) in addition to the components (A), (I) and (m1) described above.
The photosensitive composition (R1) optionally contains miscible additives such as metal oxides, silane coupling agents, sensitizer components, solvents, additional resins to improve film performance, dissolution Inhibitors, basic compounds, plasticizers, stabilizers, colorants, antihalation agents and the like can be added and contained as appropriate.

Examples of metal oxides (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. By including the component (M), a cured resin film having improved film strength and heat resistance can be easily obtained, and a resist pattern having a good shape and high resolution can be formed. The shape of component (M) is preferably particulate.

Silane coupling agents include, for example, silane coupling agents having reactive substituents such as carboxy groups, methacryloyl groups, isocyanate groups, and epoxy groups. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl). and ethyltrimethoxysilane.

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.

The photosensitive composition (R1) 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, and 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.

<<Photosensitive composition (R2)>>
As an embodiment of the second photosensitive composition, a photosensitive composition (R2) containing a polyfunctional aromatic epoxy compound and a photoacid generator (represented by the general formula (m1) excluding those containing alicyclic epoxy compounds).
As described above, the photosensitive composition (R1) and the photosensitive composition (R2) differ in whether or not they contain the alicyclic epoxy compound represented by the general formula (m1). Due to this difference, the photosensitive composition (R1) is adjusted to have higher sensitivity than the photosensitive composition (R2).

The photosensitive composition (R2), which is one embodiment of the second photosensitive composition, contains a polyfunctional aromatic epoxy compound and a photoacid generator.
When a photosensitive resin film (resist layer) is formed using such a photosensitive composition (R2), and the photosensitive resin film is selectively exposed to light, the exposed portions of the photosensitive resin film are exposed to light. Acid is generated from the acid generator, and the action of the acid causes ring-opening polymerization of the epoxy groups in the polyfunctional aromatic epoxy compound, reducing the solubility of the photosensitive resin film in a developer containing an organic solvent. On the other hand, in the unexposed portion of the photosensitive resin film, since the solubility of the photosensitive resin film in the developer containing the organic solvent does not change, , there is a difference in solubility in a developer containing an organic solvent. Therefore, when the photosensitive resin film is developed with a developer containing an organic solvent, the unexposed portion is dissolved and removed to form a negative pattern.

About Polyfunctional Aromatic Epoxy Compounds:
Examples of the polyfunctional aromatic epoxy compound contained in the photosensitive composition (R2) include those similar to the polyfunctional aromatic epoxy compound (component (A)) contained in the photosensitive composition (R1) described above. .
In the photosensitive composition (R2) of the present embodiment, as the polyfunctional aromatic epoxy compound, one containing the component (A1) is preferably used.
The content of the polyfunctional aromatic epoxy compound in the photosensitive composition (R2) of the embodiment may be adjusted according to the thickness of the second resist layer to be formed.

About the photoacid generator:
Examples of the photoacid generator contained in the photosensitive composition (R2) include those similar to the photoacid generator (component (I)) contained in the photosensitive composition (R1) described above.
In the photosensitive composition (R2) of the present embodiment, the photoacid generator is preferably at least one selected from the group consisting of the above components (I1), (I2) and (I3). ) component, more preferably a compound represented by general formula (I2-2), and still more preferably a component (I1).
In the photosensitive composition (R2) of the present embodiment, the content of the photoacid generator is 0.1 to 5 parts by mass when the total parts by mass of the polyfunctional aromatic epoxy compound is 100 parts by mass. preferably 0.15 to 3 parts by mass, even more preferably 0.2 to 2 parts by mass.

About optional ingredients:
The photosensitive composition (R2) of the present embodiment may optionally contain other components (optional components) in addition to the above-described polyfunctional aromatic epoxy compound and photoacid generator.
The photosensitive composition (R2) optionally contains miscible additives such as metal oxides, silane coupling agents, sensitizer components, solvents, additional resins to improve film performance, dissolution Inhibitors, basic compounds, plasticizers, stabilizers, colorants, antihalation agents and the like can be added and contained as appropriate.

