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CN117063121A - Photosensitive film, photosensitive element, and method for producing laminate - Google Patents

Photosensitive film, photosensitive element, and method for producing laminate Download PDF

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Publication number
CN117063121A
CN117063121A CN202280003948.5A CN202280003948A CN117063121A CN 117063121 A CN117063121 A CN 117063121A CN 202280003948 A CN202280003948 A CN 202280003948A CN 117063121 A CN117063121 A CN 117063121A
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CN
China
Prior art keywords
mass
less
group
component
compound
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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CN202280003948.5A
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Chinese (zh)
Inventor
成田真生
小野敬司
渡边祐作
桐生真奈美
武田明子
大友聪
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Lishennoco Co ltd
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Lishennoco Co ltd
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Publication of CN117063121A publication Critical patent/CN117063121A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/061—Etching masks
    • H05K3/064—Photoresists

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Laminated Bodies (AREA)

Abstract

A photosensitive film comprising (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) at least one selected from the group consisting of an anthracene compound, a pyrazoline compound and a distyrylbenzene compound, and (E) a naphthalene compound. A photosensitive element (1) is provided with a support (2) and a photosensitive resin layer (3) disposed on the support (2), wherein the photosensitive resin layer (3) is the photosensitive film. A method for producing a laminate, comprising: disposing a photosensitive resin layer on a substrate using the photosensitive film; a step of photocuring a part of the photosensitive resin layer; removing at least a part of the uncured portion of the photosensitive resin layer to form a cured pattern; and forming a metal layer on at least a part of the portion of the substrate where the cured product pattern is not formed.

Description

Photosensitive film, photosensitive element, and method for producing laminate
Technical Field
The present invention relates to a photosensitive film, a photosensitive element, a method for producing a laminate, and the like.
Background
In the production of a laminate that can be used as a wiring substrate, a resist pattern is formed to obtain a desired wiring. The resist pattern can be formed by exposing and developing a photosensitive resin layer obtained using the photosensitive resin composition. As photosensitive resin compositions, various compositions have been studied. For example, patent document 1 below describes a photosensitive resin composition containing a binder polymer, a photopolymerizable compound, and a specific photopolymerization initiator. The photosensitive film can be obtained by molding the photosensitive resin composition into a film shape.
Technical literature of the prior art
Patent literature
Patent document 1: japanese patent laid-open No. 2019-028398
Disclosure of Invention
Technical problem to be solved by the invention
When a cured product pattern that can be used as a resist pattern is formed using a photosensitive film or a photosensitive resin composition, a cured product pattern having linear line portions and linear space portions adjacent to the line portions may be formed. In addition, when forming a cured pattern having a space portion with a width (space width) smaller than that of a line portion (line width), excellent resolution is required as a characteristic of forming the line portion and the space portion satisfactorily. When forming a cured pattern having a line width smaller than the space width, excellent adhesion is required as a characteristic of forming a line portion and a space portion satisfactorily.
An object of one aspect of the present invention is to provide a photosensitive film that can obtain excellent resolution when forming a cured pattern having a smaller space width than a line width and excellent adhesion when forming a cured pattern having a smaller line width than a space width. Another object of the present invention is to provide a photosensitive element using the photosensitive film. Another object of the present invention is to provide a method for producing a laminate using the photosensitive film.
Means for solving the technical problems
An aspect of the present invention relates to a photosensitive film containing (a) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) at least one selected from the group consisting of an anthracene compound, a pyrazoline compound, and a distyrylbenzene compound, and (E) a naphthalene compound.
According to this photosensitive film, excellent resolution can be obtained when forming a cured pattern having a smaller space width than a line width, and excellent adhesion can be obtained when forming a cured pattern having a smaller line width than a space width.
Another aspect of the present invention relates to a photosensitive element including a support and a photosensitive resin layer disposed on the support, wherein the photosensitive resin layer is the photosensitive film.
Another aspect of the present invention relates to a method for producing a laminate, comprising: disposing a photosensitive resin layer on a substrate using the photosensitive film; a step of photocuring a part of the photosensitive resin layer; removing at least a part of the uncured portion of the photosensitive resin layer to form a cured pattern; and forming a metal layer on at least a part of the portion of the base material where the cured product pattern is not formed.
Effects of the invention
According to one aspect of the present invention, a photosensitive film can be provided that can achieve excellent resolution when forming a cured pattern having a smaller space width than a line width and excellent adhesion when forming a cured pattern having a smaller line width than a space width. According to another aspect of the present invention, a photosensitive element using the photosensitive film can be provided. According to another aspect of the present invention, a method for producing a laminate using the photosensitive film can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of a photosensitive element.
Fig. 2 is a schematic diagram showing an example of a method for producing a laminate.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
In the present specification, the numerical range indicated by the term "to" means a range including numerical values described before and after the term "to" as a minimum value and a maximum value, respectively. The term "a or more" in the numerical range means a and a range exceeding a. The term "a or below" in the numerical range means a and a range smaller than a. In the numerical ranges described in stages in the present specification, the upper limit value or the lower limit value of the numerical range in one stage may be arbitrarily combined with the upper limit value or the lower limit value of the numerical range in another stage. In the numerical ranges described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. "A or B" may include either or both of A and B. The materials exemplified in the present specification can be used singly or in combination of 1 or more than 2, unless otherwise specified. When a plurality of substances corresponding to the respective components are present in the composition, the content of the respective components in the composition is the total amount of the plurality of substances present in the composition unless otherwise specified. The term "layer" includes a structure having a shape formed in a part of the entire surface, as well as a structure having a shape formed in the entire surface when viewed in a plan view. The term "process" includes not only an independent process but also the term if the intended function of the process is achieved even if the process cannot be clearly distinguished from other processes. The "(meth) acrylate" means at least one of an acrylate and a methacrylate corresponding thereto. The same applies to other similar expressions such as "(meth) acrylic acid". Unless otherwise indicated, "alkyl" may be any of straight, branched, or cyclic.
In the present specification, the solid content of the photosensitive resin composition means a non-volatile component other than a volatile substance (water, solvent, etc.) in the photosensitive resin composition. That is, the solid component refers to a component (component other than a solvent) that does not volatilize and remains during drying of the photosensitive resin composition, and includes a component that is liquid, maltose-like, or waxy at room temperature (25 ℃).
Photosensitive film, photosensitive resin composition and cured product
The photosensitive film and the photosensitive resin composition according to the present embodiment contain (a) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) at least one selected from the group consisting of an anthracene compound, a pyrazoline compound, and a distyrylbenzene compound, and (E) a naphthalene compound. The photosensitive film according to the present embodiment can be obtained by forming the photosensitive resin composition according to the present embodiment into a film.
According to the photosensitive film and the photosensitive resin composition of the present embodiment, excellent resolution can be obtained when forming a cured pattern having a smaller space width than a line width, and excellent adhesion can be obtained when forming a cured pattern having a smaller line width than a space width. According to the photosensitive film and the photosensitive resin composition according to the present embodiment, in the evaluation described in the examples, for example, a resolution of 13 μm or less can be obtained, and adhesion of 3 μm or less can be obtained. The shape of the cured product pattern obtainable by the photosensitive film and the photosensitive resin composition according to the present embodiment is not particularly limited.
The present inventors speculate that the reason why the photosensitive film and the photosensitive resin composition according to the present embodiment achieve excellent resolution and adhesion is as follows. However, the main reason is not limited to the following. That is, when the component (a), the component (B) and the component (C) are used simultaneously, the component (D) absorbs light well and supplies a sufficient amount of energy to the component (C), and therefore photosensitivity can be expressed well (for example, a sufficient amount of radicals are generated in an exposed portion and diffusion of radicals into an unexposed portion is suppressed to express photosensitivity well). Further, by using the component (E), the effect of the component (D) can be enhanced. Therefore, excellent resolution and adhesion can be obtained.
According to the photosensitive film and the photosensitive resin composition according to the present embodiment, excellent sensitivity to active light can be obtained. According to the photosensitive film and the photosensitive resin composition according to the present embodiment, for example, 108mJ/cm can be obtained in the evaluation described in the examples 2 The following exposure amounts.
The photosensitive film and the photosensitive resin composition according to the present embodiment have photocurability, and a cured product can be obtained by photocuring the photosensitive film or the photosensitive resin composition. The cured product according to the present embodiment is a cured product (photo-cured product) of the photosensitive film or the photosensitive resin composition according to the present embodiment. The cured product according to the present embodiment may be patterned (cured product pattern) or may be a resist pattern.
The thickness of the photosensitive film and the cured product according to the present embodiment may be 1 μm or more, 3 μm or more, 5 μm or more, 7 μm or more, 10 μm or more, 15 μm or more, 18 μm or more, or 19 μm or more from the viewpoint of easy availability of a resist pattern for obtaining a wiring having a sufficient thickness. The thickness of the photosensitive film and the cured product according to the present embodiment may be 100 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 25 μm or less, 20 μm or less, or 19 μm or less from the viewpoint of easy obtaining of excellent resolution and adhesion. From these viewpoints, the thickness of the photosensitive film and the cured product according to the present embodiment may be 1 to 100 μm, 5 to 100 μm, or 15 to 25 μm.
The wavelength of the photosensitive expression in the photosensitive film and the photosensitive resin composition according to the present embodiment is not particularly limited. The photosensitive film and the photosensitive resin composition according to the present embodiment may have photosensitivity to light having a wavelength of 300nm or more, 340nm or more, 350nm or more, 355nm or more, 365nm or more, 375nm or more, 390nm or more, 395nm or more, or 405nm or more, for example. The photosensitive film and the photosensitive resin composition according to the present embodiment may have photosensitivity to light having a wavelength of 500nm or less, 440nm or less, less than 440nm, 436nm or less, 420nm or less, 410nm or 405nm or less, for example. In the exposure step described later, an active light having a peak in the wavelength range can be used. The photosensitive film and the photosensitive resin composition according to the present embodiment can be used as, for example, a negative photosensitive film and a photosensitive resin composition.
The absorbance of the photosensitive film and the photosensitive resin composition according to the present embodiment with respect to light having a wavelength of 405nm (for example, absorbance at a thickness of 19 μm) may be in the following range. The absorbance with respect to light having a wavelength of 405nm may be more than 0, or may be 0.01 or more, 0.05 or more, 0.1 or more, 0.15 or more, 0.2 or more, 0.25 or more, 0.27 or more, or 0.3 or more. The absorbance with respect to light having a wavelength of 405nm may be 0.5 or less, 0.45 or less, 0.4 or less, 0.35 or less, 0.3 or less, or 0.27 or less. From these viewpoints, the absorbance with respect to light having a wavelength of 405nm may exceed 0 and be 0.5 or less.
According to the present embodiment, it is possible to provide an application of the photosensitive resin composition, the photosensitive film, or the photosensitive element to formation of a cured product pattern (for example, a resist pattern). According to another aspect of the present invention, there can be provided an application of a photosensitive resin composition, a photosensitive film, or a photosensitive element in the production of a wiring board.
The photosensitive film and the photosensitive resin composition according to the present embodiment contain a binder polymer as the component (a). Examples of the component (a) include acrylic resins, styrene resins, epoxy resins, amide epoxy resins, alkyd resins, phenol resins, and the like. The acrylic resin is a resin containing a compound having a (meth) acryloyl group ((meth) acrylic compound) as a monomer unit, and a styrene resin, an epoxy resin, an amide epoxy resin, an alkyd resin, and a phenol resin each having the monomer unit belong to the acrylic resins. (A) The component (c) may or may not contain a binder polymer having no phenolic hydroxyl groups. (A) The composition may or may not contain an adhesive polymer having no epoxy groups.
From the viewpoint of easy obtaining of excellent resolution and adhesion, the component (a) may contain an acrylic resin. From the viewpoint of easy obtaining of excellent resolution and adhesion, the content of the acrylic resin may be 50 mass% or more, more than 50 mass%, 70 mass% or more, 90 mass% or more, 95 mass% or more, 98 mass% or more, 99 mass% or substantially 100 mass% ("the mode in which the component (a) is substantially formed of the acrylic resin) based on the total mass of the component (a).
