WO2023012985A1 - Photosensitive film, photosensitive element, and method for producing multilayer body - Google Patents
Photosensitive film, photosensitive element, and method for producing multilayer body Download PDFInfo
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- WO2023012985A1 WO2023012985A1 PCT/JP2021/029189 JP2021029189W WO2023012985A1 WO 2023012985 A1 WO2023012985 A1 WO 2023012985A1 JP 2021029189 W JP2021029189 W JP 2021029189W WO 2023012985 A1 WO2023012985 A1 WO 2023012985A1
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- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- G03F7/027—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
- G03F7/032—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
Definitions
- the present disclosure relates to a photosensitive film, a photosensitive element, a laminate manufacturing method, and the like.
- a resist pattern is formed to obtain desired wiring.
- a resist pattern can be formed by exposing and developing a photosensitive film, which is a film-shaped photosensitive resin composition.
- Various compositions have been studied as the photosensitive resin composition.
- Patent Document 1 describes a photosensitive resin composition containing a binder polymer, a photopolymerizable compound, and a specific photopolymerization initiator.
- the cured product pattern When forming a cured product pattern that can be used as a resist pattern using a photosensitive film, there is a case where the cured product pattern is formed while filling a recess (round hole) having a circular cross section with a photosensitive resin composition. be.
- the cured product pattern is formed with voids in the recesses, and the followability (filling property) to the shape of the recesses may not be sufficient.
- a photosensitive film having a thickness of 25 ⁇ m has been commonly used, there are cases where the thickness of the photosensitive film is required to be reduced to 20 ⁇ m or less for the purpose of reducing the thickness of the laminate.
- the thickness of the photosensitive film is reduced in this way, the amount of the photosensitive resin composition for filling the concave portions is reduced, so that the cured product pattern is likely to be formed with voids in the concave portions. . Therefore, even when the thickness is 20 ⁇ m or less, the photosensitive film is required to have excellent conformability to concave portions having a circular cross section.
- An object of one aspect of the present disclosure is to provide a photosensitive film having a thickness of 20 ⁇ m or less, which has excellent followability to concave portions having a circular cross section. Another aspect of the present disclosure aims to provide a photosensitive element using the photosensitive film. Another aspect of the present disclosure aims to provide a method for producing a laminate using the photosensitive film or photosensitive element described above.
- One aspect of the present disclosure contains (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a pyrazoline compound, and has a thickness of 20 ⁇ m or less. , on photosensitive films.
- Such a photosensitive film has a thickness of 20 ⁇ m or less, it has excellent conformability to recesses having a circular cross section.
- Another aspect of the present disclosure relates to a photosensitive element comprising a support and a photosensitive resin layer disposed on the support, wherein the photosensitive resin layer is the photosensitive film described above.
- Another aspect of the present disclosure includes an arrangement step of arranging a photosensitive resin layer on a substrate using the above-described photosensitive film or the above-described photosensitive element, and photocuring a part of the photosensitive resin layer. and removing at least part of the uncured portion of the photosensitive resin layer to form a cured product pattern.
- a photosensitive film having a thickness of 20 ⁇ m or less it is possible to provide a photosensitive film having excellent followability to concave portions having a circular cross section.
- a photosensitive element using the photosensitive film it is possible to provide a method for producing a laminate using the photosensitive film or photosensitive element described above.
- FIG. 1 is a schematic cross-sectional view showing an example of a photosensitive element
- a or more in the numerical range means A and the range exceeding A.
- a or less in a numerical range means A and a range less than A.
- the upper limit value or lower limit value of the numerical range in one step can be arbitrarily combined with the upper limit value or lower limit of the numerical range in another step.
- the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
- “A or B” may include either A or B, or may include both.
- each component in the composition means the total amount of the plurality of substances present in the composition unless otherwise specified when there are multiple substances corresponding to each component in the composition.
- layer includes not only a shape structure formed over the entire surface but also a shape structure formed partially when observed as a plan view.
- process is included in the term not only as an independent process, but also as long as the intended action of the process is achieved even if it is not clearly distinguishable from other processes.
- (Meth)acrylate means at least one of acrylate and its corresponding methacrylate. The same applies to other similar expressions such as "(meth)acrylic acid”.
- An “alkyl group” may be linear, branched or cyclic, unless otherwise specified.
- the solid content of the photosensitive resin composition refers to the non-volatile content excluding volatile substances (water, solvent, etc.) in the photosensitive resin composition. That is, the solid content refers to the components (components other than the solvent) that remain without volatilizing when the photosensitive resin composition dries, and includes components that are liquid, starch syrup-like, or wax-like at room temperature (25°C).
- the photosensitive film according to the present embodiment contains (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a pyrazoline compound, and the photosensitive film is 20 ⁇ m or less.
- the photosensitive film according to this embodiment is a film-like photosensitive resin composition, and can be obtained by molding the photosensitive resin composition according to this embodiment into a film.
- the photosensitive resin composition according to this embodiment can contain the same ingredients as the photosensitive film according to this embodiment.
- the photosensitive film according to the present embodiment has a thickness of 20 ⁇ m or less, it has a followability (a round hole followability, a filling property, and a ). According to the photosensitive film according to the present embodiment, followability of less than 20000 ⁇ m 2 (preferably 15000 ⁇ m 2 or less) can be obtained in the evaluation described in Examples.
- the present inventors presume as follows about the factors by which the photosensitive film and the photosensitive resin composition according to the present embodiment provide excellent conformability.
- the factors are not limited to the following contents. That is, by using component (D) when using component (A), component (B), and component (C) in combination, various physical properties (crystallinity, melting point, etc.) of component (D) can be adjusted to form recesses with circular cross-sections. It acts favorably in a thermal process (such as lamination) when laminating a photosensitive film on a substrate having the same.
- the photosensitive film according to the present embodiment only needs to have excellent followability when laminated on a substrate having a concave portion with a circular cross section. You may laminate
- linear line portions, linear space portions adjacent to the line portions may form a cured product pattern having.
- excellent resolution is a characteristic that the line portion and the space portion are formed well.
- excellent adhesion is required as a characteristic for good formation of line portions and space portions.
- the photosensitive film or photosensitive resin composition according to the present embodiment excellent resolution can be obtained when forming a cured pattern having a space width smaller than the line width. According to the photosensitive film according to the present embodiment, a resolution of, for example, 15 ⁇ m or less can be obtained in the evaluation described in Examples.
- adhesion can be obtained when forming a cured product pattern having a line width smaller than the space width.
- adhesion of, for example, 10 ⁇ m or less can be obtained in the evaluation described in Examples.
- the photosensitive film or photosensitive resin composition according to the present embodiment it is possible to reduce the minimum time for removing the unexposed areas, and to obtain excellent developability.
- the photosensitive film and the photosensitive resin composition according to the present embodiment excellent sensitivity to actinic rays (before change over time) can be obtained.
- an exposure dose of, for example, 105 mJ/cm 2 or less can be obtained in the evaluation described in Examples.
- the photosensitive film and photosensitive resin composition according to the present embodiment are photocurable, and a cured product can be obtained by photocuring the photosensitive film or photosensitive resin composition.
- the cured product according to this embodiment is a cured product (photocured product) of the photosensitive film or photosensitive resin composition according to this embodiment.
- the cured product according to the present embodiment may be patterned (cured product pattern) or may be a resist pattern.
- the shape of the cured product pattern that can be obtained from the photosensitive film and the photosensitive resin composition according to this embodiment is not particularly limited.
- the thickness of the photosensitive film according to this embodiment may be 20 ⁇ m or less, and the thickness of the cured product according to this embodiment may be 20 ⁇ m or less.
- the thickness of the photosensitive film and cured product according to the present embodiment is 1 ⁇ m or more, 3 ⁇ m or more, 5 ⁇ m or more, and 5 ⁇ m from the viewpoint of easily obtaining excellent followability and from the viewpoint of easily obtaining a resist pattern with a sufficient thickness. It may be greater than, 7 ⁇ m or greater, greater than 7 ⁇ m, 8 ⁇ m or greater, 10 ⁇ m or greater, 10 ⁇ m or greater, 15 ⁇ m or greater, 18 ⁇ m or greater, or 19 ⁇ m or greater.
- the thickness of the photosensitive film and the cured product according to this embodiment may be 19 ⁇ m or less from the viewpoint of easily obtaining excellent resolution and adhesion. From these viewpoints, the thickness of the photosensitive film and cured product according to the present embodiment may be 1 to 20 ⁇ m, 5 to 20 ⁇ m, or 15 to 20 ⁇ m. The thickness of the photosensitive film and cured product may be an average thickness of 10 locations.
- the wavelength at which photosensitivity is exhibited in the photosensitive film and 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 are, for example, light having a wavelength of 300 nm or more, 340 nm or more, 350 nm or more, 355 nm or more, 365 nm or more, 375 nm or more, 390 nm or more, 395 nm or more, or 405 nm or more.
- the photosensitive film and photosensitive resin composition according to the present embodiment have photosensitivity to light having a wavelength of, for example, 500 nm or less, 440 nm or less, less than 440 nm, 436 nm or less, 420 nm or less, 410 nm or less, or 405 nm or less. you can Actinic rays having peaks within these wavelength ranges can be used in the exposure step described later.
- the photosensitive film and photosensitive resin composition according to the present embodiment can be used, for example, as a negative photosensitive film and photosensitive resin composition.
- application of the photosensitive resin composition, photosensitive film, or photosensitive element to the formation of a cured product pattern can be provided.
- application of the photosensitive resin composition, photosensitive film, or photosensitive element to the production of wiring boards can be provided.
- the photosensitive film and photosensitive resin composition according to this embodiment contain a binder polymer as the (A) component.
- Component (A) includes acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, and the like.
- Acrylic resins are resins having a compound ((meth)acrylic acid compound) having a (meth)acryloyl group as a monomer unit, and styrene resins, epoxy resins, and amide resins having the monomer units.
- amidoepoxy resins, alkyd resins and phenolic resins belong to acrylic resins.
- the component (A) does not have to contain a binder polymer having a phenolic hydroxyl group.
- the (A) component may contain an acrylic resin from the viewpoint of easily obtaining excellent followability, resolution and adhesion.
- the content of the acrylic resin is 50% by mass or more, more than 50% by mass, or 70% by mass or more, based on the total mass of the component (A), from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. , 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, or substantially 100% by mass (an aspect in which component (A) is substantially composed of an acrylic resin).
- Examples of compounds having a (meth)acryloyl group include (meth)acrylic acid and (meth)acrylic acid esters.
- (Meth)acrylates include alkyl (meth)acrylates (alkyl (meth)acrylates; excluding compounds corresponding to cycloalkyl (meth)acrylates), cycloalkyl (meth)acrylates ((meth) cycloalkyl acrylate), aryl (meth)acrylate (aryl (meth)acrylate), (meth)acrylamide compounds (diacetone acrylamide, etc.), glycidyl (meth)acrylate, styryl (meth)acrylic acid, etc. is mentioned.
- the (A) component may have (meth)acrylic acid as a monomer unit from the viewpoint of easily obtaining excellent followability, resolution and adhesion.
- (A) When the component has (meth)acrylic acid as a monomer unit, the content of the (meth)acrylic acid monomer unit is from the viewpoint of easily obtaining excellent followability, resolution and adhesion. , (A) may be within the following ranges based on the total amount of the monomer units constituting component (A).
- the content of the monomer units of (meth)acrylic acid is 1% by mass or more, 5% by mass or more, 10% by mass or more, 12% by mass or more, 15% by mass or more, 18% by mass or more, 20% by mass or more, It may be 23% by mass or more, 25% by mass or more, or 27% by mass or more.
- the content of the monomer units of (meth)acrylic acid is 50% by mass or less, less than 50% by mass, 45% by mass or less, 40% by mass or less, 37% by mass or less, 35% by mass or less, 32% by mass or less, It may be 30% by mass or less, or 27% by mass or less. From these points of view, the content of the (meth)acrylic acid monomer unit may be 1 to 50% by mass.
- the (A) component may have an alkyl (meth)acrylate as a monomer unit from the viewpoint of easily obtaining excellent conformability, resolution and adhesion.
- alkyl group of alkyl (meth)acrylate include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group. and the alkyl groups may be of various structural isomers.
- the number of carbon atoms in the alkyl group of the alkyl (meth)acrylate is 1 to 4, 1 to 3, 2 to 3, or 1 to 2 from the viewpoint of easily obtaining excellent followability, resolution and adhesion. you can
- the alkyl group of the alkyl (meth)acrylate may have a substituent.
- Substituents include a hydroxy group, a carboxy group, a carboxylic acid group, an aldehyde group, an alkoxy group (unsubstituted alkoxy group (structure having an unsubstituted alkyl group bonded to an oxygen atom), or a substituted alkoxy group (hydroxyalkoxy group, etc.)), carbonyl group, alkoxycarbonyl group, alkanoyl group (alkanoyl group having 2 to 12 carbon atoms, etc.), oxycarbonyl group, carbonyloxy group, amino group, epoxy group, furyl group, cyano group, halogeno group (fluoro group, chloro group, bromo group, etc.), nitro group, acetyl group, sulfonyl group, sulfonamide group and the like.
- Component (A) includes dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3 (meth)acrylate, 3-tetrafluoropropyl, ⁇ -chloro(meth)acrylic acid, ⁇ -bromo(meth)acrylic acid and the like.
- the (A) component may have hydroxyalkyl (meth)acrylate as a monomer unit from the viewpoint of easily obtaining excellent followability, resolution and adhesion.
- Hydroxyalkyl (meth)acrylates include hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, Hydroxyhexyl (meth)acrylate and the like can be mentioned.
- the content of the monomer units of the hydroxyalkyl (meth)acrylate when it is present as a monomer unit may be within the following range based on the total amount of the monomer units constituting component (A).
- the content of the above-mentioned monomer units is 0.10% by mass or more, 0.50% by mass or more, 1.0% by mass or more, 1 .5% by mass or more, 2.0% by mass or more, 2.5% by mass or more, or 3.0% by mass or more.
- the content of the above-mentioned monomer units is 3.5% by mass or more, 4.0% by mass or more, 4.0% by mass or more, and 4 0.5% by mass or more, or 5.0% by mass or more.
- the content of the above-mentioned monomer units is 20% by mass or less, 18% by mass or less, 15% by mass or less, 12% by mass or less, and 10% by mass. % or less, 8.0 mass % or less, 6.0 mass % or less, 5.5 mass % or less, or 5.0 mass % or less.
- the content of the above-mentioned monomer units is 4.5% by mass or less, 4.0% by mass or less, 3.5% by mass or less, or 3.0% by mass from the viewpoint of easily obtaining excellent resolution. % or less. From these points of view, the content of the above monomer units may be 0.10 to 20% by mass, or 0.10 to 5.0% by mass.