In the method for manufacturing a laminate according to the first aspect described above, the second resist layer 12 is formed as the first photosensitive composition for forming the first resist layer 11 in contact with the support 20. A photosensitive composition is used that has a higher sensitivity than the second photosensitive composition for Therefore, according to the method for manufacturing the laminate, it is possible to manufacture the laminate 10 capable of forming a cured resin film that is difficult to peel off from the support 20 .

In one embodiment of the method for producing a laminate described above, a combination of compositions having resin components with different polymerization rates was employed as the first photosensitive composition and the second photosensitive composition. is a combination of different compositions, the present invention is not limited to this.

In one embodiment of the method for manufacturing the laminate described above, the third photosensitive composition for forming the third resist layer 13 and the fourth photosensitive composition for forming the fourth resist layer 14 Although it is possible to use the same composition as the second photosensitive composition for forming the second resist layer 12, the present invention is not limited to this. The third photosensitive composition and the fourth photosensitive composition can be appropriately selected within the range in which the effects of the present invention are exhibited.

In one embodiment of the method for manufacturing the laminate described above, in the steps (ii) and (iii), the method of laminating the second resist layer 12, the third resist layer 13, and the fourth resist layer 14 respectively. , a method of laminating a film-shaped photosensitive composition, but the present invention is not limited to this. For example, the second resist layer 12, the third resist layer 13, a second resist layer 12, a third resist layer 13, a second resist layer 12, a third resist layer 13, a second resist layer 12, a third resist layer 13, and a The fourth resist layers 14 can also be laminated respectively.

In one embodiment of the method for manufacturing a laminate described above, the laminate has a four-layer structure, but is not limited to this, and may have a structure of two or more layers. should be set accordingly.
In one embodiment of the method for manufacturing a laminate described above, a method having steps (i) to (iii) has been described, but the method is not limited to this, and may include steps other than these as necessary. good.

(Curing pattern forming method)
A second aspect of the present invention includes a step of exposing a laminate manufactured by the method for manufacturing a laminate according to the first aspect described above, and developing the exposed laminate to form a resist pattern. and curing the resist pattern to obtain a cured pattern.

The cured pattern is formed by the step (iv) of exposing the laminate 10 formed on the support 20 shown in FIG. 1 and the step (v) of developing the exposed laminate 10 to form a resist pattern 110. and a step (vi) of curing the resist pattern 110 to obtain a cured pattern 120 composed of the cured resin film 10c.
Each of steps (iv) to (vi) will be described below.

<Step (iv)>
In step (iv), the laminate 10 formed on the support 20 is exposed.
For example, as shown in FIG. 2, the laminate 10 is selectively exposed through a photomask 90 on which a coil-shaped pattern is formed using a known exposure apparatus.
By the exposure treatment in step (iv), the laminated body 10 after exposure becomes an exposed portion 10b whose solubility in the developing solution has changed due to the exposure and an unexposed portion 10d which has no change.

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

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

<Step (v)>
In step (v), the exposed laminate 10 is developed to form a coil-shaped resist pattern 110 .
For example, in the case of a combination of a photosensitive composition (R1) as the first photosensitive composition and a photosensitive composition (R2) as the second photosensitive composition, the laminate 10 after exposure is treated with an organic solvent. By developing with a developer (organic developer) containing 110 is formed.
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 ingredients of the photosensitive composition, 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 laminate on the support in a developer for a certain period of time (dip method), a method of applying the developer to the surface of the laminate by surface tension. A method of heaping up and standing still for a certain period of time (paddle method), a method of spraying the developer onto the laminate surface (spray method), and scanning the developer dispensing nozzle at a constant speed on the laminate rotating at a constant speed. A method of continuously applying the developer (dynamic dispensing method) and the like can be mentioned.

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

<Step (vi)>
In step (vi), the resist pattern 110 formed in step (v) is cured to obtain a cured pattern 120 .
For example, the resist pattern 110 formed in step (v) is subjected to a heat treatment (curing operation) and cured to obtain a cured pattern 120 composed of the cured resin film 10c as shown in FIG.
In the cured resin film 10c, the first to fourth resist layers are cured and integrated.
The heat treatment (curing operation) in step (vi) can be performed, for example, at a temperature of 100 to 250° C. for 0.5 to 2 hours.