Examples of the compound having a (meth) acryloyl group include (meth) acrylic acid, (meth) acrylic acid ester, and the like. Examples of the (meth) acrylic acid ester include alkyl (meth) acrylates (alkyl (meth) acrylates, cycloalkyl (meth) acrylates other than those corresponding to cycloalkyl (meth) acrylates, aryl (meth) acrylates (aryl (meth) acrylates), acrylamide compounds (diacetone acrylamide, etc.), glycidyl (meth) acrylates, styryl (meth) acrylic acid, etc.
The component (a) may have (meth) acrylic acid as a monomer unit from the viewpoint of easy obtaining of excellent resolution and adhesion. When the component (a) has (meth) acrylic acid as a monomer unit, the content of the monomer unit of (meth) acrylic acid may be in the following range based on the total amount of monomer units constituting the component (a) from the viewpoint of easy obtaining of excellent resolution and adhesion.
The content of the monomer unit of (meth) acrylic acid may be 1 mass% or more, 5 mass% or more, 10 mass% or more, 15 mass% or more, 20 mass% or more, or 25 mass% or more. The content of the monomer unit of (meth) acrylic acid may be 50 mass% or less, less than 50 mass%, 45 mass% or less, 40 mass% or less, 35 mass% or less, or 30 mass% or less. From these viewpoints, the content of the monomer unit of (meth) acrylic acid may be 1 to 50 mass%.
From the viewpoint of easy obtaining of excellent resolution and adhesion, the component (a) may have an alkyl (meth) acrylate as a monomer unit. Examples of the alkyl group of the alkyl (meth) acrylate include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and the like, and the alkyl group may be various structural isomers. The number of carbon atoms of the alkyl group of the alkyl (meth) acrylate may be 1 to 4, 1 to 3, 2 to 3, or 1 to 2 from the viewpoint of easy obtaining of excellent resolution and adhesion.
The alkyl group of the alkyl (meth) acrylate may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a carboxylate group, an aldehyde group, an alkoxy group (an unsubstituted alkoxy group (having an unsubstituted alkyl group bonded to an oxygen atom) or a substituted alkoxy group (hydroxyalkoxy group or the like)), a carbonyl group, an alkoxycarbonyl group, an alkanoyl group (alkanoyl group or the like having 2 to 12 carbon atoms), an oxycarbonyl group, a carbonyloxy group, an amino group, an epoxy group, a furyl group, a cyano group, a halo group (fluoro group, chloro group, bromo group or the like), a nitro group, an acetyl group, a sulfonyl group, a sulfonamide group and the like. Examples of the alkyl (meth) acrylate include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-trifluoroethyl (meth) acrylate, 2, 3-tetrafluoropropyl (meth) acrylate, α -chloro (meth) acrylate, and α -bromo (meth) acrylate.
The component (a) may have hydroxyalkyl (meth) acrylate as a monomer unit from the viewpoint of easy obtaining of excellent resolution and adhesion. Examples of the hydroxyalkyl (meth) acrylate include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, and hydroxyhexyl (meth) acrylate.
From the viewpoint of easy obtaining of excellent resolution and adhesion, the content of the monomer unit of the alkyl (meth) acrylate when the component (a) has an alkyl (meth) acrylate as a monomer unit or the content of the monomer unit of the hydroxyalkyl (meth) acrylate when the component (a) has a hydroxyalkyl (meth) acrylate as a monomer unit may be within the following range based on the total amount of the monomer units constituting the component (a). The content of the monomer unit may be 0.1 mass% or more, 0.5 mass% or more, 1 mass% or more, 2 mass% or more, or 3 mass% or more. The content of the monomer unit may be 20 mass% or less, 15 mass% or less, 10 mass% or less, 8 mass% or less, 5 mass% or less, or 3 mass% or less. From these viewpoints, the content of the monomer unit may be 0.1 to 20% by mass.
From the viewpoint of easy obtaining of excellent resolution and adhesion, the component (a) may have an aryl (meth) acrylate as a monomer unit. Examples of the aryl (meth) acrylate include benzyl (meth) acrylate, phenyl (meth) acrylate, and naphthyl (meth) acrylate.
When the component (a) has an aryl (meth) acrylate as a monomer unit, the content of the monomer unit of the aryl (meth) acrylate may be in the following range based on the total amount of the monomer units constituting the component (a) from the viewpoint of easily obtaining excellent resolution and adhesion. The content of the monomer unit of the aryl (meth) acrylate may be 1 mass% or more, 5 mass% or more, 10 mass% or more, 15 mass% or more, or 20 mass% or more. The content of the monomer unit of the aryl (meth) acrylate may be 50 mass% or less, less than 50 mass%, 45 mass% or less, 40 mass% or less, 35 mass% or less, 30 mass% or less, 25 mass% or less, or 20 mass% or less. From these viewpoints, the content of the monomer unit of the aryl (meth) acrylate may be 1 to 50 mass%.
From the viewpoint of easy obtaining of excellent resolution and adhesion, the component (a) may have a styrene compound (other than the compound having a (meth) acryloyl group) as a monomer unit. Examples of the styrene compound include styrene and styrene derivatives. Examples of the styrene derivative include vinyl toluene and α -methylstyrene. From the viewpoint of easy obtaining of excellent resolution and adhesion, the component (a) may have (meth) acrylic acid and a styrene compound as monomer units, hydroxyalkyl (meth) acrylate and a styrene compound as monomer units, or aryl (meth) acrylate and a styrene compound as monomer units.
When the component (a) has a styrene compound as a monomer unit, the content of the monomer unit of the styrene compound may be in the following range based on the total amount of the monomer units constituting the component (a) from the viewpoint of easy obtaining of excellent resolution and adhesion. The content of the monomer unit of the styrene compound may be 10 mass% or more, more than 10 mass%, 15 mass% or more, more than 15 mass%, 20 mass% or more, more than 20 mass%, 25 mass% or more, more than 25 mass%, and 30 mass% or more, more than 30 mass%, 35 mass% or more, more than 35 mass%, 40 mass% or more, more than 40 mass%, 45 mass% or more, more than 45 mass%, 47 mass% or more, or 50 mass% or more. The content of the monomer unit of the styrene compound may be 90 mass% or less, 85 mass% or less, 80 mass% or less, 75 mass% or less, 70 mass% or less, 65 mass% or less, 60 mass% or less, 55 mass% or less, or 50 mass% or less. From these viewpoints, the content of the monomer unit of the styrene compound may be 10 to 90 mass%.
When the component (a) has a styrene compound as a monomer unit, the content of the monomer unit of the styrene compound may be in the following range based on the total amount of the monomer units constituting the component (a) from the viewpoint of easy obtaining of excellent resolution and adhesion. The content of the monomer unit of the styrene compound may be 10mol% or more, more than 10mol%, 15mol% or more, 20mol% or more, more than 20mol%, 25mol% or more, 30mol% or more, more than 30mol%, 35mol% or more, 40mol% or more, more than 40mol%, 45mol% or more, 50mol% or more, or more than 50mol%. The content of the monomer unit of the styrene compound may be 90mol% or less, 85mol% or less, 80mol% or less, 75mol% or less, 70mol% or less, 65mol% or less, 60mol% or less, or 55mol% or less. From these viewpoints, the content of the monomer unit of the styrene compound may be 10 to 90mol%.
(A) The composition may have other monomers as monomer units. Examples of such monomers include ethers of vinyl alcohol (e.g., vinyl n-butyl ether), acrylonitrile, maleic acid, maleic anhydride, maleic monoester (e.g., monomethyl maleate, monoethyl maleate, and monoisopropyl maleate), fumaric acid, cinnamic acid, α -cyanocinnamic acid, itaconic acid, crotonic acid, and propynylic acid.
(A) The component (c) may contain a binder polymer having no nitrogen-containing group or may not contain a binder polymer having a nitrogen-containing group (for example, a binder polymer containing a compound having a nitrogen-containing group as a monomer unit). The content of the monomer unit of the compound having a nitrogen-containing group in the component (a) may be 1mol% or less, less than 1mol%, 0.1mol% or less, or 0.01mol% or less based on the total amount of the monomer units constituting the component (a).
The acid value of the component (a) may be in the following range from the viewpoint of easy obtaining of excellent resolution and adhesion. (A) The acid value of the component may be 80mgKOH/g or more, 90mgKOH/g or more, 100mgKOH/g or more, more than 100mgKOH/g, 120mgKOH/g or more, 140mgKOH/g or more, 150mgKOH/g or more, 160mgKOH/g or more, or 170mgKOH/g or more. (A) The acid value of the component may be 250mgKOH/g or less, 240mgKOH/g or less, 230mgKOH/g or less, 210mgKOH/g or less, 200mgKOH/g or 180mgKOH/g or less. From these viewpoints, the acid value of the component (A) may be 80 to 250mgKOH/g. (A) The acid value of the component (a) can be adjusted by the content of the monomer unit constituting the component (a) (for example, the monomer unit of (meth) acrylic acid).
(A) The acid value of the component (a) can be measured by the method described in examples.
The weight average molecular weight (Mw) of the component (a) may be in the following range from the viewpoint of easy obtaining of excellent resolution and adhesion. (A) The weight average molecular weight of the component (a) may be 10000 or more, 20000 or more, 25000 or more, 30000 or more, or 35000 or more. (A) The weight average molecular weight of the component may be 100000 or less, 80000 or less, 70000 or less, 65000 or less, 60000 or less, 50000 or less, 40000 or 35000 or less. From these viewpoints, the weight average molecular weight of the component (a) may be 10000 to 100000, 20000 to 50000, or 30000 to 40000.
The number average molecular weight (Mn) of the component (a) may be in the following range from the viewpoint of easy obtaining of excellent resolution and adhesion. (A) The number average molecular weight of the component (A) may be 5000 or more, 10000 or more, 12000 or more, 15000 or more, or 16000 or more. (A) The number average molecular weight of the component (a) may be 50000 or less, 40000 or less, 35000 or less, 30000 or less, 25000 or less, 20000 or 16000 or less. From these viewpoints, the number average molecular weight of the component (a) may be 5000 to 50000, 10000 to 25000, or 15000 to 20000.
The dispersivity (weight average molecular weight/number average molecular weight) of the component (a) may be in the following range from the viewpoint of easy obtaining of excellent resolution and adhesion. (A) The dispersity of the components may be 1.0 or more, 1.5 or more, 1.8 or more, 2.0 or more, or 2.1 or more. (A) The dispersity of the components may be 3.0 or less, 2.8 or less, 2.5 or less, 2.3 or less, or 2.2 or less. From these viewpoints, the dispersity of the component (a) may be 1.0 to 3.0.
The weight average molecular weight and the number average molecular weight can be measured by Gel Permeation Chromatography (GPC) using a calibration curve of standard polystyrene, for example. More specifically, the measurement can be performed under the conditions described in examples. When it is difficult to measure a compound having a low molecular weight by the above-mentioned method for measuring a weight average molecular weight and a number average molecular weight, the molecular weight can be measured by other methods and the average value can be calculated.
(A) The content of the component (c) may be in the following range based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total amount of solid content). The content of the component (a) may be 10 mass% or more, 20 mass% or more, 30 mass% or more, 40 mass% or more, 45 mass% or more, or 50 mass% or more from the viewpoint of easy obtaining of excellent resolution and adhesion and excellent film formability. The content of the component (a) may be 90 mass% or less, 80 mass% or less, 75 mass% or less, 70 mass% or less, 65 mass% or less, 60 mass% or less, or 55 mass% or less from the viewpoint of easy obtaining of excellent resolution and adhesion. From these viewpoints, the content of the component (a) may be 10 to 90 mass%.
(A) The content of the component (a) may be within the following range with respect to 100 parts by mass of the total amount of the component (B). The content of the component (a) may be 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, 45 parts by mass or more, 50 parts by mass or more, or 55 parts by mass or more from the viewpoint of easy obtaining of excellent resolution and adhesion and excellent film formability. The content of the component (a) may be 90 parts by mass or less, 80 parts by mass or less, 75 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less from the viewpoint of easy obtaining of excellent resolution and adhesion. From these viewpoints, the content of the component (a) may be 10 to 90 parts by mass or 40 to 70 parts by mass.