- the content of the monomer unit of the alkyl (meth)acrylate having 4 or more carbon atoms in the alkyl group is (A ) may be 1% by mass or less, less than 1% by mass, 0.1% by mass or less, or 0.01% by mass or less based on the total amount of the monomer units constituting the component.
- the (A) component may have aryl (meth)acrylate as a monomer unit from the viewpoint of easily obtaining excellent conformability, resolution and adhesion.
- Aryl (meth)acrylates include benzyl (meth)acrylate, phenyl (meth)acrylate, and naphthyl (meth)acrylate.
- the content of the monomer units of the aryl (meth)acrylate is the total amount of the monomer units constituting the component (A).
- the following range may be used as a reference.
- the content of the monomer unit of the aryl (meth)acrylate is 1% by mass or more, 5% by mass or more, 10% by mass or more, and 12% by mass from the viewpoint of easily obtaining excellent followability, resolution and adhesion. % or more, 15 mass % or more, 18 mass % or more, or 20 mass % or more.
- the content of the monomer unit of the aryl (meth)acrylate is 21% by mass or more, or 23% by mass, from the viewpoint of easily obtaining excellent sensitivity and developability, and from the viewpoint of easily obtaining excellent followability. or more.
- the content of the monomer unit of the aryl (meth)acrylate is 50% by mass or less, less than 50% by mass, 45% by mass or less, and 40% by mass, from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. % or less, 35 mass % or less, 30 mass % or less, 25 mass % or less, or 23 mass % or less.
- the content of the monomer units of the aryl (meth)acrylate may be 21% by mass or less, or 20% by mass or less, from the viewpoint of easily obtaining even better resolution. From these viewpoints, the content of the monomer units of the aryl (meth)acrylate may be 1 to 50% by mass.
- the (A) component may have a styrene compound (excluding compounds having a (meth)acryloyl group) as a monomer unit from the viewpoint of easily obtaining excellent followability, resolution and adhesion.
- Styrene compounds include styrene and styrene derivatives. Examples of styrene derivatives include vinyltoluene and ⁇ -methylstyrene.
- Component (A) may have (meth)acrylic acid and a styrene compound as monomer units from the viewpoint of easily obtaining excellent followability, resolution and adhesion, and hydroxyalkyl (meth)acrylate and It may have a styrene compound as a monomer unit, and may have an aryl (meth)acrylate and a styrene compound as a monomer unit.
- the content of the monomer units of the styrene compound is within the following range based on the total amount of the monomer units constituting the component (A). good.
- the content of the monomer unit of the styrene compound is 10% by mass or more, 15% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, from the viewpoint of easily obtaining excellent followability, resolution and adhesion. It may be at least 30% by mass, at least 30% by mass, at least 35% by mass, at least 40% by mass, or at least 45% by mass.
- the content of the monomer unit of the styrene compound may be 47% by mass or more, or 50% by mass or more from the viewpoint of easily obtaining even better resolution.
- the content of the monomer unit of the styrene compound is 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, from the viewpoint of easily obtaining excellent followability, resolution and adhesion. % by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, or 50% by mass or less.
- the content of the monomer unit of the styrene compound is 47% by mass or less, or 45% by mass or less from the viewpoint of easily obtaining excellent sensitivity and developability, and from the viewpoint of easily obtaining excellent followability. good. From these points of view, the content of monomer units in the styrene compound may be 10 to 90% by mass.
- the (A) component may have other monomers as monomer units.
- monomers include vinyl alcohol ethers (vinyl-n-butyl ether, etc.), (meth)acrylonitrile, maleic acid, maleic anhydride, maleic acid monoesters (monomethyl maleate, monoethyl maleate, maleic monoisopropyl acid, etc.), fumaric acid, cinnamic acid, ⁇ -cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like.
- the acid value of the component (A) is 80 mgKOH/g or more, 90 mgKOH/g or more, 100 mgKOH/g or more, and more than 100 mgKOH/g from the viewpoint of easily obtaining excellent sensitivity, developability, followability, resolution and adhesion. , 120 mg KOH/g or more, 140 mg KOH/g or more, 150 mg KOH/g or more, 160 mg KOH/g or more, 170 mg KOH/g or more, or 175 mg KOH/g or more.
- the acid value of component (A) may be 176 mgKOH/g or more from the viewpoint of easily obtaining even better resolution.
- the acid value of the component (A) is 250 mgKOH/g or less, 240 mgKOH/g or less, 230 mgKOH/g or less, or 210 mgKOH/g or less from the viewpoint of easily obtaining excellent sensitivity, developability, followability, resolution, and adhesion. , 200 mg KOH/g or less, 180 mg KOH/g or less, 178 mg KOH/g or less, or 176 mg KOH/g or less.
- the acid value of component (A) may be 175 mgKOH/g or less from the viewpoint of easily obtaining even better sensitivity, developability and followability. From these points of view, the component (A) may have an acid value of 80 to 250 mgKOH/g.
- the acid value of component (A) can be adjusted by adjusting the content of the monomer units (for example, the monomer units of (meth)acrylic acid) constituting component (A).
- the acid value of component (A) can be measured by the method described in Examples.
- the weight average molecular weight (Mw) of component (A) may be within the following range from the viewpoint of easily obtaining excellent sensitivity, developability, followability, resolution and adhesion.
- the weight average molecular weight of component (A) may be 10,000 or more, 20,000 or more, 25,000 or more, 30,000 or more, or 35,000 or more.
- the weight average molecular weight of component (A) may be 100,000 or less, 80,000 or less, 70,000 or less, less than 70,000, 65,000 or less, 60,000 or less, 50,000 or less, 40,000 or less, or 35,000 or less. From these viewpoints, the weight average molecular weight of component (A) may be 10,000 to 100,000, 20,000 to 50,000, or 30,000 to 40,000.
- the number average molecular weight (Mn) of component (A) may be within the following range.
- the number average molecular weight of component (A) is 5000 or more, 10000 or more, 12000 or more, 15000 or more, or 16000 or more from the viewpoint of easily obtaining excellent sensitivity, developability, followability, resolution and adhesion. you can
- the number average molecular weight of component (A) may be 16,500 or more from the viewpoint of easily obtaining even better sensitivity, developability, and followability.
- the number average molecular weight of component (A) is 50,000 or less, 40,000 or less, 35,000 or less, 30,000 or less, 25,000 or less, 20,000 or less, from the viewpoint of easily obtaining excellent sensitivity, developability, followability, resolution, and adhesion.
- the number average molecular weight of component (A) may be 16,000 or less from the viewpoint of easily obtaining even better resolution. From these viewpoints, the number average molecular weight of component (A) may be 5,000 to 50,000, 10,000 to 25,000, or 15,000 to 20,000.
- the degree of dispersion (weight average molecular weight/number average molecular weight) of component (A) may be within the following range.
- the dispersion degree of component (A) is 1.00 or more, 1.50 or more, 1.80 or more, 2.00 or more from the viewpoint of easily obtaining excellent sensitivity, developability, followability, resolution and adhesion. , 2.10 or greater, or 2.12 or greater.
- the dispersity of component (A) may be 2.15 or more, or 2.18 or more from the viewpoint of easily obtaining even better resolution.
- the degree of dispersion of component (A) is 3.00 or less, 2.80 or less, 2.50 or less, 2.30 or less from the viewpoint of easily obtaining excellent sensitivity, developability, followability, resolution and adhesion.
- component (A) may have a dispersity of 1.00 to 3.00.
- the weight average molecular weight and number average molecular weight can be measured, for example, by gel permeation chromatography (GPC) using a standard polystyrene calibration curve. More specifically, it can be measured under the conditions described in Examples. If it is difficult to measure a compound having a low molecular weight by the above weight average molecular weight and number average molecular weight measurement methods, the molecular weight can be measured by another method and the average value can be calculated.
- GPC gel permeation chromatography
- the content of component (A) is 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 easily obtaining excellent followability, resolution and adhesion. may be in the range of The content of component (A) is 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 45% by mass or more, or 50% by mass or more from the viewpoint of excellent film formability. It's okay.
- the content of component (A) may be 90% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, or 55% by mass or less. From these points of view, the content of component (A) may be 10 to 90% by mass.
- the content of component (A) may be within the following range with respect to the total amount of 100 parts by mass of components (A) and (B).
- the content of component (A) is 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, or 45 parts by mass or more from the viewpoint of easily obtaining excellent followability, resolution and adhesion. , 50 parts by mass or more, 55 parts by mass or more, or 56 parts by mass or more.
- the content of component (A) may be 57 parts by mass or more, or 58 parts by mass or more from the viewpoint of easily obtaining excellent developability.
- the content of component (A) is 90 parts by mass or less, 80 parts by mass or less, 75 parts by mass or less, 70 parts by mass or less, or 65 parts by mass or less from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. , 60 parts by mass or less, or 59 parts by mass or less.
- the content of component (A) may be 58 parts by mass or less, 57 parts by mass or less, or 56 parts by mass or less from the viewpoint of easily obtaining excellent followability and from the viewpoint of easily obtaining excellent sensitivity. . From these viewpoints, the content of component (A) may be 10 to 90 parts by mass, or 40 to 70 parts by mass.
- the content of the resin having a phenolic hydroxyl group is based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content). , 30% by mass or less, less than 30% by mass, 20% by mass or less, 10% by mass or less, 5% by mass or less, 1% by mass or less, or 0.1% by mass or less.
- the photosensitive film and photosensitive resin composition according to the present embodiment may not contain a resin having a phenolic hydroxyl group (the above content may be substantially 0% by mass).
- the photosensitive film and photosensitive resin composition according to the present embodiment contain photopolymerizable compounds (excluding compounds corresponding to pyrazoline compounds) as the (B) component.
- a photopolymerizable compound is a compound that is polymerized by light.
- the component (B) may be a compound having an ethylenically unsaturated bond and may be a compound ((meth)acrylic acid compound) having a (meth)acryloyl group.
- Component (B) includes bisphenol A type (meth)acrylic acid compounds (excluding (meth)acrylic acid compounds having a polyoxyalkylene group), EO-modified di(meth)acrylates, PO-modified di(meth)acrylates, EO ⁇ PO-modified di(meth)acrylate, polyalkylene glycol di(meth)acrylate (polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc.), EO-modified polyalkylene glycol di(meth)acrylate, PO-modified poly Alkylene glycol di(meth)acrylate, EO/PO-modified polyalkylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO/PO-
- EO-modified means a compound having a polyoxyethylene group.
- PO-modified means a compound having a polyoxypropylene group.
- EO/PO-modified means a compound having a polyoxyethylene group and/or a (poly)oxypropylene group.
- the (B) component may contain a bisphenol A type (meth)acrylic acid compound from the viewpoint of easily obtaining excellent conformability, resolution and adhesion.
- a bisphenol A type (meth)acrylic acid compound 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane (2,2-bis(4-((meth)acryloxypentaethoxy) phenyl)propane, etc.), 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolybutoxy)phenyl)propane, 2, 2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane and the like.
- Component (B) may contain 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane from the viewpoint of easily obtaining excellent followability, resolution and adhesion. 2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane may be included.
- the molecular weight of the bisphenol A type (meth)acrylic acid compound may be within the following range from the viewpoint of easily obtaining excellent conformability, resolution and adhesion.
- the molecular weight may be 100 or greater, 200 or greater, 300 or greater, 400 or greater, 450 or greater, 500 or greater, 600 or greater, 700 or greater, or 800 or greater.
- 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 less, or 500 or less. . From these points of view, the molecular weight may range from 100 to 10,000.
- the content of the bisphenol A type (meth)acrylic acid compound may be within the following ranges based on the total mass of the component (B).
- the content of the bisphenol A type (meth)acrylic acid compound is 50% by mass or more, more than 50% by mass, 60% by mass or more, 70% by mass or more from the viewpoint of easily obtaining excellent followability, resolution and adhesion. , or 75% by mass or more.
- the content of the bisphenol A type (meth)acrylic acid compound is 80% by mass or more, 85% by mass or more, or 90% by mass from the viewpoint of easily obtaining excellent followability and from the viewpoint of easily obtaining excellent sensitivity. or more.
- the content of the bisphenol A type (meth)acrylic acid compound is 100% by mass or less, and from the viewpoint of easily obtaining excellent followability, resolution and adhesion, it is less than 100% by mass, 99% by mass or less, and 98% by mass. % or less, 97 mass % or less, 95 mass % or less, 92 mass % or less, or 91 mass % or less.
- the content of the bisphenol A type (meth)acrylic acid compound may be 90% by mass or less, 85% by mass or less, or 80% by mass or less from the viewpoint of easily obtaining excellent developability. From these points of view, the content of the bisphenol A type (meth)acrylic acid compound may be 50 to 100% by mass.
- the content of the bisphenol A type (meth)acrylic acid compound may be within the following range with respect to 100 parts by mass of the total amount of the components (A) and (B).
- the content of the bisphenol A type (meth)acrylic acid compound is 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, or 20 parts by mass or more from the viewpoint of easily obtaining excellent followability, resolution and adhesion. , more than 20 parts by weight, more than 25 parts by weight, more than 25 parts by weight, more than 30 parts by weight, or more than 30 parts by weight.
- the content of the bisphenol A type (meth)acrylic acid compound is 32 parts by mass or more, 35 parts by mass or more, more than 35 parts by mass, from the viewpoint of easily obtaining excellent followability and excellent sensitivity. It may be 38 parts by mass or more, or 40 parts by mass or more.
- the content of the bisphenol A type (meth)acrylic acid compound is less than 100 parts by mass, 90 parts by mass or less, 80 parts by mass or less, or 70 parts by mass or less from the viewpoint of easily obtaining excellent followability, resolution and adhesion. , 60 parts by mass or less, 50 parts by mass or less, 45 parts by mass or less, or 40 parts by mass or less.
- the content of the bisphenol A type (meth)acrylic acid compound may be 38 parts by mass or less, 35 parts by mass or less, less than 35 parts by mass, or 32 parts by mass or less from the viewpoint of easily obtaining excellent developability. From these points of view, the content of the bisphenol A type (meth)acrylic acid compound may be 1 part by mass or more and less than 100 parts by mass.
- Component (B) is a (meth)acrylic acid compound having a polyoxyalkylene group (a group in which two or more alkylene groups are linked by an ether bond) from the viewpoint of easily obtaining excellent followability, resolution and adhesion. It may contain a (meth)acrylic acid compound having at least one selected from the group consisting of a polyoxyethylene group and a polyoxypropylene group.
- the molecular weight of the (meth)acrylic acid compound having a polyoxyalkylene group may be within the following range from the viewpoint of easily obtaining excellent conformability, resolution and adhesion.
- the molecular weight may be 100 or greater, 200 or greater, 300 or greater, 400 or greater, 500 or greater, 600 or greater, 700 or greater, 800 or greater, 900 or greater, 1000 or greater, or 1100 or greater.