About curing pattern 120:
In FIG. 4, the cured pattern 120 is a coil-shaped pattern, which can form the insulation in the inductor as a permanent film. Then, the space between the cured resin films 10c is plated with copper or the like.
The height (h) of the cured pattern 120 is, for example, 60-260 μm.
The width (w) of the cured pattern 120 is, for example, 1 to 100 μm.
The aspect ratio (h/w) of the cured pattern 120 is, for example, 1-80.

In the cured pattern forming method according to the second aspect described above, the laminate 10 manufactured by the laminate manufacturing method according to the first aspect is used. Therefore, according to such a cured pattern forming method, it is possible to manufacture a cured resin film 10c that is difficult to peel off from the support 20 .

In the embodiment described above, the photosensitive composition (R1) is used as the first photosensitive composition, and the photosensitive composition (R2) is used as the second photosensitive composition. The photosensitive composition (R1) and the photosensitive composition (R2) differ in whether or not they contain an alicyclic epoxy compound represented by general formula (m1) (component (m1)).
In the laminate 10, a first resist layer 11 and a second resist layer 12 are laminated in this order on a support 20. As shown in FIG. The first resist layer 11 is made of a photosensitive composition (R1), and the second resist layer 12 is made of a photosensitive composition (R2).
The component (m1) contained in the photosensitive composition (R1) has a higher rate of ring-opening polymerization of the epoxy group than the aromatic epoxy compound. For this reason, the photosensitive composition (R1) containing the (m1) component has an increased polymerization rate of the resin component, resulting in higher sensitivity.
Then, when forming the resist pattern 110, the first resist layer 11 in contact with the support 20 is the photosensitive composition for forming the second resist layer 12 adjacent to the first resist layer 11. By achieving higher sensitivity than (R2), the adhesion between the support 20 and the first resist layer 11 is strengthened. As a result, it is possible to increase the aspect ratio of the pattern, form the cured resin film 10c that is difficult to peel off from the support 20, and suppress pattern collapse, thereby stably manufacturing the coil-shaped cured pattern 120.

Further, according to such a cured pattern forming method, it is possible to stably achieve miniaturization of the insulating portion that constitutes the inductor. Therefore, such a cured pattern forming method is a useful method for manufacturing an insulating portion in an inductor.

In one embodiment of the cured pattern forming method described above, in step (v), the laminate 10 after exposure is developed with a developer containing an organic solvent (organic developer), but the present invention is limited to this. However, depending on the characteristics of the photosensitive composition, it may be developed with an alkaline developer. Examples of the alkaline developer include 0.1 to 10 mass % tetramethylammonium hydroxide (TMAH) aqueous solution.

(Laminate)
A third aspect of the present invention is a laminate of a first resist layer and a second resist layer. In such a laminate, the first resist layer is a layer containing a polyfunctional aromatic epoxy compound, a photoacid generator, and an alicyclic epoxy compound represented by the following general formula (m1), The second resist layer is characterized by being a layer containing a polyfunctional aromatic epoxy compound and a photo-acid generator (excluding those containing the alicyclic epoxy compound).

［式中、Ｒ^１～Ｒ^１８は、それぞれ独立に、水素原子、ハロゲン原子又は有機基である。Ｘは、２価の連結基又は単結合である。］

[In the formula, R ¹ to R ¹⁸ are each independently a hydrogen atom, a halogen atom or an organic group. X is a divalent linking group or a single bond. ]

As an embodiment of such a laminate, a laminate of the first resist layer 11 and the second resist layer 12 manufactured by the steps (i) and (ii) in the above-described (method for manufacturing a laminate) body.
The description of the first resist layer includes the above-described first resist layer 11 and the polyfunctional aromatic epoxy compound contained in the photosensitive composition (R1) for forming this, the photoacid generator, general The explanations for the alicyclic epoxy compound represented by formula (m1) and optional components are the same as those described above.
The description of the second resist layer includes the above-described second resist layer 12 and the polyfunctional aromatic epoxy compound, photoacid generator and optional It is the same as the description of each component.