The photosensitive film according to the present embodiment contains a photopolymerizable compound (excluding a compound corresponding to an anthracene compound, a pyrazoline compound, a distyrylbenzene compound, or a naphthalene compound) as the component (B). The photopolymerizable compound is a compound that is polymerized by light. (B) The component (c) may be a compound having an ethylenically unsaturated bond or a compound having a (meth) acryloyl group ((meth) acrylic compound).
As the component (B), a compound having a specific structure, examples thereof include bisphenol A type (meth) acrylic acid compounds, EO-modified di (meth) acrylates, PO-modified di (meth) acrylates, EO/PO-modified di (meth) acrylates, polyalkylene glycol di (meth) acrylates, polypropylene glycol di (meth) acrylates, etc., EO-modified polyalkylene glycol di (meth) acrylates, PO-modified polyalkylene glycol di (meth) acrylates, EO/PO-modified polyalkylene glycol di (meth) acrylates, trimethylol propane tri (meth) acrylates, EO-modified trimethylol propane tri (meth) acrylates, PO-modified trimethylol propane tri (meth) acrylates, tetramethylol methane tetra (meth) acrylates, EO-modified pentaerythritol tetra (meth) acrylates, EO/PO-modified pentaerythritol tetra (meth) acrylates, EO-modified dipentaerythritol hexa (meth) acrylates, PO-modified dipentaerythritol hexa (meth) acrylates, hexahydropentaerythritol di (meth) acrylates, hexahydro-modified pentaerythritol di (meth) acrylates, nonylphenoxy polyethylene oxide acrylate, phthalic acid compounds, alkyl (meth) acrylate, photopolymerizable compounds having at least 1 cyclic ether group capable of polymerizing with cations in the molecule (oxetane compounds and the like), and the like. The term "EO-modified" refers to a compound having a (poly) oxyethylene group. The term "PO modified" refers to a compound having a (poly) oxypropylene group. The term "EO/PO modified" refers to a compound having a (poly) oxyethylene group and/or a (poly) oxypropylene group.
From the viewpoint of easy availability of excellent resolution and adhesion, the component (B) may contain a photopolymerizable compound having a (poly) oxyethylene group (for example, a (meth) acrylic compound having a (poly) oxyethylene group) in the following range of the number of structural units of the oxyethylene group. The number of structural units of the oxyethylene group may be 1 or more, 2 or more, 3 or more, 4 or more, more than 4, 5 or more, 6 or more, 8 or more, or 10 or more. The number of structural units of the oxyethylene group may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or less than 4 or 3. From these viewpoints, the number of structural units of the oxyethylene group may be 1 to 20, 2 to 18, 4 to 16 or 6 to 10. The number of structural units of the oxyethylene group is the total number of structural units of the oxyethylene group in the (poly) oxyethylene group contained in the photopolymerizable compound. For example, in the case where the photopolymerizable compound has two (poly) oxyethylene groups, the total of the number of structural units of the oxyethylene group in one (poly) oxyethylene group and the number of structural units of the oxyethylene group in the other (poly) oxyethylene group is taken as the object.
The component (B) may contain a bisphenol a type (meth) acrylic compound from the viewpoint of easy obtaining of excellent resolution and adhesion. Examples of bisphenol a type (meth) acrylic compounds include 2, 2-bis (4- ((meth) acryloxypolyethoxy) phenyl) propane (2, 2-bis (4- ((meth) acryloxypentaethoxy) phenyl) propane, 2-bis (4- ((meth) acryloxypolypropoxy) phenyl) propane, 2-bis (4- ((meth) acryloxypolybutoxy) phenyl) propane, 2-bis (4- ((meth) acryloxypolyethoxypropoxy) phenyl) propane, and the like. From the viewpoint of easy availability of excellent resolution and adhesion, the component (B) may contain 2, 2-bis (4- ((meth) acryloyloxy polyethoxy) phenyl) propane, or may contain 2, 2-bis (4- ((meth) acryloyloxy pentaethoxy) phenyl) propane.
The molecular weight of the bisphenol a type (meth) acrylic compound may be in the following range from the viewpoint of easy obtaining of excellent resolution and adhesion. The molecular weight may be 100 or more, 200 or more, 300 or more, 400 or more, 450 or more, 500 or more, 600 or more, 700 or more, or 800 or more. The molecular weight may be 10000 or less, less than 10000, 8000 or less, 6000 or less, 5000 or less, 3000 or less, 2000 or less, 1500 or less, 1000 or less, 900 or less, 800 or less, 700 or less, 600 or 500 or less. From these viewpoints, the molecular weight may be 100 to 10000.
The content of the bisphenol a type (meth) acrylic compound may be within the following range based on the total mass of the component (B) from the viewpoint of easy obtaining of excellent resolution and adhesion. The content of the bisphenol a type (meth) acrylic compound may be 50 mass% or more, more than 50 mass%, 60 mass% or more, 70 mass% or more, 80 mass% or more, 85 mass% or more, or 90 mass% or more. The bisphenol a type (meth) acrylic compound may be contained in an amount of 100 mass% or less, or may be less than 100 mass%, 99 mass% or less, 98 mass% or less, 97 mass% or less, 95 mass% or less, 92 mass% or less, or 91 mass% or less. From these viewpoints, the content of the bisphenol a type (meth) acrylic compound may be 50 to 100 mass%.
The content of the bisphenol a type (meth) acrylic compound may be within the following range with respect to 100 parts by mass of the total of the component (a) and the component (B) from the viewpoint of easy obtaining of excellent resolution and adhesion. The content of the bisphenol a type (meth) acrylic compound may be 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, or 40 parts by mass or more. The content of the bisphenol a type (meth) acrylic compound may be less than 100 parts by mass, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, or 40 parts by mass or less. From these viewpoints, the content of the bisphenol a type (meth) acrylic compound may be 1 part by mass or more and less than 100 parts by mass.
The component (B) may contain a (meth) acrylic compound having a polyoxyalkylene group (a group in which an alkylene group of 2 or more is bonded by an ether bond) (excluding a compound corresponding to a bisphenol a type (meth) acrylic compound) or may contain a (meth) acrylic compound having at least one selected from the group consisting of a polyoxyethylene group and a polyoxypropylene group (excluding a compound corresponding to a bisphenol a type (meth) acrylic compound) from the viewpoint of easy availability of excellent resolution and adhesion.
The molecular weight of the (meth) acrylic compound having a polyoxyalkylene group may be in the following range from the viewpoint of easy obtaining of excellent resolution and adhesion. The molecular weight may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 600 or more, 700 or more, 800 or more, 900 or more, 1000 or more, or 1100 or more. The molecular weight may be 10000 or less, less than 10000, 8000 or less, 6000 or less, 5000 or less, 3000 or less, 2000 or less, 1500 or 1200 or less. From these viewpoints, the molecular weight may be 100 to 10000.
The content of the (meth) acrylic compound having a polyoxyalkylene group may be in the following range based on the total mass of the component (B) from the viewpoint of easy obtaining of excellent resolution and adhesion. The content of the (meth) acrylic compound having a polyoxyalkylene group may be more than 0 mass%, or may be 1 mass% or more, 2 mass% or more, 3 mass% or more, 5 mass% or more, 8 mass% or more, or 9 mass% or more. The content of the (meth) acrylic compound having a polyoxyalkylene group may be 50 mass% or less, less than 50 mass%, 40 mass% or less, 30 mass% or less, 20 mass% or less, 15 mass% or less, or 10 mass% or less. From these viewpoints, the content of the (meth) acrylic compound having a polyoxyalkylene group may be more than 0 mass% and 50 mass% or less.
From the viewpoint of easy obtaining of excellent resolution and adhesion, the content of the (meth) acrylic compound having a polyoxyalkylene group may be in the following range with respect to 100 parts by mass of the total amount of the component (a) and the component (B). The content of the (meth) acrylic compound having a polyoxyalkylene group may be 0.1 part by mass or more, 0.5 part by mass or more, 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, or 4 parts by mass or more. The content of the (meth) acrylic compound having a polyoxyalkylene group may be 50 parts by mass or less, 30 parts by mass or less, 10 parts by mass or less, 8 parts by mass or less, 6 parts by mass or less, 5 parts by mass or less, less than 5 parts by mass or 4 parts by mass or less. From these viewpoints, the content of the (meth) acrylic compound having a polyoxyalkylene group may be 0.1 to 50 parts by mass.
When the component (B) contains a bisphenol a type (meth) acrylic compound and a (meth) acrylic compound having a polyoxyalkylene group, the content of the bisphenol a type (meth) acrylic compound may be in the following range with respect to 100 parts by mass of the (meth) acrylic compound having a polyoxyalkylene group from the viewpoint of easy obtaining of excellent resolution and adhesion. The content of the bisphenol a type (meth) acrylic compound may be 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 5 parts by mass or more, 8 parts by mass or more, or 10 parts by mass or more. The content of the bisphenol a type (meth) acrylic compound may be 100 parts by mass or less, less than 100 parts by mass, 80 parts by mass or less, 50 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less. From these viewpoints, the content of the bisphenol a type (meth) acrylic compound may be 1 to 100 parts by mass.
The content of the component (B) may be in the following range based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content) from the viewpoint of easy obtaining of excellent resolution and adhesion. (B) The content of the component may be 10 mass% or more, 15 mass% or more, 20 mass% or more, 25 mass% or more, 30 mass% or more, 35 mass% or more, or 40 mass% or more. (B) The content of the component may be 90 mass% or less, 80 mass% or less, 70 mass% or less, 65 mass% or less, 60 mass% or less, 55 mass% or less, 50 mass% or less, or 45 mass% or less. From these viewpoints, the content of the component (B) may be 10 to 90 mass%.
The content of the component (B) may be within the following range with respect to 100 parts by mass of the total of the component (a) and the component (B) from the viewpoint of easy obtaining of excellent resolution and adhesion. (B) The content of the component may be 10 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, or 40 parts by mass or more. (B) The content of the component may be 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, 55 parts by mass or less, 50 parts by mass or less, or 45 parts by mass or less. From these viewpoints, the content of the component (B) may be 10 to 90 parts by mass or 30 to 60 parts by mass.
The photosensitive film and the photosensitive resin composition according to the present embodiment contain a photopolymerization initiator (excluding compounds corresponding to an anthracene compound, a pyrazoline compound, a distyrylbenzene compound, or a naphthalene compound) as the component (C).
As the component (C), hexaarylbiimidazole compounds are mentioned; aromatic ketones such as benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1, and the like; quinone compounds such as alkylanthraquinone; benzoin ether compounds such as benzoin alkyl ether; benzoin compounds such as benzoin and alkylbenzoin; benzyl derivatives such as benzyl dimethyl ketal; bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide; bis (2, 6-dimethylbenzoyl) -2, 4-trimethyl-pentylphosphine oxide; (2, 4, 6-trimethylbenzoyl) ethoxyphenylphosphine oxide, and the like.
The component (C) may contain a hexaarylbisimidazole compound from the viewpoint of easy availability of excellent resolution and adhesion. The aryl group in the hexaarylbiimidazole compound may be phenyl or the like. The hydrogen atom bonded to the aryl group in the hexaarylbiimidazole compound may be substituted with a halogen atom (chlorine atom or the like).
The hexaarylbiimidazole compound may be a 2,4, 5-triarylimidazole dimer. Examples of the 2,4, 5-triarylimidazole dimer include a 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, a 2- (o-chlorophenyl) -4, 5-bis- (m-methoxyphenyl) imidazole dimer, and a 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer. From the viewpoint of easy availability of excellent resolution and adhesion, the hexaarylbiimidazole compound may contain 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, or may contain 2,2 '-bis (o-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole.
From the viewpoint of easy availability of excellent resolution and adhesion, the content of the hexaarylbiimidazole compound may be 50 mass% or more, more than 50 mass%, 70 mass% or more, 90 mass% or more, 95 mass% or more, 98 mass% or more, 99 mass% or substantially 100 mass% ("the mode in which the (C) component substantially consists of the hexaarylbiimidazole compound) based on the total amount of the (C) component.