- the molecular weight may be 10,000 or less, less than 10,000, 8,000 or less, 6,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,500 or less, or 1,200 or less. From these points of view, the molecular weight may range from 100 to 10,000.
- the content of the (meth)acrylic acid compound having a polyoxyalkylene group may be within the following ranges based on the total mass of component (B).
- the content of the (meth)acrylic acid compound having a polyoxyalkylene group may exceed 0% by mass, 1% by mass or more, and 2% by mass from the viewpoint of easily obtaining excellent followability, resolution and adhesion. Above, it may be 3% by mass or more, 5% by mass or more, 8% by mass or more, or 9% by mass or more.
- the content of the (meth)acrylic acid compound having a polyoxyalkylene group is 10% by mass or more, 12% by mass or more, 15% by mass or more, 18% by mass or more, and 20% by mass from the viewpoint of easily obtaining excellent developability. or more, or 23% by mass or more.
- the content of the (meth)acrylic acid compound having a polyoxyalkylene group is 50% by mass or less, less than 50% by mass, 40% by mass or less, 30% by mass or less, from the viewpoint of easily obtaining excellent followability, resolution and adhesion. % by mass or less, or 25% by mass or less.
- the content of the (meth)acrylic acid compound having a polyoxyalkylene group is 23% by mass or less, 20% by mass or less, and 18% by mass from the viewpoint of easily obtaining excellent followability and from the viewpoint of easily obtaining excellent sensitivity. % or less, 15 mass % or less, 12 mass % or less, or 10 mass % or less. From these points of view, the content of the (meth)acrylic acid compound having a polyoxyalkylene group may be more than 0% by mass and 50% by mass or less.
- the content of the (meth)acrylic acid compound having a polyoxyalkylene group may be within the following range with respect to 100 parts by mass of the total amount of components (A) and (B).
- the content of the (meth)acrylic acid compound having a polyoxyalkylene group is 0.10 parts by mass or more, 0.50 parts by mass or more, from the viewpoint of easily obtaining excellent followability, resolution and adhesion.
- the content of the (meth)acrylic acid compound having a polyoxyalkylene group is 4.5 parts by mass or more, 5.0 parts by mass or more, 6.0 parts by mass or more, from the viewpoint of easily obtaining excellent developability. It may be 0 parts by mass or more, 8.0 parts by mass or more, 8.5 parts by mass or more, 9.0 parts by mass or more, or 9.5 parts by mass or more.
- the content of the (meth)acrylic acid compound having a polyoxyalkylene group is 50 parts by mass or less, 30 parts by mass or less, 25 parts by mass or less, 20 parts by mass or less, from the viewpoint of easily obtaining excellent followability, resolution and adhesion. It may be no more than 18 parts by mass, no more than 15 parts by mass, no more than 12 parts by mass, no more than 10 parts by mass, or no more than 9.5 parts by mass.
- the content of the (meth)acrylic acid compound having a polyoxyalkylene group is 9.0 parts by mass or less and 8.5 parts by mass from the viewpoint of easily obtaining excellent followability and from the viewpoint of easily obtaining excellent sensitivity.
- the content of the (meth)acrylic acid compound having a polyoxyalkylene group may be 0.10 to 50 parts by mass.
- the content of the (meth)acrylic acid compound having a polyoxyalkylene group may be in the following range with respect to 100 parts by mass of the bisphenol A type (meth)acrylic acid compound.
- the content of the (meth)acrylic acid compound having a polyoxyalkylene group is 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 5 parts by mass or more, from the viewpoint of easily obtaining excellent followability, resolution and adhesion. It may be at least 8 parts by mass, or at least 10 parts by mass.
- the content of the (meth)acrylic acid compound having a polyoxyalkylene group is 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, or 30 parts by mass or more from the viewpoint of easily obtaining excellent developability. you can
- the content of the (meth)acrylic acid compound having a polyoxyalkylene group is 100 parts by mass or less, less than 100 parts by mass, 80 parts by mass or less, 50 parts by mass or less, from the viewpoint of easily obtaining excellent followability, resolution and adhesion. It may be no more than 45 parts by mass, no more than 40 parts by mass, no more than 35 parts by mass, or no more than 30 parts by mass.
- the content of the (meth)acrylic acid compound having a polyoxyalkylene group is 25 parts by mass or less, 20 parts by mass or less, and 15 parts by mass from the viewpoint of easily obtaining excellent followability and from the viewpoint of easily obtaining excellent sensitivity. parts or less, or 10 parts by mass or less. From these points of view, the content of the (meth)acrylic acid compound having a polyoxyalkylene group may be 1 to 100 parts by mass.
- the content of component (B) may be within the following ranges based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content).
- the content of component (B) is 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, and 30% by mass or more from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. , 35% by mass or more, or 38% by mass or more.
- the content of the component (B) may be 40% by mass or more, or 41% by mass or more, from the viewpoint of easily obtaining excellent followability and from the viewpoint of easily obtaining excellent sensitivity.
- the content of component (B) is 90% by mass or less, 80% by mass or less, 70% by mass or less, 65% by mass or less, or 60% by mass or less from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. , 55 mass % or less, 50 mass % or less, 45 mass % or less, or 42 mass % or less.
- the content of component (B) may be 41% by mass or less, or 40% by mass or less from the viewpoint of easily obtaining excellent developability. From these viewpoints, the content of component (B) may be 10 to 90% by mass.
- the content of component (B) may be within the following range with respect to 100 parts by mass of the total amount of components (A) and (B).
- the content of component (B) is 10 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, or 35 parts by mass or more from the viewpoint of easily obtaining excellent followability, resolution and adhesion. , 40 parts by mass or more, or 41 parts by mass or more.
- the content of the component (B) may be 42 parts by mass or more, 43 parts by mass or more, or 44 parts by mass or more from the viewpoint of easily obtaining excellent followability and from the viewpoint of easily obtaining excellent sensitivity. .
- the content of component (B) is 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, or 55 parts by mass or less from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. , 50 parts by mass or less, 45 parts by mass or less, or 44 parts by mass or less.
- the content of component (B) may be 43 parts by mass or less, or 42 parts by mass or less from the viewpoint of easily obtaining excellent developability. From these viewpoints, the content of component (B) may be 10 to 90 parts by mass, or 30 to 60 parts by mass.
- the total amount of the compound having three or more ethylenically unsaturated groups and the di(meth)acrylate compound having a bisphenol A skeleton is the component (A) It may be 20 parts by mass or less, less than 20 parts by mass, 10 parts by mass or less, 1 part by mass or less, or 0.1 parts by mass or less with respect to 100 parts by mass of the total amount of component (B).
- the photosensitive film and photosensitive resin composition according to the present embodiment contain at least one compound selected from the group consisting of a compound having three or more ethylenically unsaturated groups and a di(meth)acrylate compound having a bisphenol A skeleton. It may not be contained (the content may be substantially 0 parts by mass with respect to 100 parts by mass of the total amount of components (A) and (B)).
- the content of the photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric ring structure is 100 parts by mass of the total amount of components (A) and (B). 1 part by mass or less, less than 1 part by mass, 0.1 part by mass or less, 0.01 part by mass or less, or 0.001 part by mass or less.
- the photosensitive film and photosensitive resin composition according to the present embodiment may not contain a photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric ring structure (the above content is substantially 0 parts by mass. may be).
- the content of is 3 parts by mass or less, less than 3 parts by mass, 1 part by mass or less, 0.1 parts by mass or less, or 0.01 parts by mass with respect to 100 parts by mass of the total amount of components (A) and (B) It may be less than or equal to parts by mass.
- the photosensitive film and the photosensitive resin composition according to the present embodiment are at least one selected from the group consisting of a photopolymerizable compound having a pentaerythritol-derived skeleton and a photopolymerizable compound having a dipentaerythritol-derived skeleton. may not be contained (the content may be substantially 0 parts by mass with respect to 100 parts by mass of the total amount of components (A) and (B)).
- the photosensitive film and photosensitive resin composition from the group consisting of a (meth)acrylic acid compound having a skeleton derived from pentaerythritol and a (meth)acrylic acid compound having a skeleton derived from dipentaerythritol
- the content of at least one selected is 3 parts by mass or less, less than 3 parts by mass, 1 part by mass or less, 0.1 parts by mass or less, or , 0.01 parts by mass or less.
- the photosensitive film and the photosensitive resin composition according to the present embodiment are selected from the group consisting of (meth)acrylic acid compounds having a pentaerythritol-derived skeleton and (meth)acrylic acid compounds having a dipentaerythritol-derived skeleton. At least one selected may not be contained (the content may be substantially 0 parts by mass with respect to 100 parts by mass of the total amount of components (A) and (B)).
- the content of the bisphenol F-type (meth)acrylic acid compound is 5% by mass or less and less than 5% by mass, based on the total mass of the component (B). , 1% by weight or less, less than 1% by weight, 0.1% by weight or less, or substantially 0% by weight.
- the content of the bisphenol F-type (meth)acrylic acid compound is the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content). 0.2% by mass or less, 0.15% by mass or less, less than 0.15% by mass, 0.1% by mass or less, or 0.01% by mass or less.
- the photosensitive film and photosensitive resin composition according to the present embodiment may not contain a bisphenol F-type (meth)acrylic acid compound (the above content may be substantially 0% by mass).
- the content of the epoxy compound having two or more oxirane rings is 20 parts by mass or less and 20 parts by mass with respect to 100 parts by mass of component (A). It may be less than, 10 parts by weight or less, less than 10 parts by weight, 1 part by weight or less, or substantially 0 parts by weight.
- the photosensitive film and photosensitive resin composition according to the present embodiment may not contain an epoxy compound having two or more oxirane rings (the content of the epoxy compound having two or more oxirane rings is It may be substantially 0% by mass based on the total amount of the film or the total amount of the photosensitive resin composition (the total solid content)).
- the photosensitive film and photosensitive resin composition according to the present embodiment contain a photopolymerization initiator (excluding compounds corresponding to pyrazoline compounds) as the (C) component.
- Component (C) includes hexaarylbiimidazole compounds; 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- Aromatic ketones such as [4-(methylthio)phenyl]-2-morpholino-propanone-1; quinone compounds such as alkylanthraquinone; benzoin ether compounds such as benzoin alkyl ether; benzoin compounds such as benzoin and alkylbenzoin; benzyl derivatives such as; bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; bis(2,6-dimethylbenzoyl)-2
- the (C) component may contain a hexaarylbiimidazole compound from the viewpoint of easily obtaining excellent followability, resolution and adhesion.
- the aryl group in the hexaarylbiimidazole compound may be a phenyl group or the like.
- a hydrogen atom bonded to an aryl group in the hexaarylbiimidazole compound may be substituted with a halogen atom (such as a chlorine atom).
- the hexaarylbiimidazole compound may be a 2,4,5-triarylimidazole dimer.
- 2,4,5-triarylimidazole dimer examples include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis-(m- methoxyphenyl)imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, and the like.
- the hexaarylbiimidazole compound may contain 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer from the viewpoint of easily obtaining excellent followability, resolution and adhesion, and 2,2' -bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.
- the content of the hexaarylbiimidazole compound is 50% by mass or more, more than 50% by mass, or 70% by mass, based on the total amount of component (C), from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. Above, 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, or substantially 100% by mass (an aspect in which the component (C) is substantially composed of a hexaarylbiimidazole compound) you can
- the content of component (C) is 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 easily obtaining excellent followability, resolution and adhesion. may be in the range of The content of component (C) is 0.10% by mass or more, 0.50% by mass or more, 1.0% by mass or more, 2.0% by mass or more, 3.0% by mass or more, 4.0% by mass or more , 4.5% by mass or more, or 4.7% by mass or more.
- the content of component (C) is 20% by mass or less, 15% by mass or less, 12% by mass or less, 10% by mass or less, 8.0% by mass or less, 7.0% by mass or less, 6.0% by mass or less, Alternatively, it may be 5.0% by mass or less. From these viewpoints, the content of component (C) may be 0.10 to 20% by mass.
- the content of component (C) may be in the following range with respect to 100 parts by mass of the total amount of components (A) and (B), from the viewpoint of easily obtaining excellent followability, resolution and adhesion. .
- the content of component (C) is 0.10 parts by mass or more, 0.50 parts by mass or more, 1.0 parts by mass or more, 2.0 parts by mass or more, 3.0 parts by mass or more, 3.5 parts by mass or more , 4.0 parts by mass or more, 4.5 parts by mass or more, or 5.0 parts by mass or more.
- the content of component (C) is 20 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, 10 parts by mass or less, 8.0 parts by mass or less, 7.0 parts by mass or less, 6.0 parts by mass or less, Alternatively, it may be 5.5 parts by mass or less. From these points of view, the content of component (C) may be 0.10 to 20 parts by mass.
- the photosensitive film and photosensitive resin composition according to the present embodiment contain a pyrazoline compound (a compound having a pyrazoline ring) as component (D).
- component (D) A component can be used as a sensitizer (photosensitizer).
- the molecular weight of component (D) may be less than 10,000.
- Pyrazoline compounds include 1-pyrazoline compounds, 2-pyrazoline compounds, and 3-pyrazoline compounds.
- the pyrazoline compound may contain a 2-pyrazoline compound from the viewpoint of easily obtaining excellent followability, resolution and adhesion.
- the pyrazoline compound may have a substituent that binds to the pyrazoline ring, and may include compounds that have a substituent that binds to at least one selected from the group consisting of the 1-, 3- and 5-positions of the pyrazoline ring.
- substituents include alkyl groups (alkyl groups having 1 to 20 carbon atoms (acyclic alkyl groups), cycloalkyl groups having 5 to 12 carbon atoms, etc.), aryl groups (phenyl groups, aralkyl groups (benzyl group, phenethyl group, etc.
- the benzene ring of the aryl group may have a substituent, such as an alkyl group, an alkoxy group (methoxy group, ethoxy group, propoxy group, etc.), a halogeno group (fluoro group, chloro group, bromo group, etc.). , a sulfonamide group, and the like.
- the substituent may be an alkylester group (eg, an alkylester group having 1 to 6 carbon atoms), an alkylamino group (eg, an alkylamino group having 1 to 20 carbon atoms), or the like.
- Component (D) consists of a compound represented by the following general formula (d1) and a compound represented by the following general formula (d2) from the viewpoint of easily obtaining excellent followability, resolution and adhesion. It may contain at least one selected from the group, and may contain a compound represented by the following general formula (d1).
- R d11 , R d12 and R d13 each independently represent an alkoxy group (eg, an alkoxy group having 1 to 10 carbon atoms) or an alkyl group (eg, an alkyl group having 1 to 3 carbon atoms); , d11, d12 and d13 each independently represent an integer of 0 to 5.
- d11 is 2 or more, a plurality of R d11 may be the same or different, and when d12 is 2 or more, a plurality of R d12 may be the same. They may be different, and when d13 is 2 or more, a plurality of R d13 may be the same or different.