In the laminate according to the third aspect described above, the first resist layer and the second resist layer contain an alicyclic epoxy compound represented by the general formula (m1) (component (m1)). or not.
This component (m1) has a higher rate of ring-opening polymerization of the epoxy group than the aromatic epoxy compound. Therefore, the first resist layer containing the component (m1) can increase the polymerization speed of the resin component in the formation of the resist pattern, thereby achieving high sensitivity.
Then, when forming a resist pattern, the first resist layer in contact with the support has higher sensitivity than the second resist layer adjacent to the first resist layer. Adhesion to the first resist layer is strengthened. Therefore, according to this laminate, it is possible to increase the aspect ratio of the pattern, form a cured resin film that is difficult to peel off from the support, suppress pattern collapse, and stably manufacture a coil-shaped cured pattern. becomes possible.

(Photosensitive composition)
A fourth aspect of the present invention is a photosensitive composition containing a polyfunctional aromatic epoxy compound, a photoacid generator, and an alicyclic epoxy compound represented by the following general formula (m1). Such a photosensitive composition is suitable as a photosensitive composition for forming the layer of the insulating part of the inductor, which is in contact with the support.

［式中、Ｒ^１～Ｒ^１８は、それぞれ独立に、水素原子、ハロゲン原子又は有機基である。Ｘは、２価の連結基又は単結合である。］

[In the formula, R ¹ to R ¹⁸ are each independently a hydrogen atom, a halogen atom or an organic group. X is a divalent linking group or a single bond. ]

The description of this photosensitive composition is the same as the description of the photosensitive composition (R1) in the above-described (Laminate production method).
Such a photosensitive composition forms the first resist layer in the above-described (laminate), the first resist layer 11 in the laminate 10 shown in FIG. It is useful as a forming material.

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 photosensitive composition>
Each component shown in Table 1 was mixed and dissolved in propylene glycol monomethyl ether acetate (PGMEA), filtered using a PTFE filter (pore size 1 μm, manufactured by PALL), and the photosensitive composition of each example (solid content 50 to 80 wt% solutions) 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 novolak type epoxy resin represented by the following chemical formula (A1-2). Trade name “EPICLON N-770” manufactured by DIC Corporation.

(I)-1: A photoacid generator represented by the following chemical formula (I2-2-1).
(I)-2: A photoacid generator represented by the following chemical formula (I1-4).
(I)-3: A photoacid generator represented by the following chemical formula (I2-1-1).
(I)-4: A photoacid generator represented by the following chemical formula (I1-5).
(I)-5: A photoacid generator represented by the following chemical formula (I3-1-1).

(m1)-1: An alicyclic epoxy compound represented by the following chemical formula (m1-1). Trade name "Celoxide 8000", manufactured by Daicel Corporation.

<Measurement of sensitivity Eop of photosensitive composition>
The sensitivities of the above photosensitive compositions (1) to (7) were measured as follows.
Using the photosensitive compositions (1) to (7), a photosensitive resin film of each composition was formed to a thickness of 25 μm on a 5-inch silicon wafer.
After that, the photosensitive resin film was irradiated with ghi rays after a mask having a pattern was brought into close contact with the photosensitive resin film using an aligner (PLA-501F manufactured by Canon Inc.).
After that, post-exposure heating was performed for 5 minutes on a hot plate at 90°C.
Thereafter, puddle development was performed with PGMEA at 23° C. for 120 seconds, followed by shaking off drying to obtain a line-and-space pattern (hereinafter sometimes simply referred to as “LS pattern”). For the evaluation of the optimum exposure dose (Eop), an LS pattern with a target size of 20 μm line width/50 μm space width was obtained.
In forming the LS pattern, the optimum exposure dose Eop (mJ/cm ² ) for forming the target LS pattern was determined. The results are shown in Table 2 as "sensitivity Eop (mJ/cm ² )".

<Formation of cured pattern>
An attempt was made to form a coil-shaped cured pattern using the photosensitive compositions (1) to (7).

Preparation of laminated film:
The photosensitive composition (4) is applied onto the base film using an applicator and dried in an oven at 70° C. for 10 minutes to form a photosensitive resin film (4) having a thickness of 20 μm. Thus, a photosensitive laminated film (F4) was obtained.