The content of the component (C) may be in the following range based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content) from the viewpoint of easy obtaining of excellent resolution and adhesion. (C) The content of the component may be 0.1 mass% or more, 0.5 mass% or more, 1 mass% or more, 2 mass% or more, 3 mass% or more, 4 mass% or more, 5 mass% or more, or 5.5 mass% or more. (C) The content of the component may be 20 mass% or less, 15 mass% or less, 12 mass% or less, 10 mass% or less, 8 mass% or less, 7 mass% or less, or 6 mass% or less. From these viewpoints, the content of the component (C) may be 0.1 to 20 mass%.
The content of the component (C) may be within the following range with respect to 100 parts by mass of the total of the component (a) and the component (B) from the viewpoint of easy obtaining of excellent resolution and adhesion. (C) The content of the component may be 0.1 part by mass or more, 0.5 part by mass or more, 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 4 parts by mass or more, 5 parts by mass or more, 5.5 parts by mass or more, or 6 parts by mass or more. (C) The content of the component may be 20 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, 10 parts by mass or less, 8 parts by mass or less, 7 parts by mass or less, or 6 parts by mass or less. From these viewpoints, the content of the component (C) may be 0.1 to 20 parts by mass.
The photosensitive film and the photosensitive resin composition according to the present embodiment contain, as the component (D), at least one selected from the group consisting of an anthracene compound (a compound having an anthracene ring; a compound corresponding to a naphthalene compound), a pyrazoline compound (a compound having a pyrazoline ring; a compound corresponding to an anthracene compound or a naphthalene compound), and a distyrylbenzene compound (a compound having a benzene ring to which 2 styryl groups are bonded; a compound corresponding to an anthracene compound, a pyrazoline compound, or a naphthalene compound). The component (D) can be used as a sensitizer (photosensitizer). The photosensitive film and the photosensitive resin composition according to the present embodiment may contain no anthracene compound, may contain no pyrazoline compound, or may contain no distyrylbenzene compound. The molecular weight of component (D) may be less than 10000.
Particularly excellent resolution can be obtained by containing an anthracene compound in the component (D). The anthracene compound may have a substituent bonded to an anthracycline, or may have a substituent bonded to at least one selected from the group consisting of 9-position and 10-position of an anthracycline. Examples of the substituent include an alkyl group (an alkyl group having 1 to 20 carbon atoms (acyclic alkyl group), a cycloalkyl group having 5 to 12 carbon atoms, etc.), an aryl group (a phenyl group, an aralkyl group (benzyl group, phenethyl group, etc.), a benzoyl group, a styryl group, etc.), a vinyl group, a hydroxyl group, a carboxyl group, a carboxylate group, an aldehyde group, an alkoxy group (unsubstituted alkoxy group or substituted alkoxy group (hydroxyalkoxy group, etc.), a carbonyl group, an alkoxycarbonyl group, an alkanoyl group (alkanoyl group having 2 to 12 carbon atoms, etc.), an oxycarbonyl group, a carbonyloxy group, an amino group, an epoxy group, a furyl group, a cyano group, a halogeno group (fluoro group, chloro group, bromo group, etc.), a nitro group, an acetyl group, a sulfonyl group, a sulfonamide group, etc.
From the viewpoint of easy obtaining of excellent resolution and adhesion, the component (D) may contain a compound represented by the following general formula (D1).
[ in formula (d 1), R d10 R is R d11 Each independently represents an alkyl group (an alkyl group having 1 to 20 carbon atoms (acyclic alkyl group), a cycloalkyl group having 5 to 12 carbon atoms, or the like), a phenyl group, a benzyl group, an alkanoyl group (e.g., an alkanoyl group having 2 to 12 carbon atoms), or a benzoyl group. R is R d12 、R d13 、R d14 、R d15 、R d16 、R d17 、R d18 R is R d19 Each independently represents a hydrogen atom, an alkyl group (e.g., an alkyl group having 1 to 12 carbon atoms), a halogen group, a cyano group, a carboxyl group, a phenyl group, an alkoxycarbonyl group (e.g., an alkoxycarbonyl group having 2 to 6 carbon atoms), or a benzoyl group.]
In the formula (d 1), when the number of carbon atoms of the alkyl group is 2 or more (for example, 2 to 12), the alkyl group may have an oxygen atom between carbon atoms of the main chain or may be substituted with a hydroxyl group. Cycloalkyl groups may have an oxygen atom in the ring or may be substituted with a hydroxyl group. The phenyl group, the benzyl group and the benzoyl group may be substituted with at least one member selected from the group consisting of an alkyl group (e.g., an alkyl group having 1 to 6 carbon atoms), a hydroxyl group, a halogen group, a cyano group, a carboxyl group, a phenyl group, an alkoxy group (e.g., an alkoxy group having 1 to 6 carbon atoms), a phenoxy group and an alkoxycarbonyl group (e.g., an alkoxycarbonyl group having 2 to 6 carbon atoms). R is from the viewpoint of easy availability of excellent resolution and adhesion d12 、R d13 、R d14 、R d15 、R d16 、R d17 、R d18 R is R d19 May be a hydrogen atom.
The anthracene compound may have no hydroxyl group in the molecule, or may have no hydroxyalkoxy group bonded to the anthracycline. The anthracene compound may have no COO group (C (=o) O group) or no COO group (C (=o) O group) bonded to the anthracycline in the molecule, and the anthracene compound may have no substituent at positions other than the 9-and 10-positions of the anthracycline.
(D) The component (a) may contain no anthracene compound having a hydroxyl group in the molecule, or may contain no anthracene compound having a hydroxyalkoxy group bonded to an anthracycline. (D) The component (a) may not contain an anthracene compound having a COO group (C (=o) O group) in a molecule, or may not contain an anthracene compound having a COO group (C (=o) O group) bonded to an anthracycline. (D) The component (a) may not contain an anthracene compound having substituents at positions other than the 9-and 10-positions of the anthracycline. (D) The component (a) may be an anthracene compound containing no substituent having 2 or more oxygen atoms bonded to an anthracene ring.
The number of carbon atoms of the alkoxy group may be in the following range from the viewpoint of easy obtaining of excellent resolution and adhesion. For example, in the above formula (d 1), R is selected from d10 R is R d11 When at least one of the groups is an alkyl group, OR is selected from the group consisting of an alkyl group, from the viewpoint of easily obtaining excellent resolution and adhesion d10 OR d11 The number of carbon atoms of the alkoxy group of (a) may be within the following range. The number of carbon atoms of the alkoxy group may be 1 or more, 2 or more, 3 or more, or 4 or more. The number of carbon atoms of the alkoxy group may be 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less. From these viewpoints, the carbon number of the alkoxy group may be 1 to 10.
Examples of the anthracene compound include 1-methylanthracene, 2-methylanthracene, 9-methylanthracene, 2-ethylanthracene, 2-butylanthracene, 9-vinylanthracene, 9-phenylanthracene, 1-aminoanthracene, 2-aminoanthracene, 9- (methylaminomethyl) anthracene, 9-acetylanthracene, 9-anthracenaldehyde, 9, 10-dimethylanthracene, 9, 10-diethoxyanthracene, 9, 10-dipropyloxyanthracene, 9, 10-dibutoxyanthracene, 9, 10-bis (2-ethylhexyloxy) anthracene, 9, 10-diphenylanthracene, 2-bromo-9, 10-diphenylanthracene, 9- (4-bromophenyl) -10-phenylanthracene, 10-methyl-9-anthracenaldehyde, 1,4,9,10-tetrahydroxyanthracene, and the like.
From the viewpoint of easy availability of excellent resolution and adhesion, the anthracene compound may include a compound having an unsubstituted alkoxy group bonded to an anthracycline (for example, a dialkoxyanthracene compound having 2 unsubstituted alkoxy groups bonded to an anthracycline), may include a compound having an unsubstituted alkoxy group bonded to at least one selected from the group consisting of 9 and 10 positions of an anthracycline, may include at least one selected from the group consisting of 9, 10-dipropoxyanthracene and 9, 10-dibutoxyanthracene, and may include 9, 10-dibutoxyanthracene. From the viewpoint of easy availability of excellent resolution and adhesion, the component (D) may not include compounds other than the compounds having unsubstituted alkoxy groups bonded to the 9-and 10-positions of the anthracycline as the anthracene compound. That is, the anthracene compound in the component (D) may be a compound having unsubstituted alkoxy groups bonded to the 9-and 10-positions of the anthracycline.
From the viewpoint of easy availability of excellent resolution and adhesion, the content of the compound having an unsubstituted alkoxy group bonded to an anthracycline or the content of the anthracene compound having an unsubstituted alkoxy group bonded to 9 and 10 positions of an anthracycline may be 50 mass% or more, more than 50 mass%, 70 mass% or more, 90 mass% or more, 95 mass% or more, 98 mass% or more, or substantially 100 mass% (the anthracene compound substantially consists of a compound having an unsubstituted alkoxy group bonded to an anthracycline) based on the total mass of the anthracene compound (the total mass of the anthracene compound contained in the photosensitive film or the photosensitive resin composition), or may be 50 to 100 mass%.
When the component (D) contains a pyrazoline compound, excellent sensitivity can be easily obtained. As the pyrazoline compound, a 1-pyrazoline compound, a 2-pyrazoline compound, and a 3-pyrazoline compound can be mentioned. The pyrazoline compound may contain a 2-pyrazoline compound from the viewpoint of easy obtaining of excellent resolution and adhesion.
The pyrazoline compound may have a substituent bonded to the pyrazoline ring, or may include a compound having a substituent bonded to at least one selected from the group consisting of 1 position, 3 position, and 5 position of the pyrazoline ring. Examples of the substituent include an alkyl group (an alkyl group having 1 to 20 carbon atoms (acyclic alkyl group), a cycloalkyl group having 5 to 12 carbon atoms, etc.), an aryl group (a phenyl group, an aralkyl group (benzyl group, phenethyl group, etc.), a benzoyl group, a styryl group, etc.), a vinyl group, a hydroxyl group, a carboxyl group, a carboxylate group, an aldehyde group, an alkoxy group (unsubstituted alkoxy group or substituted alkoxy group (hydroxyalkoxy group, etc.), a carbonyl group, an alkoxycarbonyl group, an alkanoyl group (alkanoyl group having 2 to 12 carbon atoms, etc.), an oxycarbonyl group, a carbonyloxy group, an amino group, an epoxy group, a furyl group, a cyano group, a halogeno group (fluoro group, chloro group, bromo group, etc.), a nitro group, an acetyl group, a sulfonyl group, a sulfonamide group, etc. The benzene ring of the aryl group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group (methoxy group, ethoxy group, propoxy group, etc.), a halogen group (fluoro group, chloro group, bromo group, etc.), a sulfonamide group, and the like. The substituent may be an alkyl ester group (for example, an alkyl ester group having 1 to 6 carbon atoms), an alkylamino group (for example, an alkylamino group having 1 to 20 carbon atoms), or the like.
The component (D) may contain at least one selected from the group consisting of a compound represented by the following general formula (D21) and a compound represented by the following general formula (D22) from the viewpoint of easy obtaining of excellent resolution and adhesion.
[ in formula (d 21), R d211 、R d212 R is R d213 Each independently represents an alkoxy group (e.g., an alkoxy group having 1 to 10 carbon atoms) or an alkyl group (e.g., an alkyl group having 1 to 3 carbon atoms), and d211, d212 and d213 independently represent integers of 0 to 5. When d211 is 2 or more, there are plural R d211 May be the same or different, and when d212 is 2 or more, a plurality of R's are present d212 May be the same or different, and when d213 is 2 or more, a plurality of R's are present d213 May be the same or different.]
In the formula (d 21), R d211 、R d212 R is R d213 At least one of them may be an alkoxy group (for example, an alkoxy group having 1 to 10 carbon atoms) or an alkyl group (for example, an alkyl group having 1 to 3 carbon atoms). From the viewpoint of easy availability of excellent resolution and adhesion, it is selected from the group consisting of R d212 R is R d213 At least one of the group consisting of alkoxy groups may be methoxy, ethoxy or propoxy groups. D211 may be 0 from the viewpoint of easy obtaining of excellent resolution and adhesion. From the viewpoint of easy availability of excellent resolution and adhesion, at least one selected from the group consisting of d212 and d213 may be 0, 1, 2 or 3, or may be 1. The sum of d211, d212 and d213 may be 0 to 6 or 1 to 6.