- R d11 , R d12 and R d13 is an alkoxy group (eg, an alkoxy group having 1 to 10 carbon atoms) or an alkyl group (eg, an alkyl group having 1 to 3 carbon atoms). It's okay. At least one selected from the group consisting of R d12 and R d13 may be an alkoxy group, a methoxy group, an ethoxy group or a propoxy group from the viewpoint of easily obtaining excellent followability, resolution and adhesion. good. d11 may be 0 from the viewpoint of easily obtaining excellent followability, resolution and adhesion.
- At least one selected from the group consisting of d12 and d13 may be 0, 1, 2 or 3, or 1 from the viewpoint of easily obtaining excellent followability, resolution and adhesion.
- the sum of d11, d12 and d13 may be 0-6 or 1-6.
- R d21 and R d22 are each independently 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 alkoxy group, (for example, an alkoxy group having 1 to 6 carbon atoms), an amino group, a halogeno group, a carboxy group, a cyano group, a nitro group, an acetyl group, a sulfonyl group, or a sulfonamide group, and d21 and d22 are each independently Indicates an integer from 0 to 5.
- d21 is 2 or more, a plurality of R d21 may be the same or different, and when d22 is 2 or more, a plurality of R d22 may be the same. can be different.
- R d21 may be a halogeno group, a fluoro group, a chloro group, or a bromo group.
- R d22 may be a sulfonamide group. At least one selected from the group consisting of d21 and d22 may be 0, 1, 2 or 3, and may be 1.
- pyrazoline compounds include 1-phenyl-3-(4-isopropylstyryl)-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-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,6-dimethoxy styryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,5-dimethoxystyryl)-5
- the pyrazoline compound is a compound having an aryl group bonded to the pyrazoline ring (two or more (eg, 2 to 3) aryl groups bonded to the pyrazoline ring) from the viewpoint of easily obtaining excellent followability, resolution and adhesion.
- ⁇ 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 the pyrazoline ring, 1-position of the pyrazoline ring, 3-position and 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 the 5-position, 1-phenyl-3-(4-methoxystyryl)-5- (4-Methoxyphenyl)pyrazoline and at least one selected from the group consisting of 4-[[3-(4-chlorophenyl)-4,5-dihydro-1H-pyrazol]-1-yl]benzenesulfonamide OK.
- the content of component (D) may be within the following ranges based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content).
- the content of component (D) is 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, and 0.08% by mass, from the viewpoint of easily obtaining excellent followability, resolution, and adhesion.
- % by mass or more 0.10% by mass or more, more than 0.10% by mass, 0.12% by mass or more, 0.15% by mass or more, 0.18% by mass or more, or 0.19% by mass or more good.
- the content of the component (D) is 0.20% by mass or more, 0.23% by mass or more, 0.25% by mass or more from the viewpoint of easily obtaining excellent adhesion and from the viewpoint of easily obtaining excellent sensitivity. , or 0.28% by mass or more.
- the content of component (D) is 5.0% by mass or less, 3.0% by mass or less, 1.0% by mass or less, and 0.80 from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. % by mass or less, 0.70 mass % or less, 0.60 mass % or less, 0.50 mass % or less, 0.40 mass % or less, 0.35 mass % or less, 0.30 mass % or less, or 0. It may be 28% by mass or less.
- the content of component (D) is 0.25% by mass or less, 0.23% by mass or less, 0.20% by mass or less, or 0.19% by mass or less from the viewpoint of easily obtaining excellent followability. It's okay. From these viewpoints, the content of component (D) may be 0.01 to 5.0% by mass, or 0.10 to 1.0% by mass.
- the content of component (D) may be within the following range with respect to the total amount of 100 parts by mass of components (A) and (B).
- the content of component (D) is 0.01 parts by mass or more, 0.02 parts by mass or more, more than 0.02 parts by mass, and 0.03 from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. parts by mass or more, 0.05 parts by mass or more, 0.08 parts by mass or more, 0.10 parts by mass or more, more than 0.10 parts by mass, 0.12 parts by mass or more, 0.15 parts by mass or more, 0.18 parts by mass parts or more, or 0.20 parts by mass or more.
- the content of the component (D) is 0.21 parts by mass or more, 0.23 parts by mass or more, and 0.25 parts by mass or more from the viewpoint of easily obtaining excellent adhesion and from the viewpoint of easily obtaining excellent sensitivity. , 0.28 parts by mass or more, or 0.30 parts by mass or more.
- the content of component (D) is 5.0 parts by mass or less, 3.0 parts by mass or less, 1.0 parts by mass or less, and 0.80 from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. Parts by mass or less, 0.70 parts by mass or less, 0.60 parts by mass or less, 0.50 parts by mass or less, 0.40 parts by mass or less, 0.35 parts by mass or less, or 0.30 parts by mass or less good.
- the content of component (D) is 0.28 parts by mass or less, 0.25 parts by mass or less, 0.23 parts by mass or less, 0.21 parts by mass or less, or It may be 0.20 parts by mass or less. From these viewpoints, the content of component (D) may be 0.01 to 5.0 parts by mass, 0.03 to 5.0 parts by mass, or 0.10 to 1.0 parts by mass.
- the content of component (D) may be within the following ranges per 100 parts by mass of component (A).
- the content of component (D) is 0.01 parts by mass or more, 0.03 parts by mass or more, 0.05 parts by mass or more, and 0.08 parts by mass from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. parts by mass or more, 0.10 parts by mass or more, 0.15 parts by mass or more, 0.20 parts by mass or more, 0.25 parts by mass or more, 0.30 parts by mass or more, 0.35 parts by mass or more, or 0. It may be 36 parts by mass or more.
- the content of the component (D) is 0.40 parts by mass or more, 0.45 parts by mass or more, and 0.50 parts by mass or more from the viewpoint of easily obtaining excellent adhesion and from the viewpoint of easily obtaining excellent sensitivity. , or 0.54 parts by mass or more.
- the content of component (D) is 5.0 parts by mass or less, 3.0 parts by mass or less, 1.0 parts by mass or less, and 0.80 from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. It may be 0.70 parts by mass or less, 0.60 parts by mass or less, 0.55 parts by mass or less, or 0.54 parts by mass or less.
- the content of component (D) is 0.54 parts by mass or less, 0.50 parts by mass or less, 0.45 parts by mass or less, 0.40 parts by mass or less, or It may be 0.36 parts by mass or less. From these viewpoints, the content of component (D) may be 0.01 to 5.0 parts by mass, 0.04 to 5.0 parts by mass, or 0.10 to 1.0 parts by mass.
- the content of component (D) may be within the following ranges per 100 parts by mass of component (B).
- the content of component (D) is 0.01 parts by mass or more, 0.03 parts by mass or more, 0.05 parts by mass or more, and 0.08 parts by mass from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. Parts by mass or more, 0.10 parts by mass or more, 0.15 parts by mass or more, 0.20 parts by mass or more, 0.25 parts by mass or more, 0.30 parts by mass or more, 0.35 parts by mass or more, 0.40 mass parts parts or more, or 0.45 parts by mass or more.
- the content of component (D) is 0.50 parts by mass or more, 0.51 parts by mass or more, and 0.55 parts by mass or more from the viewpoint of easily obtaining excellent adhesion and from the viewpoint of easily obtaining excellent sensitivity. , 0.60 parts by mass or more, 0.65 parts by mass or more, or 0.68 parts by mass or more.
- the content of component (D) is 5.0 parts by mass or less, 3.0 parts by mass or less, 1.0 parts by mass or less, and 0.80 from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. It may be 0.70 parts by mass or less, or 0.68 parts by mass or less.
- the content of component (D) is 0.65 parts by mass or less, 0.60 parts by mass or less, 0.55 parts by mass or less, 0.51 parts by mass or less, 0.65 parts by mass or less, 0.51 parts by mass or less, or 0.60 parts by mass or less, from the viewpoint of easily obtaining excellent followability. It may be 50 parts by mass or less, or 0.45 parts by mass or less. From these viewpoints, the content of component (D) may be 0.01 to 5.0 parts by mass, 0.05 to 5.0 parts by mass, or 0.10 to 1.0 parts by mass.
- the content of component (D) may be within the following range with respect to 100 parts by mass of the total amount of components (C) and (D).
- the content of component (D) is 0.10 parts by mass or more, 0.50 parts by mass or more, 0.80 parts by mass or more, and 1.0 part by mass from the viewpoint of easily obtaining excellent followability, resolution and adhesion. Parts by mass or more, 1.5 parts by mass or more, 2.0 parts by mass or more, 2.5 parts by mass or more, 3.0 parts by mass or more, 3.5 parts by mass or more, or 3.8 parts by mass or more good.
- the content of component (D) is 4.0 parts by mass or more, 4.5 parts by mass or more, and 5.0 parts by mass or more from the viewpoint of easily obtaining excellent adhesion and from the viewpoint of easily obtaining excellent sensitivity. , more than 5.0 parts by mass, 5.5 parts by mass or more, or 5.7 parts by mass or more.
- the content of component (D) is 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, 9.0 parts by mass or less, from the viewpoint of easily obtaining excellent followability, resolution and adhesion. It may be 0 parts by mass or less, 7.0 parts by mass or less, 6.0 parts by mass or less, or 5.7 parts by mass or less.
- the content of component (D) is 5.5 parts by mass or less, 5.0 parts by mass or less, less than 5.0 parts by mass, 4.5 parts by mass or less, 4. It may be 0 parts by mass or less, or 3.8 parts by mass or less. From these viewpoints, the content of component (D) may be 0.10 to 20 parts by mass, or 1.0 to 10 parts by mass.
- the photosensitive film and photosensitive resin composition according to the present embodiment may contain a polymerization inhibitor (excluding compounds corresponding to any of the components (A) to (D)), and contains a polymerization inhibitor. It doesn't have to be.
- a polymerization inhibitor suppresses polymerization in an unexposed area during formation of a resist pattern, and tends to improve stability of sensitivity over time and resolution.
- Polymerization inhibitors include catechol compounds (eg, tert-butylcatechol such as 4-tert-butylcatechol), hindered amines (eg, 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl), 4 -hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl and the like.
- the photosensitive film and the photosensitive resin composition according to the present embodiment may contain a catechol compound from the viewpoint of easily obtaining excellent sensitivity and stability over time.
- the content of the polymerization inhibitor may be within the following range with respect to the total amount of 100 parts by mass of components (A) and (B).
- the content of the polymerization inhibitor is 0.001 parts by mass or more, 0.003 parts by mass or more, 0.005 parts by mass or more, and 0.008 parts by mass from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. parts or more, or 0.010 parts by mass or more.
- the content of the polymerization inhibitor may be 0.011 parts by mass or more, 0.012 parts by mass or more, or 0.015 parts by mass or more from the viewpoint of easily obtaining even better resolution.
- the content of the polymerization inhibitor is 0.100 parts by mass or less, 0.050 parts by mass or less, 0.040 parts by mass or less, and 0.030 parts by mass from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. parts or less, 0.020 parts by mass or less, or 0.015 parts by mass or less.
- the content of the polymerization inhibitor is 0.012 parts by mass or less, 0.011 parts by mass or less, or 0.010 parts by mass from the viewpoint of easily obtaining excellent followability and from the viewpoint of easily obtaining excellent sensitivity. may be: From these points of view, the content of the polymerization inhibitor may be 0.001 to 0.100 parts by mass.
- the content of the polymerization inhibitor may be 0 parts by mass or may exceed 0 parts by mass.
- the photosensitive resin composition according to this embodiment may contain an organic solvent.
- Organic solvents include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether and the like.
- the photosensitive film and photosensitive resin composition according to the present embodiment may contain other components (excluding compounds corresponding to any of components (A) to (D)) other than the components described above.
- Other components include hydrogen donors (bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, leuco crystal violet, N-phenylglycine, etc.) and dyes (malachite green, etc.).
- mercapto group-containing Hydrogen donor sensitizer, photocoloring agent, anti-thermocoloring agent, plasticizer (p-toluenesulfonamide, etc.), pigment, filler, antifoaming agent, flame retardant, stabilizer, adhesion imparting agent, leveling agents, release accelerators, antioxidants, perfumes, imaging agents, thermal cross-linking agents, thermal radical polymerization initiators, and the like.
- the content of the thermal radical polymerization initiator is based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content), It may be 0.5% by mass or less, less than 0.5% by mass, 0.1% by mass or less, 0.01% by mass or less, or 0.001% by mass or less.
- the photosensitive film and photosensitive resin composition according to the present embodiment may not contain a thermal radical polymerization initiator (the above content may be substantially 0% by mass).
- a vinyl polymer e.g., a vinyl polymer containing a side chain having an epoxy group
- an oxetane compound e.g., even if it has a substituent
- the content of at least one selected from the group consisting of oxetane compounds having two or more good oxetane rings is 20% by mass based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content). Below, it may be less than 20% by mass, 10% by mass or less, 1% by mass or less, 0.1% by mass or less, 0.01% by mass or less, or 0.001% by mass or less.
- the photosensitive film and photosensitive resin composition according to the present embodiment include a vinyl polymer (e.g., a vinyl polymer containing a side chain having an epoxy group) and an oxetane compound (e.g., even if it has a substituent oxetane compounds having two or more good oxetane rings) may not be contained (the above content may be substantially 0% by mass).
- a vinyl polymer e.g., a vinyl polymer containing a side chain having an epoxy group
- an oxetane compound e.g., even if it has a substituent oxetane compounds having two or more good oxetane rings
- the content of at least one selected from the group consisting of anthracene compounds, distyrylbenzene compounds and naphthalene compounds is the total amount of the photosensitive film or the photosensitive resin It may be 0.01% by mass or less, less than 0.01% by mass, 0.001% by mass or less, or 0.0001% by mass or less based on the total amount of the composition (total solid content).
- the photosensitive film and photosensitive resin composition according to the present embodiment may not contain at least one selected from the group consisting of an anthracene compound, a distyrylbenzene compound and a naphthalene compound (the above content is substantially 0). % by mass).
- the content of the nitroxyl compound is based on 100 parts by mass of component (A) or 100 parts by mass of the total amount of components (A) and (B). , 0.005 parts by weight or less, less than 0.005 parts by weight, 0.001 parts by weight or less, or 0.0001 parts by weight or less.
- the photosensitive film and photosensitive resin composition according to the present embodiment may not contain a nitroxyl compound (the above content may be substantially 0 parts by mass).
- the content of the mercapto compound is 0.1 part by mass or less, 0.1 part by mass or less with respect to 100 parts by mass as the total amount of components (A) and (B). It may be less than 1 part by weight, 0.001 parts by weight or less, less than 0.001 parts by weight, or 0.0001 parts by weight or less.