Except for changing the photosensitive composition (4) to the photosensitive composition (5), a photosensitive resin film (5) having a thickness of 20 μm was formed on the base film by coating and drying as described above. to obtain a photosensitive laminated film (F5).

Except for changing the photosensitive composition (4) to the photosensitive composition (1), a photosensitive resin film (1) having a thickness of 55 μm was formed on the base film by coating and drying as described above. formed to obtain a photosensitive laminated film (F1).

A photosensitive resin film (2a) having a thickness of 65 μm was formed on the base film by coating and drying as described above, except that the photosensitive composition (4) was changed to the photosensitive composition (2). formed to obtain a photosensitive laminated film (F2a).

Except that the photosensitive composition (4) was changed to the photosensitive composition (2), a photosensitive resin film (2b) having a thickness of 55 μm was formed on the base film by applying and drying as described above. to obtain a photosensitive laminated film (F2b).

(Example 1)
Step of forming the first resist layer:
The photosensitive resin film (4) formed on the base film of the laminated film (F4) and the 5-inch silicon substrate (support) containing the bismaleimide triazine resin are combined with the photosensitive resin film (4) and the A first resist layer was formed on the support by laminating under the conditions of 45° C., 0.3 MPa, and 0.5 m/min so as to be adjacent to the support.

Step of forming a second resist layer:
Next, the base film in contact with the photosensitive resin film (4) constituting the first resist layer is peeled off, and the exposed photosensitive resin film (4) and the base film of the laminated film (F2a) are The formed photosensitive resin film (2a) is laminated under the conditions of 50° C., 0.3 MPa, and 0.5 m/min to obtain a laminate of the support, the first resist layer, and the second resist layer. (4a) was obtained.

Step of forming a third resist layer:
Next, the base film in contact with the photosensitive resin film (2a) constituting the second resist layer is peeled off, and the exposed photosensitive resin film (2a) and the base film of the laminated film (F2a) are The formed photosensitive resin film (2a) is laminated under conditions of 50° C., 0.3 MPa, and 0.5 m/min to obtain a laminate (4a) and a laminate (4b) of a third resist layer. got

Step of forming a fourth resist layer:
Next, the base film in contact with the photosensitive resin film (2a) constituting the third resist layer is peeled off, and the exposed photosensitive resin film (2a) and the base film of the laminated film (F2a) are The formed photosensitive resin film (2a) was laminated under the conditions of 50° C., 0.3 MPa, and 0.5 m/min, and the first to fourth resist layers were laminated in this order on the support. A laminate (4) was obtained.
Then, the obtained laminate (4) was subjected to baking treatment (PAB) at a temperature of 40° C. for 30 minutes.

Laminate (4) Support: 5 inch silicon substrate containing bismaleimide triazine resin First resist layer: 20 μm thick photosensitive resin film (4)
Second resist layer: photosensitive resin film (2a) with a thickness of 65 μm
Third resist layer: photosensitive resin film (2a) with a film thickness of 65 μm
Fourth resist layer: photosensitive resin film (2a) with a film thickness of 65 μm

Step of exposing the laminate:
Next, using an aligner (PLA-501F, manufactured by Canon Inc.), 1000 mJ/cm ² (i-line integrated value) were exposed.
After that, post-exposure heating was performed for 45 minutes on a hot plate at 60°C.

Developing process:
Then, the laminate (4) after the post-exposure heating was subjected to solvent development (Dip, Vertical) at 23° C. for 45 minutes using PGMEA as a developer to obtain a coil-shaped resist pattern. .
After that, a rinse treatment was performed for 1 minute using PGMEA.

Steps to obtain cured pattern:
Then, the rinsed resist pattern was heat-treated in an oven at a temperature of 200° C. for 1 hour to obtain a coil-shaped cured pattern.

(Example 2)
Steps of forming first to fourth resist layers:
First to fourth resist layers were formed on a 5-inch silicon substrate (support) containing a bismaleimide triazine resin in the same manner as in Example 1, except that the laminated film (F4) was changed to the laminated film (F5). A laminate (5) was obtained by laminating in this order.
Then, the obtained laminate (5) was subjected to baking (PAB) at a temperature of 40° C. for 30 minutes.