[ in formula (d 22), R d221 R is R d222 Each independently represents an alkyl group (an alkyl group having 1 to 20 carbon atoms (acyclic alkyl group), a cycloalkyl group having 5 to 12 carbon atoms, or the like), an alkoxy group (e.g., an alkoxy group having 1 to 6 carbon atoms), an amino group, a halo group, a carboxyl group, a cyano group, a nitro group, an acetyl group, a sulfonyl group, or a sulfonamide group, and d221 and d222 each independently represent an integer of 0 to 5. When d221 is 2 or more, there are a plurality of R d221 May be the same or different, and when d222 is 2 or more, there are plural R' s d222 May be the same or different.]
In the formula (d 22), R is from the viewpoint of easy obtaining of excellent resolution and adhesion d221 May be a halogenated group, or may be a fluoro group, a chloro group or a bromo group. R is from the viewpoint of easy availability of excellent resolution and adhesion d222 May be a sulfonamide group. From the viewpoint of easy availability of excellent resolution and adhesion, at least one selected from the group consisting of d221 and d222 may be 0, 1, 2 or 3, or may be 1.
As the pyrazoline compound, there may be mentioned 1-phenyl-3- (4-isopropylphenyl-vinyl) -5- (4-isopropylphenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butylphenyl) -pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline, 1-phenyl-3- (3, 5-dimethoxystyryl) -5- (3, 5-dimethoxystyryl) -pyrazoline, 1-phenyl-3- (3, 4-dimethoxystyryl) -5- (3, 4-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 6-dimethoxystyryl) -5- (2, 6-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 5-dimethoxystyryl) -5- (2, 5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 3-dimethoxystyryl) -5- (2, 3-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 4-dimethoxystyryl) -5- (2, 4-dimethoxystyryl) -pyrazoline, 4- [ [3- (4-chlorophenyl) -4, 5-dihydro-1H-pyrazol ] -1-yl ] benzenesulfonamide, and the like.
From the viewpoint of easy availability of excellent resolution and adhesion, the pyrazoline compound may include a compound having an aryl group bonded to a pyrazoline ring (a compound having 2 or more (for example, 2 to 3) aryl groups bonded to a pyrazoline ring, or the like), may include a compound having an aryl group bonded to at least one selected from the group consisting of 1 position, 3 position, and 5 position of a pyrazoline ring, may include a compound having a phenyl group (a phenyl group which may have a substituent) bonded to at least one selected from the group consisting of 1 position, 3 position, and 5 position of a pyrazoline ring, and may include at least one selected from the group consisting of 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline and 4- [ [3- (4-chlorophenyl) -4, 5-dihydro-1H-pyrazol ] -1-yl ] benzenesulfonamide.
Particularly excellent sensitivity can be obtained by containing a distyrylbenzene compound in the component (D). In the distyrylbenzene compound, a benzene ring of a styryl group may have a substituent, and a benzene ring formed by bonding 2 styryl groups thereto. Examples of the substituent include an alkyl group (an alkyl group having 1 to 20 carbon atoms (acyclic alkyl group), a cycloalkyl group having 5 to 12 carbon atoms, etc.), an aryl group (a phenyl group, an aralkyl group (benzyl group, phenethyl group, etc.), a benzoyl group, etc.), a vinyl group, a hydroxyl group, a carboxyl group, a carboxylate group, an aldehyde group, an alkoxy group (an unsubstituted alkoxy group or a substituted alkoxy group (hydroxyalkoxy group, etc.), a carbonyl group, an alkoxycarbonyl group, an alkanoyl group (an alkanoyl group having 2 to 12 carbon atoms, etc.), an oxycarbonyl group, a carbonyloxy group, an amino group, an epoxy group, a furyl group, a cyano group, a halo group (fluoro group, chloro group, bromo group, etc.), a nitro group, an acetyl group, a sulfonyl group, a sulfonamide group, etc.
From the viewpoint of easy obtaining of excellent resolution and adhesion, the component (D) may contain a compound represented by the following general formula (D3).
[ in formula (d 3), R d31 、R d32 R is R d33 Cyano groups are represented, d31 and d32 are each independently an integer of 0 to 5, and d33 is an integer of 0 to 4.]
In the formula (d 3), at least one selected from the group consisting of d31 and d32 may be 1, 2, 3, 4 or 5, or may be 1, from the viewpoint of easy obtaining of excellent resolution and adhesion. From the viewpoint of easy obtaining of excellent resolution and adhesion, d33 may be 0, 1, 2 or 3, or may be 0.
Examples of the distyrylbenzene compound include distyrylbenzene and dicyanodistyrylbenzene compounds. Examples of the dicyanostilbene compound include 4' - (2-cyanostyrene) -2-stilbene carbonitrile, 4' - (2-cyanostyrene) -3-stilbene carbonitrile, 4' - (2-cyanostyrene) -4-stilbene carbonitrile, and 1, 4-bis (4-cyanostyrene) benzene. The distyrylbenzene compound may contain dicyanodistyrylbenzene compound or 4' - (2-cyanostyrene) -3-distyrene carbonitrile from the viewpoint of easy obtaining of excellent resolution and adhesion.
The content D1 may be in the following range from the viewpoint of easily obtaining excellent resolution and adhesion, and the content of the component (D) (the total amount of the anthracene compound, the pyrazoline compound, and the distyrylbenzene compound, the same as described below), the content of the anthracene compound, the content of the pyrazoline compound, or the content of the distyrylbenzene compound may be based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content). The content D1 may be 0.01 mass% or more, 0.05 mass% or more, 0.1 mass% or more, 0.2 mass% or more, 0.25 mass% or more, 0.3 mass% or more, 0.4 mass% or more, 0.5 mass% or more, or 0.6 mass% or more. The content D1 may be 5 mass% or less, 3 mass% or less, 1 mass% or less, 0.8 mass% or less, 0.7 mass% or less, 0.6 mass% or less, 0.5 mass% or less, 0.4 mass% or less, 0.3 mass% or less, or 0.25 mass% or less. From these viewpoints, the content D1 may be 0.01 to 5 mass% or 0.1 to 1 mass%.
The content D2 may be in the following range from the viewpoint of easily obtaining excellent resolution and adhesion, and the content of the component (D), the content of the anthracene compound, the content of the pyrazoline compound, or the content of the distyrylbenzene compound may be in the range with respect to 100 parts by mass of the total of the component (a) and the component (B). The content D2 may be 0.01 part by mass or more, 0.05 part by mass or more, 0.1 part by mass or more, 0.2 part by mass or more, 0.25 part by mass or more, 0.3 part by mass or more, 0.4 part by mass or more, 0.5 part by mass or more, 0.6 part by mass or more, or 0.65 part by mass or more. The content D2 may be 5 parts by mass or less, 3 parts by mass or less, 1 part by mass or less, 0.8 parts by mass or less, 0.7 parts by mass or less, 0.65 parts by mass or less, 0.6 parts by mass or less, 0.5 parts by mass or less, 0.4 parts by mass or less, 0.3 parts by mass or less, or 0.25 parts by mass or less. From these viewpoints, the content D2 may be 0.01 to 5 parts by mass or 0.1 to 1 part by mass.
The content D3 may be in the following range with respect to 100 parts by mass of the component (a) from the viewpoint of easily obtaining excellent resolution and adhesion. The content D3 may be 0.1 part by mass or more, 0.3 part by mass or more, 0.4 part by mass or more, 0.5 part by mass or more, 0.8 part by mass or more, 1 part by mass or more, more than 1 part by mass or 1.1 part by mass or more. The content D3 may be 10 parts by mass or less, 8 parts by mass or less, 5 parts by mass or less, 3 parts by mass or less, 2 parts by mass or less, 1.5 parts by mass or less, 1.2 parts by mass or less, 1.1 parts by mass or less, 1 part by mass or less, less than 1 part by mass, 0.8 parts by mass or less, or 0.5 parts by mass or less. From these viewpoints, the content D3 may be 0.1 to 10 parts by mass, 0.5 to 5 parts by mass, or 1 to 3 parts by mass.
The photosensitive film and the photosensitive resin composition according to the present embodiment contain a naphthalene compound (a compound having a naphthalene ring) as the component (E). (E) The component (c) can be used as a sensitization aid (photo sensitization aid). The molecular weight of component (E) may be less than 10000.
The naphthalene compound may have a substituent bonded to the naphthalene ring, or may have a substituent bonded to at least one selected from the group consisting of 1-position and 4-position of the naphthalene ring. Examples of the substituent include an alkyl group (an alkyl group having 1 to 20 carbon atoms (acyclic alkyl group), a cycloalkyl group having 5 to 12 carbon atoms, etc.), an aryl group (a phenyl group, an aralkyl group (benzyl group, phenethyl group, etc.), a benzoyl group, a styryl group, etc.), a vinyl group, a hydroxyl group, a carboxyl group, a carboxylate group, an aldehyde group, an alkoxy group (unsubstituted alkoxy group or substituted alkoxy group (hydroxyalkoxy group, etc.), a carbonyl group, an alkoxycarbonyl group, an alkanoyl group (alkanoyl group having 2 to 12 carbon atoms, etc.), an oxycarbonyl group, a carbonyloxy group, an amino group, an epoxy group, a furyl group, a cyano group, a halogeno group (fluoro group, chloro group, bromo group, etc.), a nitro group, an acetyl group, a sulfonyl group, a sulfonamide group, an aryloxy group (phenoxy group, etc.), and the like. The naphthalene compound may have no substituent at positions other than the 1-position and the 4-position of the naphthalene ring.
The naphthalene compound may be a naphthalene compound having no oxazole skeleton. The naphthalene compound may be a different compound from the vinyl naphthalene compound. The naphthalene compound may be a naphthalene compound having no ethylenically unsaturated bond. The naphthalene compound may be a naphthalene compound having no anthracycline.
The number of carbon atoms of the alkoxy group in the naphthalene compound may be in the following range from the viewpoint of easy obtaining of excellent resolution and adhesion. The number of carbon atoms of the alkoxy group may be 1 or more or 2 or more. The number of carbon atoms of the alkoxy group may be 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, 3 or less, or 2 or less. From these viewpoints, the carbon number of the alkoxy group may be 1 to 10.
From the viewpoint of easy obtaining of excellent resolution and adhesion, the naphthalene compound may include a compound represented by the following general formula (e).
[ in formula (e), R e1 R is R e2 Each independently represents a halogeno group, an alkyl group (e.g., an alkyl group having 1 to 8 carbon atoms), an aralkyl group, an alkoxy group or an aryloxy group, R e3 R is R e4 Each independently represents an alkyl group or a glycidyl group, e1 represents an integer of 0 to 2, and e2 represents an integer of 0 to 4. When e1 is 2, there are a plurality of R e1 May be the same or different, and when e2 is 2 or more, a plurality of R's are present e2 May be the same or different.]
In formula (e), R e1 、R e2 、R e3 R is R e4 The alkyl group of (2) may be a C1-9 alkyl group in which an oxygen atom may be substituted. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, 2-hydroxyethyl, 3-hydroxyethyl, 2-hydroxypropyl, 2-methoxyethoxy, 2-ethoxyethoxy, and 2-phenoxyethoxy. At R e1 R is R e2 Examples of the halogenated group include a fluoro group, a chloro group, a bromo group, etc., examples of the aralkyl group include a benzyl group, a phenethyl group, etc., examples of the alkoxy group include a methoxy group, an ethoxy group, etc., and examples of the aryloxy group include a phenoxy group, etc.
Examples of the naphthalene compound include 1-methoxynaphthalene, 1-ethoxynaphthalene, 1-propoxynaphthalene, 1-butoxynaphthalene, 1, 4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1, 4-diethoxynaphthalene, 1, 4-bis (n-propoxynaphthalene), 1, 4-bis (n-butoxynaphthalene, 1, 4-bis (isobutyloxynaphthalene), 1, 4-bis (n-pentyloxy) naphthalene, 1, 4-bis (isopentyloxy) naphthalene, 1, 4-bis (n-hexyloxy) naphthalene, 1, 4-bis (n-heptyloxy) naphthalene, 1, 4-bis (n-octyloxy) naphthalene, 1, 4-bis (2-ethylhexyloxy) naphthalene, 1, 4-bis (n-nonyloxy) naphthalene, 1, 4-dibenzyloxy naphthalene, 1, 4-diphenylethoxynaphthalene, 1, 4-diglycidyl naphthalene, 1, 4-bis (2-methylglycidoxy) naphthalene, 1-hydroxy-2- (2-hydroxyethoxy) naphthalene, and the like.