- the photosensitive film and photosensitive resin composition according to the present embodiment may not contain a mercapto compound (the above content may be substantially 0 parts by mass).
- a photosensitive element according to this embodiment includes a support and a photosensitive resin layer disposed on the support, and the photosensitive resin layer is the photosensitive film according to this embodiment.
- the photosensitive element according to this embodiment may comprise a protective layer disposed on the photosensitive resin layer.
- the photosensitive element according to this embodiment may comprise a cushion layer, an adhesive layer, a light absorbing layer, a gas barrier layer, and the like.
- the photosensitive element may be in the form of a sheet, or in the form of a photosensitive element roll wound around a core.
- FIG. 1 is a schematic cross-sectional view showing an example of a photosensitive element.
- the photosensitive element 1 includes a support (support film) 2, a photosensitive resin layer (photosensitive film) 3 disposed on the support 2, and a photosensitive resin layer 3 disposed on the and a protective layer (protective film) 4.
- the photosensitive resin layer 3 is made of the photosensitive resin composition according to this embodiment.
- the photosensitive element 1 can be obtained, for example, by the following procedure.
- the photosensitive resin layer 3 is formed on the support 2 .
- the photosensitive resin layer 3 can be formed, for example, by drying a coating layer formed by applying a photosensitive resin composition containing an organic solvent.
- a protective layer 4 is arranged on the photosensitive resin layer 3 .
- Each of the support and the protective layer may be a polymer film having heat resistance and solvent resistance, such as a polyester film (polyethylene terephthalate film, etc.), a polyolefin film (polyethylene film, polypropylene film, etc.), a hydrocarbon-based polymer (polyolefin film, etc.). excluding film).
- the type of film forming the protective layer and the type of film forming the support may be the same or different.
- the thickness of the support may be 1 ⁇ m or more, 5 ⁇ m or more, 10 ⁇ m or more, or 15 ⁇ m or more from the viewpoint of easily suppressing damage to the support when the support is peeled off from the photosensitive resin layer.
- the thickness of the support may be 100 ⁇ m or less, 50 ⁇ m or less, 30 ⁇ m or less, or 20 ⁇ m or less from the viewpoint of favorable exposure when exposed through the support.
- the thickness of the protective layer is 1 ⁇ m or more, 5 ⁇ m or more, 10 ⁇ m or more, or It may be 15 ⁇ m or more.
- the thickness of the protective layer may be 100 ⁇ m or less, 50 ⁇ m or less, or 30 ⁇ m or less from the viewpoint of easily improving productivity.
- the method for producing a laminate according to the present embodiment includes an arrangement step of arranging a photosensitive resin layer on a substrate (for example, a substrate) using the photosensitive film, the photosensitive element, or the photosensitive resin composition according to the present embodiment. (Photosensitive resin layer arranging step), an exposure step of photocuring (exposing) a part of the photosensitive resin layer, and removing at least a part of the uncured portion (unexposed portion) of the photosensitive resin layer and a developing step of forming a cured product pattern.
- the laminate according to this embodiment is obtained by the method for producing a laminate according to this embodiment, and may be a wiring board (for example, a printed wiring board).
- the laminate according to the present embodiment may be in a mode including a substrate and a cured product pattern (cured product according to the present embodiment) arranged on the substrate.
- the base material may have recesses.
- the cross-sectional shape of the concave portion (cross-sectional shape perpendicular to the stacking direction) may be circular (for example, substantially perfect circular), rectangular, linear (linear), or the like.
- the concave portion of the substrate may be a bottomed concave portion.
- the diameter (for example, maximum diameter) or depth (length in the stacking direction) of the recess may be within the following ranges.
- the diameter of the recess may be 10 ⁇ m or more, 30 ⁇ m or more, 50 ⁇ m or more, 80 ⁇ m or more, 100 ⁇ m or more, 120 ⁇ m or more, 150 ⁇ m or more, 180 ⁇ m or more, or 200 ⁇ m or more.
- the diameter of the recess may be 500 ⁇ m or less, 400 ⁇ m or less, 300 ⁇ m or less, 250 ⁇ m or less, or 200 ⁇ m or less. From these points of view, the diameter of the recess may be 10 to 500 ⁇ m.
- the depth of the recess may be 1 ⁇ m or more, 3 ⁇ m or more, 5 ⁇ m or more, 6 ⁇ m or more, or 8 ⁇ m or more.
- the depth of the recess may be 20 ⁇ m or less, 18 ⁇ m or less, 15 ⁇ m or less, 12 ⁇ m or less, 10 ⁇ m or less, or 8 ⁇ m or less.
- the depth of the recess may be 1-20 ⁇ m.
- a photosensitive resin layer made of the photosensitive resin composition according to the present embodiment is placed on the substrate.
- the photosensitive resin layer may be formed by removing the protective layer from the photosensitive element and pressing the photosensitive resin layer of the photosensitive element onto the substrate while heating. It may be formed by coating and drying on the material.
- the base material has a concave portion having the above diameter (for example, a diameter of 500 ⁇ m or less), and at least a part of the photosensitive resin layer is arranged in the concave portion in the placing step. It's okay.
- an actinic ray is irradiated with a mask placed on the photosensitive resin layer, and a region other than the region where the mask is placed in the photosensitive resin layer may be exposed and photocured. Instead, a part of the photosensitive resin layer may be exposed and photocured by irradiating actinic rays in a desired pattern by a direct drawing exposure method such as an LDI exposure method or a DLP exposure method.
- an ultraviolet light source or a visible light source may be used, such as 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), a semiconductor laser, and the like. is mentioned.
- the development method in the development process may be, for example, wet development or dry development.
- Wet development can be carried out by using a developer corresponding to the photosensitive resin composition, for example, by dipping, puddle, spraying, brushing, slapping, scrubbing, rocking immersion, and the like.
- the developer is appropriately selected according to the constitution of the photosensitive resin composition, and may be an alkaline developer or an organic solvent developer.
- Alkaline developers include alkali hydroxides such as lithium, sodium or potassium hydroxide; alkali carbonates such as lithium, sodium, potassium or ammonium carbonates or bicarbonates; alkali metals such as potassium phosphate and sodium phosphate. Phosphates; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; borax; sodium metasilicate; tetramethylammonium hydroxide; ethanolamine; ethylenediamine; diethylenetriamine; It may be an aqueous solution containing a base such as 3-propanediol; 1,3-diamino-2-propanol; morpholine.
- alkali hydroxides such as lithium, sodium or potassium hydroxide
- alkali carbonates such as lithium, sodium, potassium or ammonium carbonates or bicarbonates
- alkali metals such as potassium phosphate and sodium phosphate.
- Phosphates alkali metal pyrophosphates such as sodium
- the organic solvent developer may contain organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methylisobutylketone and ⁇ -butyrolactone.
- organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methylisobutylketone and ⁇ -butyrolactone.
- the method for producing a laminate according to the present embodiment may include, after the developing step, a metal layer forming step of forming a metal layer on at least part of the portion of the substrate where the cured product pattern is not formed.
- the laminate according to the present embodiment includes a substrate, a cured product pattern (cured product according to the present embodiment) arranged on the substrate, and at least one part of the substrate where the cured product pattern is not formed. and a metal layer disposed on the part.
- the metal layer in the metal layer forming step may be, for example, a metal copper layer.
- the metal layer can be formed by plating, for example.
- the plating treatment may be one or both of electrolytic plating treatment and electroless plating treatment.
- the method for manufacturing a laminate according to the present embodiment includes a step of further curing the resist pattern by heating at 60 to 250° C. or exposing at 0.2 to 10 J/cm 2 after the developing step. you can
- the method for manufacturing a laminate according to this 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, developing with a strong alkaline aqueous solution by an immersion method, a spray method, or the like.
- Solution (a) 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 parts by mass of azobisisobutyronitrile was prepared.
- a solution (b) was prepared by dissolving 0.5 parts by mass of azobisisobutyronitrile in 50 parts by mass of a mixture of 30 parts by mass of methyl cellosolve and 20 parts by mass of toluene.
- the solution (a) was dropped into the flask over 4 hours at a constant dropping rate, the solution in the flask was stirred at 80° C. for 2 hours.
- the solution (b) was added dropwise into the flask over 10 minutes at a constant dropping rate, and then the solution in the flask was stirred at 80° C. for 3 hours.
- the solution in the flask was heated to 95°C over 1 hour and kept at 90°C for 2 hours, then stirring was stopped and the solution was cooled to room temperature (25°C) to obtain a solution of binder polymer A1.
- the non-volatile content (solid content) of the solution of binder polymer A1 was 49% by mass.
- the acid value of binder polymer A1 was 176 mgKOH/g.
- the binder polymer A1 had a weight average molecular weight (Mw) of 35,000 and a number average molecular weight (Mn) of 16,000.
- Mw weight average molecular weight
- Mn number average molecular weight
- the weight-average molecular weight and number-average molecular weight were measured by gel permeation chromatography (GPC) under the following conditions and derived by conversion using a standard polystyrene calibration curve.
- the non-volatile content (solid content) of the solution of binder polymer A2 was 49% by mass.
- the binder polymer A2 had an acid value of 175 mgKOH/g, a weight average molecular weight (Mw) of 35,000, and a number average molecular weight (Mn) of 16,500.
- a photosensitive resin composition was prepared by mixing each component shown in Table 1, 16 parts by mass of toluene, 6 parts by mass of methanol, and 10 parts by mass of acetone.
- Table 1 shows the amount (parts by mass) of each component, and the amount of the binder polymer and FA-321M (70) is the weight of the non-volatile matter (solid content). Details of each component shown in Table 1 are as follows.
- BCIM 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Hampford)
- TBC 4-tert-butyl catechol (manufactured by DIC Corporation, trade name “DIC-TBC”)
- LCV Leuco Crystal Violet (manufactured by Yamada Chemical Industry Co., Ltd.)
- MKG Malachite Green (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
- SF-808H a mixture of carboxybenzotriazole, 5-amino-1H-tetrazole and methoxypropanol (manufactured by Sanwa Kasei Co., Ltd.)
- a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name “FB-40”) having a thickness of 16 ⁇ m was prepared as a support. After coating the above-mentioned photosensitive resin composition on the support so that the thickness becomes uniform, the photosensitive resin composition is sequentially dried in a hot air convection dryer at 70° C. and 110° C. to obtain a photosensitive resin layer (photosensitive film. An average thickness of 10 locations after drying: 19 ⁇ m) was formed.
- a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name "NF-15") was laminated as a protective layer to this photosensitive resin layer to obtain a photosensitive element comprising a support, a photosensitive resin layer and a protective layer in this order. .
- a copper-clad laminate (substrate, manufactured by Showa Denko Materials Co., Ltd., trade name: MCL-E-67) with copper foil (thickness: 18 ⁇ m) arranged on both sides of a glass epoxy material is pickled and washed with water. Afterwards, the substrate was obtained by drying with an air stream. Next, after heating this substrate to 80° C., while peeling off the protective layer, the photosensitive element is laminated so that the photosensitive resin layer is in contact with the copper surface, thereby forming a substrate (copper-clad laminate ), a photosensitive resin layer, and a support in this order to obtain a laminate A. Lamination was performed using heat rolls at 110° C. at a pressure of 0.4 MPa and a roll speed of 1.5 m/min.
- a copper-clad laminate (substrate, manufactured by Showa Denko Materials Co., Ltd., trade name: MCL-E-67) with copper foil (thickness: 18 ⁇ m) arranged on both sides of a glass epoxy material is pickled and washed with water. Afterwards, the substrate was obtained by drying with an air flow. Next, round holes (cross-sectional shape: substantially perfect circle) having a diameter of 200 ⁇ m and a depth of 8 ⁇ m were formed in this substrate at 25 locations (arrangement: 5 ⁇ 5, shortest distance between adjacent round holes: 2 cm).
- the support After exposure, the support is peeled off from the laminate A to expose the photosensitive resin layer, and a 1% by weight sodium carbonate aqueous solution is sprayed at 30° C. for twice the minimum development time described above, thereby removing the unexposed area. removed.
- the resolution was evaluated by Table 1 shows the results. A smaller value means better resolution.
- the support After exposure, the support is peeled off from the laminate A to expose the photosensitive resin layer, and a 1% by weight sodium carbonate aqueous solution is sprayed at 30° C. for twice the minimum development time described above, thereby removing the unexposed area. removed.
- the adhesion was evaluated by Table 1 shows the results. A smaller value means better adhesion.
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Abstract
A photosensitive film which comprises (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a pyrazoline compound, and which has a thickness of 20 μm or less. A photosensitive element 1 which is provided with a supporting body 2 and a photosensitive resin layer 3 that is arranged on the supporting body 2, wherein the photosensitive resin layer 3 is the above-described photosensitive film. A method for producing a multilayer body, the method comprising: an arrangement step in which a photosensitive resin layer is arranged on a base material with use of the above-described photosensitive film or the above-described photosensitive element 1; a step in which a part of the photosensitive resin layer is photocured; and a step in which a cured product pattern is formed by removing at least a part of an uncured portion of the photosensitive resin layer.
Description
本開示は、感光性フィルム、感光性エレメント、積層体の製造方法等に関する。
The present disclosure relates to a photosensitive film, a photosensitive element, a laminate manufacturing method, and the like.
配線基板等として用いることが可能な積層体の製造においては、所望の配線を得るためにレジストパターンが形成される。レジストパターンは、フィルム状の感光性樹脂組成物である感光性フィルムを露光及び現像することにより形成することができる。感光性樹脂組成物としては、各種組成物が検討されている。例えば、下記特許文献１では、バインダーポリマーと、光重合性化合物と、特定の光重合開始剤と、を含有する感光性樹脂組成物が記載されている。
In the production of a laminate that can be used as a wiring board or the like, a resist pattern is formed to obtain desired wiring. A resist pattern can be formed by exposing and developing a photosensitive film, which is a film-shaped photosensitive resin composition. Various compositions have been studied as the photosensitive resin composition. For example, Patent Document 1 below describes a photosensitive resin composition containing a binder polymer, a photopolymerizable compound, and a specific photopolymerization initiator.