Laminate (5) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: 20 μm-thick photosensitive resin film (5)
Second resist layer: photosensitive resin film (2a) with a thickness of 65 μm
Third resist layer: photosensitive resin film (2a) with a film thickness of 65 μm
Fourth resist layer: photosensitive resin film (2a) with a film thickness of 65 μm

Steps of exposing the laminate, developing, and obtaining a cured pattern:
Next, in the same manner as in Example 1, the laminated body (5) after baking (PAB) was subjected to the steps of exposing the laminated body, developing, and obtaining a cured pattern. A cure pattern of .

(Comparative example 1)
Steps of forming first to fourth resist layers:
5 containing a bismaleimide triazine resin in the same manner as in Example 1, except that the laminated film (F4) was changed to the laminated film (F1), and the laminated film (F2a) was changed to the laminated film (F2b). A laminate (1) was obtained in which the first to fourth resist layers were laminated in this order on an inch silicon substrate (support).
Then, the obtained laminate (1) was subjected to baking (PAB) at a temperature of 40° C. for 30 minutes.

Laminate (1) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: Photosensitive resin film (1) having a thickness of 55 µm
Second resist layer: photosensitive resin film (2b) with a film thickness of 55 μm
Third resist layer: photosensitive resin film (2b) with a film thickness of 55 μm
Fourth resist layer: photosensitive resin film (2b) with a film thickness of 55 μm

Step of exposing and developing the laminate:
Then, in the same manner as in Example 1, the laminate (1) after the baking treatment (PAB) was subjected to the steps of exposing and developing the laminate. (1) was peeled off and removed, making it impossible to form a coil-shaped resist pattern.

(Comparative example 2)
Steps of forming first to fourth resist layers:
5 containing a bismaleimide triazine resin in the same manner as in Example 1, except that the laminated film (F4) was changed to the laminated film (F2b), and in addition, the laminated film (F2a) was changed to the laminated film (F2b). A laminate (2) was obtained in which the first to fourth resist layers were laminated in this order on an inch silicon substrate (support).
Then, the resulting laminate (2) was subjected to baking (PAB) at a temperature of 40° C. for 30 minutes.

Laminate (2) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: 55 μm-thick photosensitive resin film (2b)
Second resist layer: photosensitive resin film (2b) with a film thickness of 55 μm
Third resist layer: photosensitive resin film (2b) with a film thickness of 55 μm
Fourth resist layer: photosensitive resin film (2b) with a film thickness of 55 μm

Step of exposing and developing the laminate:
Then, in the same manner as in Example 1, the laminated body (2) after the baking treatment (PAB) was subjected to the steps of exposing the laminated body and developing. (2) was peeled off and removed, making it impossible to form a coil-shaped resist pattern.

(Example 3)
Step of forming the first resist layer:
On the support, the photosensitive composition (6) is applied using a spinner, pre-baked (PAB) on a hot plate at a temperature of 90 ° C. for 5 minutes, and dried to obtain the first A photosensitive resin film (6) having a thickness of 25 μm was formed as a resist layer.

Step of forming a second resist layer:
Next, the photosensitive resin film (6) constituting the first resist layer and the photosensitive resin film (2b) formed on the base film of the laminated film (F2b) were heated at 40° C. and 0.3 MPa. , and 0.5 m/min to obtain a laminate (6a) of the support, the first resist layer, and the second resist layer.

Step of forming a third resist layer:
Next, the base film in contact with the photosensitive resin film (2b) constituting the second resist layer is peeled off, and the exposed photosensitive resin film (2b) and the base film of the laminated film (F2b) are coated with The formed photosensitive resin film (2b) is laminated under conditions of 40° C., 0.3 MPa, and 0.5 m/min to obtain a laminate (6a) and a laminate (6b) of the third resist layer. got

Step of forming a fourth resist layer:
Next, the base film in contact with the photosensitive resin film (2b) constituting the third resist layer is peeled off, and the exposed photosensitive resin film (2b) and the base film of the laminated film (F2b) are The formed photosensitive resin film (2b) was laminated under the conditions of 40° C., 0.3 MPa, and 0.5 m/min, and the first to fourth resist layers were laminated in this order on the support. A laminate (6) was obtained.
Then, the obtained laminate (6) was subjected to a baking treatment (PAB) at a temperature of 40° C. for 60 minutes.