From the viewpoint of easy availability of excellent resolution and adhesion, the naphthalene compound may include a compound having an alkoxy group bonded to a naphthalene ring (for example, a compound having 2 alkoxy groups bonded to a naphthalene ring), may include a compound having an alkoxy group bonded to at least one selected from the group consisting of 1-and 4-positions of a naphthalene ring, may include at least one selected from the group consisting of 1, 4-dimethoxynaphthalene and 1, 4-diethoxynaphthalene, and may include 1, 4-diethoxynaphthalene.
(E) The content of the component (c) may be in the following range based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total amount of solid content). From the viewpoint of easy obtaining of excellent adhesion and sensitivity, the content of the component (E) may be 0.01 mass% or more, 0.05 mass% or more, 0.1 mass% or more, 0.15 mass% or more, 0.19 mass% or more, 0.2 mass% or more, 0.4 mass% or more, 0.5 mass% or more, 0.8 mass% or more, 0.9 mass% or more, 1 mass% or more, 1.5 mass% or more, 2 mass% or more, or 2.3 mass% or more. From the viewpoint of easy obtaining of excellent resolution and adhesion, the content of the component (E) may be 10 mass% or less, 8 mass% or less, 5 mass% or less, 3 mass% or less, 2.5 mass% or less, 2.3 mass% or less, 2 mass% or less, 1.5 mass% or less, 1 mass% or less, 0.9 mass% or less, 0.8 mass% or less, 0.5 mass% or less, 0.4 mass% or 0.2 mass% or less. From these viewpoints, the content of the component (E) may be 0.01 to 10 mass% or 0.1 to 5 mass%.
(E) The content of the component (a) may be within the following range with respect to 100 parts by mass of the total amount of the component (B). The content of the component (E) may be 0.01 part by mass or more, 0.05 part by mass or more, 0.1 part by mass or more, 0.15 part by mass or more, 0.2 part by mass or more, 0.3 part by mass or more, 0.5 part by mass or more, 0.8 part by mass or more, 1 part by mass or more, 1.5 part by mass or more, 2 parts by mass or more, 2.5 parts by mass or more, or 2.6 parts by mass or more, from the viewpoint of easy obtaining of excellent adhesion and sensitivity. The content of the component (E) may be 10 parts by mass or less, 5 parts by mass or less, 3 parts by mass or less, 2.6 parts by mass or less, 2.5 parts by mass or less, 2 parts by mass or less, 1.5 parts by mass or less, 1 part by mass or less, 0.8 parts by mass or less, 0.5 parts by mass or less, 0.3 parts by mass or 0.2 parts by mass or less, from the viewpoint of easy obtaining of excellent resolution and adhesion. From these viewpoints, the content of the component (E) may be 0.01 to 10 parts by mass or 0.1 to 5 parts by mass.
(E) The content of the component (c) may be within the following range with respect to 100 parts by mass of the component (D). The content of the component (E) may be 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, 70 parts by mass or more, 80 parts by mass or more, 90 parts by mass or more, 100 parts by mass or more, 150 parts by mass or more, 200 parts by mass or more, 300 parts by mass or more, or 400 parts by mass or more from the viewpoint of easy obtaining of excellent adhesion and sensitivity. The content of the component (E) may be 1000 parts by mass or less, 800 parts by mass or less, 500 parts by mass or less, 400 parts by mass or less, 300 parts by mass or less, 200 parts by mass or less, 150 parts by mass or less, 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 50 parts by mass or 40 parts by mass or less, from the viewpoint of easy obtaining of excellent resolution and adhesion. From these viewpoints, the content of the component (E) may be 1 to 1000 parts by mass or 10 to 500 parts by mass.
The photosensitive film and the photosensitive resin composition according to the present embodiment may contain a polymerization inhibitor (excluding compounds corresponding to any of the components (a) to (E)) as the component (F). (F) The composition suppresses polymerization of the unexposed portion when forming the resist pattern, and easily improves resolution. Examples of the polymerization inhibitor include t-butylcatechol (e.g., 4-t-butylcatechol), hindered amine (e.g., 2, 6-tetramethyl-4-hydroxypiperidine-1-oxy), and 4-hydroxy-2, 6-tetramethylpiperidine-N-oxy.
(F) The content of the component (a) may be within the following range with respect to 100 parts by mass of the total amount of the component (B). The content of the component (F) may be 0.001 parts by mass or more, 0.003 parts by mass or more, 0.005 parts by mass or more, 0.01 parts by mass or more, or 0.015 parts by mass or more from the viewpoint of easy obtaining of excellent resolution and adhesion. The content of the component (F) may be 0.1 part by mass or less, 0.05 part by mass or less, 0.04 part by mass or less, 0.03 part by mass or less, or 0.02 part by mass or less from the viewpoint of easy achievement of excellent resolution and adhesion. From these viewpoints, the content of the component (F) may be 0.001 to 0.1 part by mass.
The photosensitive resin composition according to the present embodiment may contain an organic solvent. Examples of the organic solvent include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N-dimethylformamide, propylene glycol monomethyl ether, and the like.
The photosensitive film and the photosensitive resin composition according to the present embodiment may contain other components (excluding compounds corresponding to any of the components (a) to (E)) than the above components. Examples of the other component include hydrogen donors (bis [4- (dimethylamino) phenyl ] methane, bis [4- (diethylamino) phenyl ] methane, leuco crystal violet, N-phenylglycine, etc.), dyes (malachite green, etc.), sensitizers, tribromophenyl sulfone, photocolor-developing agents, thermal color-developing inhibitors, plasticizers (p-toluenesulfonamide, etc.), pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion-imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc.
In the photosensitive film and the photosensitive resin composition according to the present embodiment, the content of the thermal radical polymerization initiator may be 0.5 mass% or less, less than 0.5 mass%, 0.1 mass% or less, 0.01 mass% or less, or 0.001 mass% or less based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content). The photosensitive film and the photosensitive resin composition according to the present embodiment may contain no thermal radical polymerization initiator (the content may be substantially 0 mass%).
In the photosensitive film and the photosensitive resin composition according to the present embodiment, the content of at least one selected from the group consisting of a vinyl polymer (for example, a vinyl polymer having a side chain having an epoxy group) and an oxetane compound (for example, an oxetane compound having 2 or more oxetane rings which may have a substituent) may be 20 mass% or less, less than 20 mass%, 10 mass% or less, 1 mass% or less, 0.1 mass% or less, 0.01 mass% or 0.001 mass% or less based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content). The photosensitive film and the photosensitive resin composition according to the present embodiment may contain no at least one (the content may be substantially 0 mass%) selected from the group consisting of a vinyl polymer (e.g., a vinyl polymer having a side chain having an epoxy group) and an oxetane compound (e.g., an oxetane compound having 2 or more oxetane rings which may have a substituent).
In the photosensitive film and the photosensitive resin composition according to the present embodiment, the content of the copolymer having an epoxy group and a carboxyl group may be 20 mass% or less, less than 20 mass%, 10 mass% or less, 1 mass% or less, 0.1 mass% or less, or 0.01 mass% or less based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content). The photosensitive film and the photosensitive resin composition according to the present embodiment may not contain a copolymer having an epoxy group and a carboxyl group (the content may be substantially 0 mass%).
In the photosensitive film and the photosensitive resin composition according to the present embodiment, the content of the aromatic iodide salt may be 0.5 mass% or less, less than 0.5 mass%, 0.1 mass% or less, 0.01 mass% or less, or 0.001 mass% or less based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content). The photosensitive film and the photosensitive resin composition according to the present embodiment may contain no aromatic iodinated salt (the content may be substantially 0 mass%).
In the photosensitive film and the photosensitive resin composition according to the present embodiment, the content of the resin having a phenolic hydroxyl group or the content of the novolak resin having a phenolic hydroxyl group may be 30 mass% or less, less than 30 mass%, 15 mass% or less, less than 15 mass%, 10 mass% or less, 1 mass% or less, 0.1 mass% or less, or 0.01 mass% or less, based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content). The photosensitive film and the photosensitive resin composition according to the present embodiment may contain no resin having a phenolic hydroxyl group (the content may be substantially 0 mass%) or may contain no novolak resin having a phenolic hydroxyl group (the content may be substantially 0 mass%).
In the photosensitive film and the photosensitive resin composition according to the present embodiment, the content of the epoxy compound having 2 or more oxirane rings or the content of the aliphatic or alicyclic epoxy compound having 2 or more oxirane rings may be 40 parts by mass or less, less than 40 parts by mass, 20 parts by mass or less, less than 20 parts by mass, 10 parts by mass or less, less than 10 parts by mass, 1 part by mass or less, 0.1 part by mass or 0.01 part by mass or less with respect to 100 parts by mass of the component (a). The photosensitive film and the photosensitive resin composition according to the present embodiment may contain no epoxy compound having 2 or more oxirane rings (the content may be substantially 0 parts by mass), or may contain no aliphatic or alicyclic epoxy compound having 2 or more oxirane rings (the content may be substantially 0 parts by mass).
The photosensitive film and the photosensitive resin composition according to the present embodiment may contain no polymerizable compound having a cyclic aliphatic group (the content of the polymerizable compound may be substantially 0 mass% based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content)).
In the photosensitive film and the photosensitive resin composition according to the present embodiment, the total amount of the onium borate and the onium gallate may be 0.1 part by mass or less, less than 0.1 part by mass, 0.01 part by mass or less, or 0.001 part by mass or less, based on 100 parts by mass of the component (a). The photosensitive film and the photosensitive resin composition according to the present embodiment may contain no onium borate or onium gallate (the total amount may be substantially 0 parts by mass).
In the photosensitive film and the photosensitive resin composition according to the present embodiment, the content of the multifunctional epoxy resin may be 75 mass% or less, less than 75 mass%, 50 mass% or less, 10 mass% or less, 1 mass% or less, 0.1 mass% or less, or 0.01 mass% or less based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content). The photosensitive film and the photosensitive resin composition according to the present embodiment may not contain a polyfunctional epoxy resin (the content may be substantially 0 mass%).
The photosensitive film and the photosensitive resin composition according to the present embodiment may be free of polyimide having at least one selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and a thiol group (the content of the polyimide may be substantially 0 mass% based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content)).
In the photosensitive film and the photosensitive resin composition according to the present embodiment, the content of the mercapto compound may be 0.001 parts by mass or less, less than 0.001 parts by mass, 0.0001 parts by mass or less, or 0.00001 parts by mass or less, based on 100 parts by mass of the total of the component (a) and the component (B). The photosensitive film and the photosensitive resin composition according to the present embodiment may contain no thiol-group-containing compound (the content may be substantially 0 parts by mass).
In the photosensitive film and the photosensitive resin composition according to the present embodiment, the content of the bisphenol F type (meth) acrylic compound (the (meth) acrylic compound having a bisphenol F structure) or the content of the bisphenol F type acrylic compound may be 5 mass% or less, less than 5 mass%, 1 mass% or less, less than 1 mass%, 0.1 mass% or less, 0.01 mass% or 0.001 mass% or less based on the total mass of the component (B). In the photosensitive film and the photosensitive resin composition according to the present embodiment, the content of the bisphenol F type (meth) acrylic compound or the content of the bisphenol F type acrylic compound may be 0.2 mass% or less, 0.15 mass% or less, less than 0.15 mass%, 0.1 mass% or less, or 0.01 mass% or less based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content). The photosensitive film and the photosensitive resin composition according to the present embodiment may contain no bisphenol F type (meth) acrylic compound (the content of each may be substantially 0 mass%), or may contain no bisphenol F type acrylic compound (the content of each may be substantially 0 mass%).
In the photosensitive film and the photosensitive resin composition according to the present embodiment, the content (total solid content) of the components other than the component (a) and the component (B) may be 15 parts by mass or more, 19 parts by mass or more, more than 19 parts by mass, 20 parts by mass or more, 21 parts by mass or more, 22 parts by mass or more, or 23 parts by mass or more, based on 100 parts by mass of the component (B).