感光性フィルムを用いて、レジストパターンとして用いることが可能な硬化物パターンを形成するに際して、断面円形の凹部（丸穴）内に感光性樹脂組成物を充填しつつ硬化物パターンを形成する場合がある。しかしながら、従来の感光性フィルムでは、凹部内に空隙が生じた状態で硬化物パターンが形成され、凹部の形状に対する追従性（充填性）が充分でない場合がある。また、従来、厚さ２５μｍの感光性フィルムが常用されているものの、積層体の厚さの低減等を目的として、感光性フィルムの厚さを２０μｍ以下に低減することが求められる場合がある。しかしながら、このように感光性フィルムの厚さを低減すると、凹部を充填するための感光性樹脂組成物の量が減少することから、凹部内に空隙が生じた状態で硬化物パターンが形成されやすい。そのため、感光性フィルムに対しては、厚さが２０μｍ以下である場合であっても、断面円形の凹部に対する追従性に優れることが求められる。
When forming a cured product pattern that can be used as a resist pattern using a photosensitive film, there is a case where the cured product pattern is formed while filling a recess (round hole) having a circular cross section with a photosensitive resin composition. be. However, in conventional photosensitive films, the cured product pattern is formed with voids in the recesses, and the followability (filling property) to the shape of the recesses may not be sufficient. In addition, although a photosensitive film having a thickness of 25 μm has been commonly used, there are cases where the thickness of the photosensitive film is required to be reduced to 20 μm or less for the purpose of reducing the thickness of the laminate. However, when the thickness of the photosensitive film is reduced in this way, the amount of the photosensitive resin composition for filling the concave portions is reduced, so that the cured product pattern is likely to be formed with voids in the concave portions. . Therefore, even when the thickness is 20 μm or less, the photosensitive film is required to have excellent conformability to concave portions having a circular cross section.
本開示の一側面は、厚さ２０μｍ以下の感光性フィルムとして、断面円形の凹部に対する追従性に優れる感光性フィルムを提供することを目的とする。本開示の他の一側面は、当該感光性フィルムを用いた感光性エレメントを提供することを目的とする。本開示の他の一側面は、上述の感光性フィルム又は感光性エレメントを用いた積層体の製造方法を提供することを目的とする。
An object of one aspect of the present disclosure is to provide a photosensitive film having a thickness of 20 μm or less, which has excellent followability to concave portions having a circular cross section. Another aspect of the present disclosure aims to provide a photosensitive element using the photosensitive film. Another aspect of the present disclosure aims to provide a method for producing a laminate using the photosensitive film or photosensitive element described above.
本開示の一側面は、（Ａ）バインダーポリマーと、（Ｂ）光重合性化合物と、（Ｃ）光重合開始剤と、（Ｄ）ピラゾリン化合物と、を含有し、厚さが２０μｍ以下である、感光性フィルムに関する。
One aspect of the present disclosure contains (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a pyrazoline compound, and has a thickness of 20 μm or less. , on photosensitive films.
このような感光性フィルムは、厚さが２０μｍ以下であるものの、断面円形の凹部に対する追従性に優れる。
Although such a photosensitive film has a thickness of 20 μm or less, it has excellent conformability to recesses having a circular cross section.
本開示の他の一側面は、支持体と、当該支持体上に配置された感光性樹脂層と、を備え、前記感光性樹脂層が上述の感光性フィルムである、感光性エレメントに関する。
Another aspect of the present disclosure relates to a photosensitive element comprising a support and a photosensitive resin layer disposed on the support, wherein the photosensitive resin layer is the photosensitive film described above.
本開示の他の一側面は、上述の感光性フィルム又は上述の感光性エレメントを用いて感光性樹脂層を基材上に配置する配置工程と、前記感光性樹脂層の一部を光硬化させる工程と、前記感光性樹脂層の未硬化部の少なくとも一部を除去して硬化物パターンを形成する工程と、を備える、積層体の製造方法に関する。
Another aspect of the present disclosure includes an arrangement step of arranging a photosensitive resin layer on a substrate using the above-described photosensitive film or the above-described photosensitive element, and photocuring a part of the photosensitive resin layer. and removing at least part of the uncured portion of the photosensitive resin layer to form a cured product pattern.
本開示の一側面によれば、厚さ２０μｍ以下の感光性フィルムとして、断面円形の凹部に対する追従性に優れる感光性フィルムを提供することができる。本開示の他の一側面によれば、当該感光性フィルムを用いた感光性エレメントを提供することができる。本開示の他の一側面によれば、上述の感光性フィルム又は感光性エレメントを用いた積層体の製造方法を提供することができる。
According to one aspect of the present disclosure, as a photosensitive film having a thickness of 20 μm or less, it is possible to provide a photosensitive film having excellent followability to concave portions having a circular cross section. According to another aspect of the present disclosure, it is possible to provide a photosensitive element using the photosensitive film. According to another aspect of the present disclosure, it is possible to provide a method for producing a laminate using the photosensitive film or photosensitive element described above.
以下、本開示の実施形態について詳細に説明する。但し、本開示は以下の実施形態に限定されるものではない。
Hereinafter, embodiments of the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments.
数値範囲の「Ａ以上」とは、Ａ、及び、Ａを超える範囲を意味する。数値範囲の「Ａ以下」とは、Ａ、及び、Ａ未満の範囲を意味する。本明細書に段階的に記載されている数値範囲において、ある段階の数値範囲の上限値又は下限値は、他の段階の数値範囲の上限値又は下限値と任意に組み合わせることができる。本明細書に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてよい。「Ａ又はＢ」とは、Ａ及びＢのどちらか一方を含んでいればよく、両方とも含んでいてもよい。本明細書に例示する材料は、特に断らない限り、１種を単独で又は２種以上を組み合わせて用いることができる。組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。「層」との語は、平面図として観察したときに、全面に形成されている形状の構造に加え、一部に形成されている形状の構造も包含される。「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。「（メタ）アクリレート」とは、アクリレート、及び、それに対応するメタクリレートの少なくとも一方を意味する。「（メタ）アクリル酸」等の他の類似の表現においても同様である。「アルキル基」は、特に断らない限り、直鎖状、分岐又は環状のいずれであってもよい。
"A or more" in the numerical range means A and the range exceeding A. "A or less" in a numerical range means A and a range less than A. In the numerical ranges described stepwise in this specification, the upper limit value or lower limit value of the numerical range in one step can be arbitrarily combined with the upper limit value or lower limit of the numerical range in another step. In the numerical ranges described herein, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples. "A or B" may include either A or B, or may include both. The materials exemplified in this specification can be used singly or in combination of two or more unless otherwise specified. The content of each component in the composition means the total amount of the plurality of substances present in the composition unless otherwise specified when there are multiple substances corresponding to each component in the composition. The term "layer" includes not only a shape structure formed over the entire surface but also a shape structure formed partially when observed as a plan view. The term "process" is included in the term not only as an independent process, but also as long as the intended action of the process is achieved even if it is not clearly distinguishable from other processes. "(Meth)acrylate" means at least one of acrylate and its corresponding methacrylate. The same applies to other similar expressions such as "(meth)acrylic acid". An "alkyl group" may be linear, branched or cyclic, unless otherwise specified.
本明細書において、感光性樹脂組成物の固形分は、感光性樹脂組成物において、揮発する物質（水、溶媒等）を除いた不揮発分を指す。すなわち、当該固形分は、感光性樹脂組成物の乾燥において揮発せずに残る成分（溶媒以外の成分）を指し、室温（２５℃）で液状、水飴状又はワックス状の成分も含む。
In this specification, the solid content of the photosensitive resin composition refers to the non-volatile content excluding volatile substances (water, solvent, etc.) in the photosensitive resin composition. That is, the solid content refers to the components (components other than the solvent) that remain without volatilizing when the photosensitive resin composition dries, and includes components that are liquid, starch syrup-like, or wax-like at room temperature (25°C).
＜感光性フィルム及び感光性樹脂組成物＞
本実施形態に係る感光性フィルムは、（Ａ）バインダーポリマーと、（Ｂ）光重合性化合物と、（Ｃ）光重合開始剤と、（Ｄ）ピラゾリン化合物と、を含有し、当該感光性フィルムの厚さは、２０μｍ以下である。本実施形態に係る感光性フィルムは、フィルム状の感光性樹脂組成物であり、本実施形態に係る感光性樹脂組成物をフィルム状に成形することにより得ることができる。本実施形態に係る感光性樹脂組成物は、本実施形態に係る感光性フィルムと同様の含有成分を含有することができる。 <Photosensitive film and photosensitive resin composition>
The photosensitive film according to the present embodiment contains (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a pyrazoline compound, and the photosensitive film is 20 μm or less. The photosensitive film according to this embodiment is a film-like photosensitive resin composition, and can be obtained by molding the photosensitive resin composition according to this embodiment into a film. The photosensitive resin composition according to this embodiment can contain the same ingredients as the photosensitive film according to this embodiment.
本実施形態に係る感光性フィルムは、（Ａ）バインダーポリマーと、（Ｂ）光重合性化合物と、（Ｃ）光重合開始剤と、（Ｄ）ピラゾリン化合物と、を含有し、当該感光性フィルムの厚さは、２０μｍ以下である。本実施形態に係る感光性フィルムは、フィルム状の感光性樹脂組成物であり、本実施形態に係る感光性樹脂組成物をフィルム状に成形することにより得ることができる。本実施形態に係る感光性樹脂組成物は、本実施形態に係る感光性フィルムと同様の含有成分を含有することができる。 <Photosensitive film and photosensitive resin composition>
The photosensitive film according to the present embodiment contains (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a pyrazoline compound, and the photosensitive film is 20 μm or less. The photosensitive film according to this embodiment is a film-like photosensitive resin composition, and can be obtained by molding the photosensitive resin composition according to this embodiment into a film. The photosensitive resin composition according to this embodiment can contain the same ingredients as the photosensitive film according to this embodiment.
本実施形態に係る感光性フィルムは、厚さが２０μｍ以下であるものの、断面円形（例えば略真円）の凹部（例えば、直径２００μｍ及び深さ８μｍ）に対する追従性（丸穴追従性、充填性）に優れる。本実施形態に係る感光性フィルムによれば、実施例に記載の評価において、２００００μｍ２未満（好ましくは１５０００μｍ２以下）の追従性を得ることができる。
Although the photosensitive film according to the present embodiment has a thickness of 20 μm or less, it has a followability (a round hole followability, a filling property, and a ). According to the photosensitive film according to the present embodiment, followability of less than 20000 μm 2 (preferably 15000 μm 2 or less) can be obtained in the evaluation described in Examples.
本実施形態に係る感光性フィルム及び感光性樹脂組成物により優れた追従性が得られる要因について、本発明者は下記のとおり推測している。但し、要因は下記の内容に限定されない。すなわち、（Ａ）成分、（Ｂ）成分及び（Ｃ）成分を併用するに際して（Ｄ）成分を用いることにより、（Ｄ）成分の各種物性（結晶性、融点等）が、断面円形の凹部を有する基材に感光性フィルムを積層する際の熱プロセス（ラミネート等）において好適に作用する。これにより、熱プロセスにおいて好適な流動性が得られやすいことから、感光性フィルムの厚さが２０μｍ以下であっても（凹部を充填するための感光性樹脂組成物の量が少なくても）優れた追従性が得られる。
The present inventors presume as follows about the factors by which the photosensitive film and the photosensitive resin composition according to the present embodiment provide excellent conformability. However, the factors are not limited to the following contents. That is, by using component (D) when using component (A), component (B), and component (C) in combination, various physical properties (crystallinity, melting point, etc.) of component (D) can be adjusted to form recesses with circular cross-sections. It acts favorably in a thermal process (such as lamination) when laminating a photosensitive film on a substrate having the same. As a result, suitable fluidity can be easily obtained in the thermal process, so even if the thickness of the photosensitive film is 20 μm or less (even if the amount of the photosensitive resin composition for filling the recesses is small), it is excellent. Followability is obtained.
本実施形態に係る感光性フィルムは、断面円形の凹部を有する基材に積層した際に優れた追従性を有していればよく、円形とは異なる断面形状の凹部を有する基材、凹部を有さない基材等に積層してもよい。
The photosensitive film according to the present embodiment only needs to have excellent followability when laminated on a substrate having a concave portion with a circular cross section. You may laminate|stack on the base material etc. which do not have.
ところで、感光性フィルム又は感光性樹脂組成物を用いて、レジストパターンとして用いることが可能な硬化物パターンを形成するに際して、直線状のライン部分と、ライン部分に隣接する直線状のスペース部分と、を有する硬化物パターンを形成する場合がある。そして、ライン部分の幅（ライン幅）よりもスペース部分の幅（スペース幅）が小さい硬化物パターンを形成する場合においてライン部分及びスペース部分が良好に形成される特性として、優れた解像性が求められる場合がある。また、スペース幅よりもライン幅が小さい硬化物パターンを形成する場合においてライン部分及びスペース部分が良好に形成される特性として、優れた密着性が求められる場合がある。
By the way, when forming a cured product pattern that can be used as a resist pattern using a photosensitive film or a photosensitive resin composition, linear line portions, linear space portions adjacent to the line portions, may form a cured product pattern having. Then, when forming a cured product pattern in which the width of the space portion (space width) is smaller than the width of the line portion (line width), excellent resolution is a characteristic that the line portion and the space portion are formed well. may be requested. Further, in the case of forming a cured product pattern having a line width smaller than the space width, there are cases where excellent adhesion is required as a characteristic for good formation of line portions and space portions.
本実施形態に係る感光性フィルム又は感光性樹脂組成物によれば、ライン幅よりもスペース幅が小さい硬化物パターンを形成する場合における優れた解像性を得ることができる。本実施形態に係る感光性フィルムによれば、実施例に記載の評価において、例えば１５μｍ以下の解像性を得ることができる。
According to the photosensitive film or photosensitive resin composition according to the present embodiment, excellent resolution can be obtained when forming a cured pattern having a space width smaller than the line width. According to the photosensitive film according to the present embodiment, a resolution of, for example, 15 μm or less can be obtained in the evaluation described in Examples.
本実施形態に係る感光性フィルム又は感光性樹脂組成物によれば、スペース幅よりもライン幅が小さい硬化物パターンを形成する場合における優れた密着性を得ることができる。本実施形態に係る感光性フィルム及び感光性樹脂組成物によれば、実施例に記載の評価において、例えば１０μｍ以下の密着性を得ることができる。
According to the photosensitive film or photosensitive resin composition according to the present embodiment, excellent adhesion can be obtained when forming a cured product pattern having a line width smaller than the space width. According to the photosensitive film and the photosensitive resin composition according to the present embodiment, adhesion of, for example, 10 μm or less can be obtained in the evaluation described in Examples.
本実施形態に係る感光性フィルム又は感光性樹脂組成物によれば、未露光部が除去される最小時間を低減可能であり、優れた現像性を得ることができる。
According to the photosensitive film or photosensitive resin composition according to the present embodiment, it is possible to reduce the minimum time for removing the unexposed areas, and to obtain excellent developability.
本実施形態に係る感光性フィルム及び感光性樹脂組成物によれば、活性光線に対する優れた感度（経時変化前）を得ることができる。本実施形態に係る感光性フィルム及び感光性樹脂組成物によれば、実施例に記載の評価において、例えば１０５ｍＪ／ｃｍ２以下の露光量を得ることができる。
According to the photosensitive film and the photosensitive resin composition according to the present embodiment, excellent sensitivity to actinic rays (before change over time) can be obtained. According to the photosensitive film and the photosensitive resin composition according to the present embodiment, an exposure dose of, for example, 105 mJ/cm 2 or less can be obtained in the evaluation described in Examples.