Laminate (6) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: 25 μm-thick photosensitive resin film (6)
Second resist layer: photosensitive resin film (2b) with a film thickness of 55 μm
Third resist layer: photosensitive resin film (2b) with a film thickness of 55 μm
Fourth resist layer: photosensitive resin film (2b) with a film thickness of 55 μm

Step of exposing the laminate:
Next, an aligner (PLA-501F manufactured by Canon Inc.) was applied to the laminate (6) after baking (PAB) through a mask having a coil-shaped pattern at 1000 mJ/cm ² (i-line integrated value) were exposed.
After that, post-exposure heating was performed for 45 minutes on a hot plate at 60°C.

Developing process:
Then, the laminate (6) after the post-exposure heating was subjected to solvent development (Dip, Vertical) at 23° C. for 40 minutes using PGMEA as a developer to obtain a coil-shaped resist pattern. .
After that, a rinse treatment was performed for 5 minutes using PGMEA.

Steps to obtain cured pattern:
Then, the rinsed resist pattern was heat-treated in an oven at a temperature of 200° C. for 1 hour to obtain a coil-shaped cured pattern.

(Example 4)
Step of forming the first resist layer:
On the support, the photosensitive composition (7) is applied using a spinner, pre-baked (PAB) on a hot plate at a temperature of 90 ° C. for 5 minutes, and dried to obtain the first A photosensitive resin film (7) having a thickness of 25 μm was formed as a resist layer.

Steps of forming second to fourth resist layers:
Next, on the photosensitive resin film (7), which is the first resist layer, in the same manner as in Example 3, a laminated film (F2b) is used to form the second to fourth resist layers (each of the photosensitive resin Each operation of the step of forming the film (2b)) was carried out to obtain a laminate (7) in which the first to fourth resist layers were laminated in this order on the support.
Then, the obtained laminate (7) was subjected to baking treatment (PAB) at a temperature of 40° C. for 60 minutes.

Laminate (7) Support: 5-inch silicon substrate containing bismaleimide triazine resin First resist layer: 25 μm-thick photosensitive resin film (7)
Second resist layer: photosensitive resin film (2b) with a film thickness of 55 μm
Third resist layer: photosensitive resin film (2b) with a film thickness of 55 μm
Fourth resist layer: photosensitive resin film (2b) with a film thickness of 55 μm

Steps of exposing the laminate, developing, and obtaining a cured pattern:
Next, in the same manner as in Example 3, the laminated body (7) after the baking treatment (PAB) was subjected to the steps of exposing the laminated body, developing, and obtaining a cured pattern. A cure pattern of .

(Comparative Example 3)
Step of forming the first resist layer:
The photosensitive composition (3) is applied onto the support using a spinner, pre-baked (PAB) on a hot plate at a temperature of 90° C. for 5 minutes, and dried to form the first layer. A photosensitive resin film (3) having a thickness of 25 μm was formed as a resist layer.

Steps of forming second to fourth resist layers:
Next, on the photosensitive resin film (3) which is the first resist layer, in the same manner as in Example 3, using the laminated film (F2b), the second to fourth resist layers (each of the photosensitive resin Each operation of the step of forming the film (2b)) was carried out to obtain a laminate (3) in which the first to fourth resist layers were laminated in this order on the support.
Then, the resulting laminate (3) was subjected to baking (PAB) at a temperature of 40° C. for 60 minutes.

Laminate (3) Support: 5 inch silicon substrate containing bismaleimide triazine resin First resist layer: 25 μm thick photosensitive resin film (3)
Second resist layer: photosensitive resin film (2b) with a film thickness of 55 μm
Third resist layer: photosensitive resin film (2b) with a film thickness of 55 μm
Fourth resist layer: photosensitive resin film (2b) with a film thickness of 55 μm

Step of exposing and developing the laminate:
Then, in the same manner as in Example 3, the laminate (3) after the baking treatment (PAB) was subjected to the steps of exposing the laminate to light and developing the laminate. (3) was peeled off and removed, making it impossible to form a coil-shaped resist pattern.