The photosensitive film and the photosensitive resin composition according to the present embodiment may contain no polymer having a nitrogen-containing group (the content of the polymer having a nitrogen-containing group may be substantially 0 mass% based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content)).
In the photosensitive film and the photosensitive resin composition according to the present embodiment, the content of the acridine compound (compound having an acridine ring) may be 0.1 mass% or less, less than 0.1 mass%, 0.01 mass% or less, or 0.001 mass% or less based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content). The photosensitive film and the photosensitive resin composition according to the present embodiment may contain no acridine compound (the content may be substantially 0 mass%).
< photosensitive element >)
The photosensitive element according to the present embodiment includes a support and a photosensitive resin layer disposed on the support, and the photosensitive resin layer is the photosensitive film according to the present embodiment. The photosensitive element according to the present embodiment may include a protective layer disposed on the photosensitive resin layer. The photosensitive element according to the present embodiment may include a buffer layer, an adhesive layer, a light absorbing layer, a gas barrier layer, and the like. The photosensitive element may be sheet-shaped or may be wound in a roll around a core.
Fig. 1 is a schematic cross-sectional view showing an example of a photosensitive element. As shown in fig. 1, the photosensitive element 1 includes a support (support film) 2, a photosensitive resin layer (photosensitive film) 3 disposed on the support 2, and a protective layer (protective film) 4 disposed on the photosensitive resin layer 3. The photosensitive resin layer 3 is composed of the photosensitive resin composition according to the present embodiment.
The photosensitive element 1 can be obtained, for example, by the following steps. First, the photosensitive resin layer 3 is formed on the support 2. The photosensitive resin layer 3 can be formed by, for example, drying a coating layer formed by coating a photosensitive resin composition containing an organic solvent. Next, a protective layer 4 is disposed on the photosensitive resin layer 3.
The support and the protective layer may be polymer films having heat resistance and solvent resistance, or may be polyester films (polyethylene terephthalate films, etc.), polyolefin films (polyethylene films, polypropylene films, etc.), hydrocarbon polymers (excluding polyolefin films), etc. The type of film constituting the protective layer may be the same as or different from the type of film constituting the support.
The thickness of the support may be 1 μm or more, 5 μm or more, 10 μm or more, or 15 μm or more from the viewpoint of easily suppressing breakage of the support when the support is peeled from the photosensitive resin layer. The thickness of the support may be 100 μm or less, 50 μm or less, 30 μm or less, or 20 μm or less from the viewpoint of ease of proper exposure when exposure is performed through the support.
The thickness of the protective layer may be 1 μm or more, 5 μm or more, 10 μm or more, or 15 μm or more from the viewpoint of easily suppressing the peeling of the protective layer and breakage of the protective layer when the photosensitive resin layer and the support are laminated on the substrate. The thickness of the protective layer may be 100 μm or less, 50 μm or less, or 30 μm or less from the viewpoint of easy improvement of productivity.
Method for producing laminate
The method for manufacturing a laminate according to the present embodiment includes: a photosensitive resin layer arrangement step of arranging a photosensitive resin layer on a base material (for example, a substrate) using the photosensitive element or the photosensitive resin composition according to the present embodiment; an exposure step of photocuring (exposing) a part of the photosensitive resin layer; a developing step of removing at least a part of an uncured portion (unexposed portion) of the photosensitive resin layer to form a cured pattern; and a metal layer forming step of forming a metal layer on at least a part of the portion of the base material where the cured product pattern is not formed. The laminate according to the present embodiment may be a wiring board (e.g., a printed wiring board) obtained by the method for manufacturing a laminate according to the present embodiment. The laminate according to the present embodiment may be a laminate including a substrate, a cured product pattern (cured product according to the present embodiment) disposed on the substrate, and a metal layer disposed on at least a part of a portion of the substrate where the cured product pattern is not formed.
In the photosensitive resin layer arrangement step, a photosensitive resin layer composed of the photosensitive resin composition according to the present embodiment is arranged on a substrate. For example, the photosensitive resin layer may be formed by heating and pressing the photosensitive resin layer of the photosensitive element to the substrate after removing the protective layer from the photosensitive element, or may be formed by applying and drying the photosensitive resin composition on the substrate.
In the exposure step, the photosensitive resin layer may be irradiated with an active light beam in a state where a mask is disposed thereon, and the region other than the region where the mask is disposed in the photosensitive resin layer may be exposed to light for curing, or a part of the photosensitive resin layer may be exposed to light for curing by irradiation of an active light beam in a desired pattern by a direct drawing exposure method such as an LDI exposure method or a DLP exposure method without using a mask. As the light source of the active light, an ultraviolet light source or a visible light source may be used, and examples thereof include a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, a xenon lamp, a gas laser (such as an argon laser), a solid-state laser (such as a YAG laser), and a semiconductor laser.
The developing method in the developing step may be, for example, wet developing or dry developing. Wet development can be performed by, for example, immersion, paddle (paddle), spray, brush (brushing), slapping (sliding), doctor blade (scraping), shaking, or the like using a developer corresponding to the photosensitive resin composition. The developer is appropriately selected according to the composition of the photosensitive resin composition, and may be an alkali developer or an organic solvent developer.
The alkali developer may be an alkali hydroxide including a hydroxide of lithium, sodium or potassium; alkali carbonates such as lithium, sodium, potassium or ammonium carbonates or bicarbonates; alkali metal phosphates such as potassium phosphate and sodium phosphate; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; borax; sodium metasilicate; tetramethyl ammonium hydroxide; ethanolamine; ethylenediamine; diethylenetriamine; 2-amino-2-hydroxymethyl-1, 3-propanediol; 1, 3-diamino-2-propanol; aqueous solutions of bases such as morpholine.
The organic solvent developer may contain 1, 1-trichloroethane, N-methylpyrrolidone, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, gamma-butyrolactone and other organic solvents.
The metal layer in the metal layer forming step may be, for example, a metal copper layer. The metal layer can be formed by, for example, performing a plating process. The plating treatment may be one or both of an electrolytic plating treatment and an electroless plating treatment.
The method for producing a laminate according to the present embodiment comprises heating at 60 to 250 ℃ or heating at 0.2 to 10J/cm after a developing step 2 Further curing the resist pattern by exposure to light.
The method for manufacturing a laminate according to the present embodiment may include a step of removing the cured product pattern after the metal layer forming step. The cured product pattern can be removed by, for example, development using a strong alkaline aqueous solution by dipping, spraying, or the like.
Fig. 2 is a schematic diagram showing an example of a method for manufacturing a laminate (a method for manufacturing a wiring board). In an example of a method for producing a laminate, first, as shown in fig. 2 (a), a base material (e.g., a circuit-forming substrate) 10 including an insulating layer 10a and a conductor layer 10b disposed on the insulating layer 10a is prepared. The conductor layer 10b may be, for example, a metallic copper layer.
Next, as shown in fig. 2 b, a photosensitive resin layer 12 is disposed on the conductor layer 10b of the base material 10 (photosensitive resin layer disposing step). In the photosensitive resin layer disposing step, the photosensitive element or the photosensitive resin composition according to the present embodiment is used to dispose the photosensitive resin layer 12 on the conductor layer 10b of the base material 10.
Next, as shown in fig. 2 (c), the active light L is irradiated in a state where the mask 14 is disposed on the photosensitive resin layer 12, and the region of the photosensitive resin layer 12 other than the region where the mask 14 is disposed is exposed to light to be cured.
Next, after removing the mask 14, as shown in fig. 2 d, the region (uncured portion) other than the photo-cured portion in the photosensitive resin layer is removed from the substrate 10 by development, thereby forming a resist pattern 12a composed of the photo-cured portion (cured product of the photosensitive resin layer).
Next, as shown in fig. 2 (e), a wiring layer (metal layer) 16 is formed on the conductor layer 10b of the base material 10 at a portion where the resist pattern 12a is not formed. The wiring layer 16 may be formed of the same kind of material as the conductor layer 10b, or may be formed of a different kind of material.
Next, as shown in fig. 2 (f), the resist pattern 12a is removed, and the conductor layer 10b provided at a position corresponding to the resist pattern 12a is removed, thereby forming a conductor layer 10c. Thus, the wiring board 18 including the conductor layer 10c and the wiring layer 16 disposed on the insulating layer 10a can be obtained. The conductor layer 10b can be removed by etching treatment. The etching liquid is appropriately selected according to the type of the conductor layer 10b, and may be, for example, a copper chloride solution, an iron chloride solution, an alkali etching solution, a hydrogen peroxide etching solution, or the like.
Examples
Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.
< Synthesis of adhesive Polymer >
The solution (a) was prepared by mixing 27 parts by mass of methacrylic acid, 3 parts by mass of 2-hydroxyethyl methacrylate, 20 parts by mass of benzyl methacrylate, 50 parts by mass of styrene and 0.9 part by mass of azobisisobutyronitrile. The solution (b) was prepared by dissolving 0.5 part by mass of azobisisobutyronitrile in 50 parts by mass of a mixed solution of 30 parts by mass of methyl cellosolve and 20 parts by mass of toluene. 500g of a mixture of 30 parts by mass of methyl cellosolve and 20 parts by mass of toluene was charged into a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen inlet tube, and then nitrogen was blown into the flask and stirred, and the temperature was raised to 80 ℃. After the solution (a) was added dropwise to the above flask at a constant dropping rate over 4 hours, the solution in the flask was stirred at 80℃for 2 hours. Then, the solution (b) was added dropwise to the flask over 10 minutes at a constant dropping rate, and the solution in the flask was stirred at 80℃for 3 hours. Further, the solution in the flask was heated to 90℃over 30 minutes, and after keeping the temperature at 90℃for 2 hours, stirring was stopped, and the solution was cooled to room temperature (25 ℃) to obtain a solution of the binder polymer. The nonvolatile content (solid content) of the binder polymer solution was 49 mass%.
The acid value of the binder polymer was 176mgKOH/g. The acid value was measured by the following procedure. First, the binder polymer was weighed in an Erlenmeyer flask. Next, a mixed solvent (mass ratio: toluene/methanol=70/30) was added and the binder polymer was dissolved, and then a phenolphthalein solution was added as an indicator. Then, the acid value was obtained by titration using 0.1mol/L (N/10) potassium hydroxide solution (ethanol solution).
The weight average molecular weight (Mw) of the binder polymer was 35000 and the number average molecular weight (Mn) was 16000. The weight average molecular weight and the number average molecular weight were determined by Gel Permeation Chromatography (GPC) under the following conditions, and converted using a calibration curve of standard polystyrene.
(GPC conditions)
And (3) a pump: hitachi L-6000 type (Hitachi, ltd. Product name)
Column: the following total 3 roots (Showa Denko Materials co., ltd. Product name)
Gelpack GL-R440
Gelpack GL-R450
Gelpack GL-R400M
Eluent: tetrahydrofuran (THF)
Measuring temperature: 40 DEG C
Injection amount: 200 mu L
Flow rate: 2.05 mL/min
A detector: hitachi L-3300 RI (Hitachi, ltd. Product name)
Preparation of photosensitive resin composition
Example 1
By mixing the above-mentioned binder polymer solution (binder polymer (non-volatile component): 56 parts by mass), 2-bis (4- (methacryloxypentaethoxy) phenyl) propane (EO average 10mol adduct, molecular weight: 804) 35 parts by mass of propylene glycol monomethyl ether (Showa Denko Materials Co., ltd., product name: FA-321M), 6 parts by mass of 2, 2-bis (4- (methacryloxypolyethoxy) phenyl) propane (EO base: 2.6 (total), molecular weight: 478, KYOEISHA CHEMICAL CO., LTD., product name: BP-2 EM) 5 parts by mass, (PO) (EO) (PO) modified dimethacrylate (EO average 6mol and PO average 12mol adduct (total), molecular weight: 1114, showa Denko Materials Co., ltd., product name: FA-024M), 6 parts by mass of photopolymerization initiator (2, 2 '-bis (o-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -bisimidazole, manufactured by Co., BCIM, hampford), 0.650 parts by mass of sensitizer A1 (9, 10-dibutoxyanthracene, DBA, manufactured by KAWASAKI KASEI CHEMICALS), 0.650 parts by mass of sensitizer A (1, 4-diethoxynaphthalene, KAWASAKI KASEI CHEMICALS, product name: FA-024M), 0.2170 parts by mass of crystallization inhibitor, DIC (DIC) 0.015 parts by mass, 6 parts by mass of crystal inhibitor (DIC), 0.015 parts by mass of crystal-violet, 3, product name: DIC, 3, 6 parts by mass of crystal-violet (DIC) and 3.015 parts by mass of the product name: DIC A photosensitive resin composition was prepared from 0.02 part by mass of a dye (manufactured by malachite green, MKG, OSAKA ORGANIC CHEMICAL INDUSTRY LTD. Co.), 0.5 part by mass of an additive (a mixture of carboxybenzotriazole, 5-amino-1H-tetrazole, and methoxypropanol; manufactured by SANWA KASEI CORP. Co., ltd., product name: SF-808H), 16 parts by mass of toluene, 6 parts by mass of methanol, and 10 parts by mass of acetone.