本実施形態に係る感光性フィルム及び感光性樹脂組成物は、光硬化性を有し、当該感光性フィルム又は感光性樹脂組成物を光硬化することで硬化物を得ることができる。本実施形態に係る硬化物は、本実施形態に係る感光性フィルム又は感光性樹脂組成物の硬化物（光硬化物）である。本実施形態に係る硬化物は、パターン状（硬化物パターン）であってよく、レジストパターンであってよい。本実施形態に係る感光性フィルム及び感光性樹脂組成物により得ることが可能な硬化物パターンの形状は、特に限られない。
The photosensitive film and photosensitive resin composition according to the present embodiment are photocurable, and a cured product can be obtained by photocuring the photosensitive film or photosensitive resin composition. The cured product according to this embodiment is a cured product (photocured product) of the photosensitive film or photosensitive resin composition according to this embodiment. The cured product according to the present embodiment may be patterned (cured product pattern) or may be a resist pattern. The shape of the cured product pattern that can be obtained from the photosensitive film and the photosensitive resin composition according to this embodiment is not particularly limited.
本実施形態に係る感光性フィルムの厚さは２０μｍ以下であり、本実施形態に係る硬化物の厚さは、２０μｍ以下であってよい。本実施形態に係る感光性フィルム及び硬化物の厚さは、優れた追従性を得やすい観点、及び、充分な厚さのレジストパターンを得やすい観点から、１μｍ以上、３μｍ以上、５μｍ以上、５μｍ超、７μｍ以上、７μｍ超、８μｍ以上、１０μｍ以上、１０μｍ超、１５μｍ以上、１８μｍ以上、又は、１９μｍ以上であってよい。本実施形態に係る感光性フィルム及び硬化物の厚さは、優れた解像性及び密着性を得やすい観点から、１９μｍ以下であってよい。これらの観点から、本実施形態に係る感光性フィルム及び硬化物の厚さは、１～２０μｍ、５～２０μｍ、又は、１５～２０μｍであってよい。感光性フィルム及び硬化物の厚さは、１０箇所の平均厚さであってよい。
The thickness of the photosensitive film according to this embodiment may be 20 μm or less, and the thickness of the cured product according to this embodiment may be 20 μm or less. The thickness of the photosensitive film and cured product according to the present embodiment is 1 μm or more, 3 μm or more, 5 μm or more, and 5 μm from the viewpoint of easily obtaining excellent followability and from the viewpoint of easily obtaining a resist pattern with a sufficient thickness. It may be greater than, 7 μm or greater, greater than 7 μm, 8 μm or greater, 10 μm or greater, 10 μm or greater, 15 μm or greater, 18 μm or greater, or 19 μm or greater. The thickness of the photosensitive film and the cured product according to this embodiment may be 19 μm or less from the viewpoint of easily obtaining excellent resolution and adhesion. From these viewpoints, the thickness of the photosensitive film and cured product according to the present embodiment may be 1 to 20 μm, 5 to 20 μm, or 15 to 20 μm. The thickness of the photosensitive film and cured product may be an average thickness of 10 locations.
本実施形態に係る感光性フィルム及び感光性樹脂組成物において感光性が発現する波長は特に限定されない。本実施形態に係る感光性フィルム及び感光性樹脂組成物は、例えば、３００ｎｍ以上、３４０ｎｍ以上、３５０ｎｍ以上、３５５ｎｍ以上、３６５ｎｍ以上、３７５ｎｍ以上、３９０ｎｍ以上、３９５ｎｍ以上、又は、４０５ｎｍ以上の波長の光に対する感光性を有してよい。本実施形態に係る感光性フィルム及び感光性樹脂組成物は、例えば、５００ｎｍ以下、４４０ｎｍ以下、４４０ｎｍ未満、４３６ｎｍ以下、４２０ｎｍ以下、４１０ｎｍ以下、又は、４０５ｎｍ以下の波長の光に対する感光性を有してよい。後述の露光工程においては、これらの波長の範囲内にピークを有する活性光線を用いることができる。本実施形態に係る感光性フィルム及び感光性樹脂組成物は、例えば、ネガ型の感光性フィルム及び感光性樹脂組成物として用いることができる。
The wavelength at which photosensitivity is exhibited in the photosensitive film and 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 are, for example, light having a wavelength of 300 nm or more, 340 nm or more, 350 nm or more, 355 nm or more, 365 nm or more, 375 nm or more, 390 nm or more, 395 nm or more, or 405 nm or more. may be sensitive to The photosensitive film and photosensitive resin composition according to the present embodiment have photosensitivity to light having a wavelength of, for example, 500 nm or less, 440 nm or less, less than 440 nm, 436 nm or less, 420 nm or less, 410 nm or less, or 405 nm or less. you can Actinic rays having peaks within these wavelength ranges can be used in the exposure step described later. The photosensitive film and photosensitive resin composition according to the present embodiment can be used, for example, as a negative photosensitive film and photosensitive resin composition.
本実施形態によれば、硬化物パターン（例えばレジストパターン）の形成への感光性樹脂組成物、感光性フィルム又は感光性エレメントの応用を提供することができる。本実施形態によれば、配線基板の製造への感光性樹脂組成物、感光性フィルム又は感光性エレメントの応用を提供することができる。
According to this embodiment, application of the photosensitive resin composition, photosensitive film, or photosensitive element to the formation of a cured product pattern (eg, resist pattern) can be provided. According to this embodiment, application of the photosensitive resin composition, photosensitive film, or photosensitive element to the production of wiring boards can be provided.
本実施形態に係る感光性フィルム及び感光性樹脂組成物は、（Ａ）成分としてバインダーポリマーを含有する。（Ａ）成分としては、アクリル系樹脂、スチレン系樹脂、エポキシ系樹脂、アミド系樹脂、アミドエポキシ系樹脂、アルキド系樹脂、フェノール系樹脂等が挙げられる。アクリル系樹脂は、（メタ）アクリロイル基を有する化合物（（メタ）アクリル酸化合物）を単量体単位として有する樹脂であり、当該単量体単位を有するスチレン系樹脂、エポキシ系樹脂、アミド系樹脂、アミドエポキシ系樹脂、アルキド系樹脂及びフェノール系樹脂はアクリル系樹脂に帰属する。（Ａ）成分は、フェノール性水酸基を有するバインダーポリマーを含まなくてよい。
The photosensitive film and photosensitive resin composition according to this embodiment contain a binder polymer as the (A) component. Component (A) includes acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, and the like. Acrylic resins are resins having a compound ((meth)acrylic acid compound) having a (meth)acryloyl group as a monomer unit, and styrene resins, epoxy resins, and amide resins having the monomer units. , amidoepoxy resins, alkyd resins and phenolic resins belong to acrylic resins. The component (A) does not have to contain a binder polymer having a phenolic hydroxyl group.
（Ａ）成分は、優れた追従性、解像性及び密着性を得やすい観点から、アクリル系樹脂を含んでよい。アクリル系樹脂の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、（Ａ）成分の全質量を基準として、５０質量％以上、５０質量％超、７０質量％以上、９０質量％以上、９５質量％以上、９８質量％以上、９９質量％以上、又は、実質的に１００質量％（（Ａ）成分が実質的にアクリル系樹脂からなる態様）であってよい。
The (A) component may contain an acrylic resin from the viewpoint of easily obtaining excellent followability, resolution and adhesion. The content of the acrylic resin is 50% by mass or more, more than 50% by mass, or 70% by mass or more, based on the total mass of the component (A), from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. , 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, or substantially 100% by mass (an aspect in which component (A) is substantially composed of an acrylic resin).
（メタ）アクリロイル基を有する化合物としては、（メタ）アクリル酸、（メタ）アクリル酸エステル等が挙げられる。（メタ）アクリル酸エステルとしては、（メタ）アクリル酸アルキル（（メタ）アクリル酸アルキルエステル;（メタ）アクリル酸シクロアルキルに該当する化合物を除く）、（メタ）アクリル酸シクロアルキル（（メタ）アクリル酸シクロアルキルエステル）、（メタ）アクリル酸アリール（（メタ）アクリル酸アリールエステル）、（メタ）アクリルアミド化合物（ジアセトンアクリルアミド等）、（メタ）アクリル酸グリシジルエステル、スチリル（メタ）アクリル酸などが挙げられる。
Examples of compounds having a (meth)acryloyl group include (meth)acrylic acid and (meth)acrylic acid esters. (Meth)acrylates include alkyl (meth)acrylates (alkyl (meth)acrylates; excluding compounds corresponding to cycloalkyl (meth)acrylates), cycloalkyl (meth)acrylates ((meth) cycloalkyl acrylate), aryl (meth)acrylate (aryl (meth)acrylate), (meth)acrylamide compounds (diacetone acrylamide, etc.), glycidyl (meth)acrylate, styryl (meth)acrylic acid, etc. is mentioned.
（Ａ）成分は、優れた追従性、解像性及び密着性を得やすい観点から、（メタ）アクリル酸を単量体単位として有してよい。（Ａ）成分が（メタ）アクリル酸を単量体単位として有する場合、（メタ）アクリル酸の単量体単位の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、（Ａ）成分を構成する単量体単位の全量を基準として下記の範囲であってよい。（メタ）アクリル酸の単量体単位の含有量は、１質量％以上、５質量％以上、１０質量％以上、１２質量％以上、１５質量％以上、１８質量％以上、２０質量％以上、２３質量％以上、２５質量％以上、又は、２７質量％以上であってよい。（メタ）アクリル酸の単量体単位の含有量は、５０質量％以下、５０質量％未満、４５質量％以下、４０質量％以下、３７質量％以下、３５質量％以下、３２質量％以下、３０質量％以下、又は、２７質量％以下であってよい。これらの観点から、（メタ）アクリル酸の単量体単位の含有量は、１～５０質量％であってよい。
The (A) component may have (meth)acrylic acid as a monomer unit from the viewpoint of easily obtaining excellent followability, resolution and adhesion. (A) When the component has (meth)acrylic acid as a monomer unit, the content of the (meth)acrylic acid monomer unit is from the viewpoint of easily obtaining excellent followability, resolution and adhesion. , (A) may be within the following ranges based on the total amount of the monomer units constituting component (A). The content of the monomer units of (meth)acrylic acid is 1% by mass or more, 5% by mass or more, 10% by mass or more, 12% by mass or more, 15% by mass or more, 18% by mass or more, 20% by mass or more, It may be 23% by mass or more, 25% by mass or more, or 27% by mass or more. The content of the monomer units of (meth)acrylic acid is 50% by mass or less, less than 50% by mass, 45% by mass or less, 40% by mass or less, 37% by mass or less, 35% by mass or less, 32% by mass or less, It may be 30% by mass or less, or 27% by mass or less. From these points of view, the content of the (meth)acrylic acid monomer unit may be 1 to 50% by mass.
（Ａ）成分は、優れた追従性、解像性及び密着性を得やすい観点から、（メタ）アクリル酸アルキルを単量体単位として有してよい。（メタ）アクリル酸アルキルのアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基等が挙げられ、アルキル基は、各種構造異性体であってよい。（メタ）アクリル酸アルキルのアルキル基の炭素数は、優れた追従性、解像性及び密着性を得やすい観点から、１～４、１～３、２～３、又は、１～２であってよい。
The (A) component may have an alkyl (meth)acrylate as a monomer unit from the viewpoint of easily obtaining excellent conformability, resolution and adhesion. Examples of the alkyl group of alkyl (meth)acrylate include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group. and the alkyl groups may be of various structural isomers. The number of carbon atoms in the alkyl group of the alkyl (meth)acrylate is 1 to 4, 1 to 3, 2 to 3, or 1 to 2 from the viewpoint of easily obtaining excellent followability, resolution and adhesion. you can
（メタ）アクリル酸アルキルのアルキル基は、置換基を有してよい。置換基としては、ヒドロキシ基、カルボキシ基、カルボン酸塩基、アルデヒド基、アルコキシ基（無置換のアルコキシ基（酸素原子に結合した無置換のアルキル基を有する構造）、又は、置換アルコキシ基（ヒドロキシアルコキシ基等））、カルボニル基、アルコキシカルボニル基、アルカノイル基（炭素数２～１２のアルカノイル基等）、オキシカルボニル基、カルボニルオキシ基、アミノ基、エポキシ基、フリル基、シアノ基、ハロゲノ基（フルオロ基、クロロ基、ブロモ基等）、ニトロ基、アセチル基、スルホニル基、スルホンアミド基などが挙げられる。（Ａ）成分としては、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ジエチルアミノエチル、（メタ）アクリル酸２，２，２－トリフルオロエチル、（メタ）アクリル酸２，２，３，３－テトラフルオロプロピル、α－クロロ（メタ）アクリル酸、α－ブロモ（メタ）アクリル酸等が挙げられる。
The alkyl group of the alkyl (meth)acrylate may have a substituent. Substituents include a hydroxy group, a carboxy group, a carboxylic acid group, an aldehyde group, an alkoxy group (unsubstituted alkoxy group (structure having an unsubstituted alkyl group bonded to an oxygen atom), or a substituted alkoxy group (hydroxyalkoxy group, etc.)), carbonyl group, alkoxycarbonyl group, alkanoyl group (alkanoyl group having 2 to 12 carbon atoms, etc.), oxycarbonyl group, carbonyloxy group, amino group, epoxy group, furyl group, cyano group, halogeno group (fluoro group, chloro group, bromo group, etc.), nitro group, acetyl group, sulfonyl group, sulfonamide group and the like. Component (A) includes dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3 (meth)acrylate, 3-tetrafluoropropyl, α-chloro(meth)acrylic acid, α-bromo(meth)acrylic acid and the like.
（Ａ）成分は、優れた追従性、解像性及び密着性を得やすい観点から、（メタ）アクリル酸ヒドロキシアルキルを単量体単位として有してよい。（メタ）アクリル酸ヒドロキシアルキルとしては、（メタ）アクリル酸ヒドロキシメチル、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチル、（メタ）アクリル酸ヒドロキシペンチル、（メタ）アクリル酸ヒドロキシヘキシル等が挙げられる。
The (A) component may have hydroxyalkyl (meth)acrylate as a monomer unit from the viewpoint of easily obtaining excellent followability, resolution and adhesion. Hydroxyalkyl (meth)acrylates include hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, Hydroxyhexyl (meth)acrylate and the like can be mentioned.