In <Formation of cured pattern>, the state after pattern formation in each example was visually evaluated by SEM observation (magnification: 500). Such evaluation was performed based on the following evaluation criteria, and the results are shown in Table 2.
Evaluation Criteria A: Formation of a coil-shaped cured pattern was confirmed.
B: No laminate or cured pattern was observed.
If the evaluation is A, it can be said that the adhesion between the support and the cured pattern (resin cured film) is strong and the cured pattern is difficult to peel off from the support.

From the results shown in Table 2, according to the cured pattern forming method of Examples 1 to 4, a laminate that can achieve a high aspect ratio of the pattern and can be a resin cured film that is difficult to peel off from the support, and a coil-shaped cured pattern. was confirmed to be able to form

The photosensitive compositions (4) to (7) used in Examples 1 to 4 are compared to the photosensitive compositions (1) to (3) used in Comparative Examples 1 to 3, the lowest layer of the laminate It was confirmed that it is useful as a material for forming

Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, it goes without saying that the present invention is not limited to such embodiments. The various shapes, combinations, etc., of the constituent members shown in the above examples are merely examples, and various modifications can be made based on design requirements and the like without departing from the gist of the present invention.

10 Laminate 10b Exposed portion 10c Resin cured film 10d Unexposed portion 11 First resist layer 12 Second resist layer 13 Third resist layer 14 Fourth resist layer 20 Support 90 photomask, 110 resist pattern, 120 curing pattern

Claims (9)

forming a first resist layer on a support using a first photosensitive composition;
forming a second resist layer on the first resist layer using a second photosensitive composition;
A method for manufacturing a laminate,
A method for producing a laminate, wherein a photosensitive composition having higher sensitivity than the second photosensitive composition is used as the first photosensitive composition. The first photosensitive composition is a photosensitive composition containing a polyfunctional aromatic epoxy compound, a photoacid generator, and an alicyclic epoxy compound represented by the following general formula (m1). The manufacturing method of the laminated body of Claim 1.

[In the formula, R ¹ to R ¹⁸ are each independently a hydrogen atom, a halogen atom or an organic group. X is a divalent linking group or a single bond. ] The second photosensitive composition is a photosensitive composition containing a polyfunctional aromatic epoxy compound and a photoacid generator (excluding those containing the alicyclic epoxy compound). Item 3. A method for producing a laminate according to item 2. The method for producing a laminate according to any one of claims 1 to 3, wherein the support comprises a substrate containing a bismaleimide triazine resin. A step of exposing a laminate produced by the method for producing a laminate according to any one of claims 1 to 4;
A step of developing the exposed laminate to form a resist pattern;
a step of curing the resist pattern to obtain a cured pattern;
A method for forming a cured pattern. 6. The cured pattern forming method according to claim 5, wherein the cured pattern is a coil-shaped pattern. 7. The method of forming a hardening pattern according to claim 6, wherein the hardening pattern constitutes an insulating portion in an inductor. A laminate of a first resist layer and a second resist layer,
The first resist layer is a layer containing a polyfunctional aromatic epoxy compound, a photoacid generator, and an alicyclic epoxy compound represented by the following general formula (m1),
The laminate, wherein the second resist layer is a layer containing a polyfunctional aromatic epoxy compound and a photoacid generator (excluding the layer containing the alicyclic epoxy compound).

[In the formula, R ¹ to R ¹⁸ are each independently a hydrogen atom, a halogen atom or an organic group. X is a divalent linking group or a single bond. ] a polyfunctional aromatic epoxy compound;
a photoacid generator;
and an alicyclic epoxy compound represented by the following general formula (m1),
A photosensitive composition for forming a layer of an insulator in an inductor, the layer being in contact with a support.

[In the formula, R ¹ to R ¹⁸ are each independently a hydrogen atom, a halogen atom or an organic group. X is a divalent linking group or a single bond. ]

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