Examples 2 to 4
A photosensitive resin composition was prepared in the same manner as in example 1 except that the amount of the sensitizer a used was changed to the amount shown in table 1.
Example 5
A photosensitive resin composition was prepared in the same manner as in example 1 except that the sensitization aid a was changed to the sensitization aid B (1, 4-dimethoxynaphthalene, FUJIFILM Wako Pure Chemical Corporation).
Example 6
A photosensitive resin composition was prepared in the same manner as in example 1 except that the sensitizer A1 was changed to sensitizer A2 (9, 10-dipropoxyanthracene).
Example 7
A photosensitive resin composition was prepared in the same manner as in example 1 except that 0.650 parts by mass of sensitizer A1 was changed to 0.234 parts by mass of sensitizer B1 (1-phenyl-3- (4-methoxyphenyl) -5- (4-methoxyphenyl) -pyrazoline, nippon Chemical Industry co., ltd., product name: PZ-501D).
Example 8
A photosensitive resin composition was produced in the same manner as in example 7 except that the sensitizer a was changed to the sensitizer B.
Example 9
A photosensitive resin composition was produced in the same manner as in example 1 except that 0.650 parts by mass of sensitizer A1 was changed to 0.400 parts by mass of sensitizer B2 (4- [ [3- (4-chlorophenyl) -4, 5-dihydro-1H-pyrazol ] -1-yl ] benzenesulfonamide, tanatex Chemicals BV, product name: blankophor MAN 01).
Example 10
A photosensitive resin composition was prepared in the same manner as in example 1 except that sensitizer A1 was changed to sensitizer C (4' - (2-cyanostyrene) -3-diphenylvinylcarbonitrile, manufactured by BOC Sciences, product name: fluorescent Brightener ER-III).
Comparative example 1
A photosensitive resin composition was prepared in the same manner as in example 1, except that the sensitization auxiliary a was not used.
Comparative example 2
A photosensitive resin composition was prepared in the same manner as in example 7 except that the sensitization auxiliary a was not used.
Comparative example 3
A photosensitive resin composition was prepared in the same manner as in example 9, except that the sensitization auxiliary a was not used.
Comparative example 4
A photosensitive resin composition was prepared in the same manner as in example 10, except that the sensitization auxiliary a was not used.
< production of photosensitive element >)
A polyethylene terephthalate film (product name "FB-40" manufactured by TORAY INDUSTRIES, INC.) having a thickness of 16 μm was prepared as a support. The photosensitive resin composition was applied to a support to have a uniform thickness, and then dried by a hot air convection dryer at 70℃and 110℃in this order, whereby a photosensitive resin layer (photosensitive film, thickness after drying: 19 μm) was formed. A polyethylene film (tamopoly co., ltd. Product name "NF-15") was bonded to the photosensitive resin layer as a protective layer, thereby obtaining a photosensitive element having a support, a photosensitive resin layer, and a protective layer in this order.
< evaluation >
(evaluation of absorbance)
The absorbance (Abs) at a wavelength of 405nm was measured in the photosensitive resin layer of the photosensitive element using an ultraviolet-visible Spectrophotometer (manufactured by Hitachi High-Technologies Corporation, product name: U-3310 Spectrophotometer). Polyethylene terephthalate film and polyethylene film were used as references. The results are shown in table 1.
(production of laminate)
Copper-clad laminated sheets (substrate, showa Denko Materials Co., ltd., product name: MCL-E-67) comprising copper foils (thickness: 18 μm) disposed on both sides of a glass epoxy material were subjected to acid washing and water washing, and then dried with an air stream. Next, after the copper-clad laminate was heated to 80 ℃, the protective layer was peeled off and the photosensitive element was laminated so that the photosensitive resin layer was in contact with the copper surface, thereby obtaining a laminate comprising the copper-clad laminate, the photosensitive resin layer, and the support in this order. Lamination was performed using a 110℃heated roll and a roll speed of 1.5 m/min at a crimping pressure of 0.4 MPa.
(evaluation of sensitivity)
After a 41-stage step plate (Showa Denko Materials Co., ltd.) was placed on the support of the laminate, the photosensitive resin layer was exposed to light through the support by a direct-write exposure machine (Via Mechanics, ltd., product name: DE-1 UH) using a blue-violet laser diode having a wavelength of 405nm as a light source, with the number of remaining steps after development of the 41-stage step plate being 15-stage exposure (irradiation energy). By the exposure amount (unit: mJ/cm) 2 ) Sensitivity (light sensitivity) was evaluated. The results are shown in table 1. The smaller the exposure amount, the better the sensitivity.
(evaluation of resolution)
After a 41-stage step plate (Showa Denko Materials co., ltd.) was placed on the support of the laminate, a direct-writing exposure machine (Via Mechanics, ltd., product name: DE-1 UH) using a blue-violet laser diode having a wavelength of 405nm as a light source was used to expose (draw) the photosensitive resin layer through the support without performing Offset, using a drawing pattern having a line width (L)/space width (S) (hereinafter, referred to as "L/S") of 3x/x (x=1 to 20, units: μm, 1 μm interval), with an exposure amount (irradiation energy) having a residual number of 15 stages after the development of the 41-stage step plate. Post-Exposure heating (PEB: post-Exposure-Bake) was performed at 80℃for 30 seconds using a heating oven for less than 3 minutes after Exposure.
After exposure, the support was peeled off from the laminate to expose the photosensitive resin layer, and a 1 mass% aqueous sodium carbonate solution was sprayed at 30 ℃ for a time 2 times the minimum development time, thereby removing the unexposed portion. After development, the resolution was evaluated by the minimum value (unit: μm) in the space width in the resist pattern in which the space portion (unexposed portion) was removed without residue and the line portion (exposed portion) was formed without meandering and deficiency. The results are shown in table 1. The smaller the value, the better the resolution.
The minimum development time was evaluated in advance by the following steps. First, the laminate was cut into square shapes (5 cm×5 cm), and then the support was peeled off, whereby a test piece was obtained. Subsequently, the unexposed photosensitive resin layer in the test piece was subjected to spray development using a 1 mass% aqueous sodium carbonate solution at 30℃under a pressure of 0.15MPa, and the shortest time in which the unexposed photosensitive resin layer was visually confirmed to be removed was obtained as the minimum development time (MD). The nozzle uses a full cone shape. The distance between the test piece and the tip of the nozzle was 6cm, and the center of the test piece was aligned with the center of the nozzle.
(evaluation of adhesion)
After a 41-level step plate (Showa Denko Materials Co., ltd.) was placed on the support of the laminate, a direct-write exposure machine (Via Mechanics, ltd., product name: DE-1 UH) using a blue-violet laser diode having a wavelength of 405nm as a light source was used to expose (draw) the photosensitive resin layer through the support without performing Offset with an exposure (irradiation energy) having a residual number of 15-level after development of the 41-level step plate, using a drawing pattern having an L/S of x/3x (x=1 to 20, unit: μm, 1 μm interval). Post-Exposure heating (PEB: post-Exposure-Bake) was performed at 80℃for 30 seconds using a heating oven for less than 3 minutes after Exposure.
After exposure, the support was peeled off from the laminate to expose the photosensitive resin layer, and a 1 mass% aqueous sodium carbonate solution was sprayed at 30 ℃ for a time 2 times the minimum development time, thereby removing the unexposed portion. After development, adhesion was evaluated by the minimum value (unit: μm) of line widths in the resist pattern in which the space portion (unexposed portion) was removed without residue and the line portion (exposed portion) was formed without meandering and defects. The results are shown in table 1. The smaller the number, the better the adhesion.
TABLE 1
Symbol description
1-photosensitive element, 2-support, 3, 12-photosensitive resin layer, 4-protective layer, 10-substrate, 10 a-insulating layer, 10b,10 c-conductor layer, 12 a-resist pattern, 14-mask, 16-wiring layer, 18-wiring substrate, L-active light.

Claims (17)

1. A photosensitive film, comprising:
(A) A binder polymer;
(B) A photopolymerizable compound;
(C) A photopolymerization initiator;
(D) At least one selected from the group consisting of an anthracene compound, a pyrazoline compound, and a distyrylbenzene compound; and
(E) Naphthalene compounds.
2. The photosensitive film according to claim 1, wherein,
the component (A) has an aryl (meth) acrylate and a styrene compound as monomer units.
3. The photosensitive film according to claim 1 or 2, wherein,
the content of the monomer units of the styrene compound in the component (A) is 40 mass% or more based on the total amount of the monomer units constituting the component (A).
4. The photosensitive film according to any one of claim 1 to 3, wherein,
the weight average molecular weight of the component (A) is 20000 to 50000.
5. The photosensitive film according to any one of claims 1 to 4, wherein,
the component (B) contains a bisphenol A type (meth) acrylic compound.
6. The photosensitive film according to any one of claims 1 to 5, wherein,
the component (B) contains a (meth) acrylic compound having a polyoxyalkylene group.
7. The photosensitive film according to any one of claims 1 to 6, wherein,
the content of the component (B) is 30 to 60 parts by mass based on 100 parts by mass of the total amount of the component (A) and the component (B).
8. The photosensitive film according to any one of claims 1 to 7, wherein,
the component (D) contains an anthracene compound,
the content of the anthracene compound having an unsubstituted alkoxy group bonded to 9 and 10 positions of the anthracycline is 50 to 100% by mass based on the total mass of the anthracene compound.
9. The photosensitive film according to claim 8, wherein,
the component (D) contains no anthracene compound other than an anthracene compound having an unsubstituted alkoxy group bonded to the 9-and 10-positions of the anthracycline.
10. The photosensitive film according to any one of claims 1 to 9, wherein,
the component (D) contains a compound having 2 or more aryl groups bonded to a pyrazoline ring.
11. The photosensitive film according to any one of claims 1 to 10, wherein,
the (D) component contains a dicyanostilbene benzene compound.
12. The photosensitive film according to any one of claims 1 to 11, wherein,
the content of the component (D) is 0.1 to 1 part by mass based on 100 parts by mass of the total amount of the component (A) and the component (B).
13. The photosensitive film according to any one of claims 1 to 12, wherein,
the (E) component comprises a compound having 2 alkoxy groups bonded to a naphthalene ring.
14. The photosensitive film according to any one of claims 1 to 13, wherein,
the content of the component (E) is 0.1 to 5 parts by mass relative to 100 parts by mass of the total amount of the component (A) and the component (B).
15. The photosensitive film according to any one of claims 1 to 14, wherein,
The content of the component (E) is 10 to 500 parts by mass based on 100 parts by mass of the component (D).
16. A photosensitive element comprising a support and a photosensitive resin layer disposed on the support,
the photosensitive resin layer is the photosensitive film according to any one of claims 1 to 15.
17. A method for producing a laminate, comprising:
a step of disposing a photosensitive resin layer on a substrate using the photosensitive film according to any one of claims 1 to 15;
a step of photocuring a part of the photosensitive resin layer;
removing at least a part of the uncured portion of the photosensitive resin layer to form a cured pattern; and
And forming a metal layer on at least a part of the portion of the base material where the cured product pattern is not formed.
CN202280003948.5A 2021-03-09 2022-03-07 Photosensitive film, photosensitive element, and method for producing laminate Pending CN117063121A (en)

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