（Ａ）成分が（メタ）アクリル酸アルキルを単量体単位として有する場合における（メタ）アクリル酸アルキルの単量体単位の含有量、又は、（Ａ）成分が（メタ）アクリル酸ヒドロキシアルキルを単量体単位として有する場合における（メタ）アクリル酸ヒドロキシアルキルの単量体単位の含有量は、（Ａ）成分を構成する単量体単位の全量を基準として下記の範囲であってよい。上述の単量体単位の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、０．１０質量％以上、０．５０質量％以上、１．０質量％以上、１．５質量％以上、２．０質量％以上、２．５質量％以上、又は、３．０質量％以上であってよい。上述の単量体単位の含有量は、優れた感度及び現像性を得やすい観点、並びに、更に優れた追従性を得やすい観点から、３．５質量％以上、４．０質量％以上、４．５質量％以上、又は、５．０質量％以上であってよい。上述の単量体単位の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、２０質量％以下、１８質量％以下、１５質量％以下、１２質量％以下、１０質量％以下、８．０質量％以下、６．０質量％以下、５．５質量％以下、又は、５．０質量％以下であってよい。上述の単量体単位の含有量は、更に優れた解像性を得やすい観点から、４．５質量％以下、４．０質量％以下、３．５質量％以下、又は、３．０質量％以下であってよい。これらの観点から、上述の単量体単位の含有量は、０．１０～２０質量％、又は、０．１０～５．０質量％であってよい。
(A) content of alkyl (meth)acrylate monomer units when component (A) has alkyl (meth)acrylate as a monomer unit, or component (A) contains hydroxyalkyl (meth)acrylate The content of the monomer units of the hydroxyalkyl (meth)acrylate when it is present as a monomer unit may be within the following range based on the total amount of the monomer units constituting component (A). From the viewpoint of easily obtaining excellent followability, resolution and adhesion, the content of the above-mentioned monomer units is 0.10% by mass or more, 0.50% by mass or more, 1.0% by mass or more, 1 .5% by mass or more, 2.0% by mass or more, 2.5% by mass or more, or 3.0% by mass or more. The content of the above-mentioned monomer units is 3.5% by mass or more, 4.0% by mass or more, 4.0% by mass or more, and 4 0.5% by mass or more, or 5.0% by mass or more. From the viewpoint of easily obtaining excellent followability, resolution and adhesion, the content of the above-mentioned monomer units is 20% by mass or less, 18% by mass or less, 15% by mass or less, 12% by mass or less, and 10% by mass. % or less, 8.0 mass % or less, 6.0 mass % or less, 5.5 mass % or less, or 5.0 mass % or less. The content of the above-mentioned monomer units is 4.5% by mass or less, 4.0% by mass or less, 3.5% by mass or less, or 3.0% by mass from the viewpoint of easily obtaining excellent resolution. % or less. From these points of view, the content of the above monomer units may be 0.10 to 20% by mass, or 0.10 to 5.0% by mass.
本実施形態に係る感光性フィルム及び感光性樹脂組成物に含まれる（Ａ）成分において、アルキル基の炭素数が４以上の（メタ）アクリル酸アルキルの単量体単位の含有量は、（Ａ）成分を構成する単量体単位の全量を基準として、１質量％以下、１質量％未満、０．１質量％以下、又は、０．０１質量％以下であってよい。
In the component (A) contained in the photosensitive film and photosensitive resin composition according to the present embodiment, the content of the monomer unit of the alkyl (meth)acrylate having 4 or more carbon atoms in the alkyl group is (A ) may be 1% by mass or less, less than 1% by mass, 0.1% by mass or less, or 0.01% by mass or less based on the total amount of the monomer units constituting the component.
（Ａ）成分は、優れた追従性、解像性及び密着性を得やすい観点から、（メタ）アクリル酸アリールを単量体単位として有してよい。（メタ）アクリル酸アリールとしては、（メタ）アクリル酸ベンジル、（メタ）アクリル酸フェニル、（メタ）アクリル酸ナフチル等が挙げられる。
The (A) component may have aryl (meth)acrylate as a monomer unit from the viewpoint of easily obtaining excellent conformability, resolution and adhesion. Aryl (meth)acrylates include benzyl (meth)acrylate, phenyl (meth)acrylate, and naphthyl (meth)acrylate.
（Ａ）成分が（メタ）アクリル酸アリールを単量体単位として有する場合、（メタ）アクリル酸アリールの単量体単位の含有量は、（Ａ）成分を構成する単量体単位の全量を基準として下記の範囲であってよい。（メタ）アクリル酸アリールの単量体単位の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、１質量％以上、５質量％以上、１０質量％以上、１２質量％以上、１５質量％以上、１８質量％以上、又は、２０質量％以上であってよい。（メタ）アクリル酸アリールの単量体単位の含有量は、優れた感度及び現像性を得やすい観点、並びに、更に優れた追従性を得やすい観点から、２１質量％以上、又は、２３質量％以上であってよい。（メタ）アクリル酸アリールの単量体単位の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、５０質量％以下、５０質量％未満、４５質量％以下、４０質量％以下、３５質量％以下、３０質量％以下、２５質量％以下、又は、２３質量％以下であってよい。（メタ）アクリル酸アリールの単量体単位の含有量は、更に優れた解像性を得やすい観点から、２１質量％以下、又は、２０質量％以下であってよい。これらの観点から、（メタ）アクリル酸アリールの単量体単位の含有量は、１～５０質量％であってよい。
When the component (A) has an aryl (meth)acrylate as a monomer unit, the content of the monomer units of the aryl (meth)acrylate is the total amount of the monomer units constituting the component (A). The following range may be used as a reference. The content of the monomer unit of the aryl (meth)acrylate is 1% by mass or more, 5% by mass or more, 10% by mass or more, and 12% by mass from the viewpoint of easily obtaining excellent followability, resolution and adhesion. % or more, 15 mass % or more, 18 mass % or more, or 20 mass % or more. The content of the monomer unit of the aryl (meth)acrylate is 21% by mass or more, or 23% by mass, from the viewpoint of easily obtaining excellent sensitivity and developability, and from the viewpoint of easily obtaining excellent followability. or more. The content of the monomer unit of the aryl (meth)acrylate is 50% by mass or less, less than 50% by mass, 45% by mass or less, and 40% by mass, from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. % or less, 35 mass % or less, 30 mass % or less, 25 mass % or less, or 23 mass % or less. The content of the monomer units of the aryl (meth)acrylate may be 21% by mass or less, or 20% by mass or less, from the viewpoint of easily obtaining even better resolution. From these viewpoints, the content of the monomer units of the aryl (meth)acrylate may be 1 to 50% by mass.
（Ａ）成分は、優れた追従性、解像性及び密着性を得やすい観点から、スチレン化合物（（メタ）アクリロイル基を有する化合物を除く）を単量体単位として有してよい。スチレン化合物としては、スチレン、スチレン誘導体等が挙げられる。スチレン誘導体は、ビニルトルエン、α－メチルスチレン等が挙げられる。（Ａ）成分は、優れた追従性、解像性及び密着性を得やすい観点から、（メタ）アクリル酸及びスチレン化合物を単量体単位として有してよく、（メタ）アクリル酸ヒドロキシアルキル及びスチレン化合物を単量体単位として有してよく、（メタ）アクリル酸アリール及びスチレン化合物を単量体単位として有してよい。
The (A) component may have a styrene compound (excluding compounds having a (meth)acryloyl group) as a monomer unit from the viewpoint of easily obtaining excellent followability, resolution and adhesion. Styrene compounds include styrene and styrene derivatives. Examples of styrene derivatives include vinyltoluene and α-methylstyrene. Component (A) may have (meth)acrylic acid and a styrene compound as monomer units from the viewpoint of easily obtaining excellent followability, resolution and adhesion, and hydroxyalkyl (meth)acrylate and It may have a styrene compound as a monomer unit, and may have an aryl (meth)acrylate and a styrene compound as a monomer unit.
（Ａ）成分がスチレン化合物を単量体単位として有する場合、スチレン化合物の単量体単位の含有量は、（Ａ）成分を構成する単量体単位の全量を基準として下記の範囲であってよい。スチレン化合物の単量体単位の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、１０質量％以上、１５質量％以上、１５質量％超、２０質量％以上、２５質量％以上、３０質量％以上、３０質量％超、３５質量％以上、４０質量％以上、又は、４５質量％以上であってよい。スチレン化合物の単量体単位の含有量は、更に優れた解像性を得やすい観点から、４７質量％以上、又は、５０質量％以上であってよい。スチレン化合物の単量体単位の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、９０質量％以下、８５質量％以下、８０質量％以下、７５質量％以下、７０質量％以下、６５質量％以下、６０質量％以下、５５質量％以下、又は、５０質量％以下であってよい。スチレン化合物の単量体単位の含有量は、優れた感度及び現像性を得やすい観点、並びに、更に優れた追従性を得やすい観点から、４７質量％以下、又は、４５質量％以下であってよい。これらの観点から、スチレン化合物の単量体単位の含有量は、１０～９０質量％であってよい。
When the component (A) has a styrene compound as a monomer unit, the content of the monomer units of the styrene compound is within the following range based on the total amount of the monomer units constituting the component (A). good. The content of the monomer unit of the styrene compound is 10% by mass or more, 15% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, from the viewpoint of easily obtaining excellent followability, resolution and adhesion. It may be at least 30% by mass, at least 30% by mass, at least 35% by mass, at least 40% by mass, or at least 45% by mass. The content of the monomer unit of the styrene compound may be 47% by mass or more, or 50% by mass or more from the viewpoint of easily obtaining even better resolution. The content of the monomer unit of the styrene compound is 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, from the viewpoint of easily obtaining excellent followability, resolution and adhesion. % by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, or 50% by mass or less. The content of the monomer unit of the styrene compound is 47% by mass or less, or 45% by mass or less from the viewpoint of easily obtaining excellent sensitivity and developability, and from the viewpoint of easily obtaining excellent followability. good. From these points of view, the content of monomer units in the styrene compound may be 10 to 90% by mass.
（Ａ）成分は、その他の単量体を単量体単位として有してよい。このような単量体としては、ビニルアルコールのエーテル類（ビニル－ｎ－ブチルエーテル等）、（メタ）アクリロニトリル、マレイン酸、マレイン酸無水物、マレイン酸モノエステル（マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノイソプロピル等）、フマール酸、ケイ皮酸、α－シアノケイ皮酸、イタコン酸、クロトン酸、プロピオール酸などが挙げられる。
The (A) component may have other monomers as monomer units. Such monomers include vinyl alcohol ethers (vinyl-n-butyl ether, etc.), (meth)acrylonitrile, maleic acid, maleic anhydride, maleic acid monoesters (monomethyl maleate, monoethyl maleate, maleic monoisopropyl acid, etc.), fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like.
（Ａ）成分の酸価は、優れた感度、現像性、追従性、解像性及び密着性を得やすい観点から、８０ｍｇＫＯＨ／ｇ以上、９０ｍｇＫＯＨ／ｇ以上、１００ｍｇＫＯＨ／ｇ以上、１００ｍｇＫＯＨ／ｇ超、１２０ｍｇＫＯＨ／ｇ以上、１４０ｍｇＫＯＨ／ｇ以上、１５０ｍｇＫＯＨ／ｇ以上、１６０ｍｇＫＯＨ／ｇ以上、１７０ｍｇＫＯＨ／ｇ以上、又は、１７５ｍｇＫＯＨ／ｇ以上であってよい。（Ａ）成分の酸価は、更に優れた解像性を得やすい観点から、１７６ｍｇＫＯＨ／ｇ以上であってよい。（Ａ）成分の酸価は、優れた感度、現像性、追従性、解像性及び密着性を得やすい観点から、２５０ｍｇＫＯＨ／ｇ以下、２４０ｍｇＫＯＨ／ｇ以下、２３０ｍｇＫＯＨ／ｇ以下、２１０ｍｇＫＯＨ／ｇ以下、２００ｍｇＫＯＨ／ｇ以下、１８０ｍｇＫＯＨ／ｇ以下、１７８ｍｇＫＯＨ／ｇ以下、又は、１７６ｍｇＫＯＨ／ｇ以下であってよい。（Ａ）成分の酸価は、更に優れた感度、現像性及び追従性を得やすい観点から、１７５ｍｇＫＯＨ／ｇ以下であってよい。これらの観点から、（Ａ）成分の酸価は、８０～２５０ｍｇＫＯＨ／ｇであってよい。（Ａ）成分の酸価は、（Ａ）成分を構成する単量体単位（例えば（メタ）アクリル酸の単量体単位）の含有量により調整できる。（Ａ）成分の酸価は、実施例に記載の方法で測定することができる。
The acid value of the component (A) is 80 mgKOH/g or more, 90 mgKOH/g or more, 100 mgKOH/g or more, and more than 100 mgKOH/g from the viewpoint of easily obtaining excellent sensitivity, developability, followability, resolution and adhesion. , 120 mg KOH/g or more, 140 mg KOH/g or more, 150 mg KOH/g or more, 160 mg KOH/g or more, 170 mg KOH/g or more, or 175 mg KOH/g or more. The acid value of component (A) may be 176 mgKOH/g or more from the viewpoint of easily obtaining even better resolution. The acid value of the component (A) is 250 mgKOH/g or less, 240 mgKOH/g or less, 230 mgKOH/g or less, or 210 mgKOH/g or less from the viewpoint of easily obtaining excellent sensitivity, developability, followability, resolution, and adhesion. , 200 mg KOH/g or less, 180 mg KOH/g or less, 178 mg KOH/g or less, or 176 mg KOH/g or less. The acid value of component (A) may be 175 mgKOH/g or less from the viewpoint of easily obtaining even better sensitivity, developability and followability. From these points of view, the component (A) may have an acid value of 80 to 250 mgKOH/g. The acid value of component (A) can be adjusted by adjusting the content of the monomer units (for example, the monomer units of (meth)acrylic acid) constituting component (A). The acid value of component (A) can be measured by the method described in Examples.
（Ａ）成分の重量平均分子量（Ｍｗ）は、優れた感度、現像性、追従性、解像性及び密着性を得やすい観点から、下記の範囲であってよい。（Ａ）成分の重量平均分子量は、１００００以上、２００００以上、２５０００以上、３００００以上、又は、３５０００以上であってよい。（Ａ）成分の重量平均分子量は、１０００００以下、８００００以下、７００００以下、７００００未満、６５０００以下、６００００以下、５００００以下、４００００以下、又は、３５０００以下であってよい。これらの観点から、（Ａ）成分の重量平均分子量は、１００００～１０００００、２００００～５００００、又は、３００００～４００００であってよい。
The weight average molecular weight (Mw) of component (A) may be within the following range from the viewpoint of easily obtaining excellent sensitivity, developability, followability, resolution and adhesion. The weight average molecular weight of component (A) may be 10,000 or more, 20,000 or more, 25,000 or more, 30,000 or more, or 35,000 or more. The weight average molecular weight of component (A) may be 100,000 or less, 80,000 or less, 70,000 or less, less than 70,000, 65,000 or less, 60,000 or less, 50,000 or less, 40,000 or less, or 35,000 or less. From these viewpoints, the weight average molecular weight of component (A) may be 10,000 to 100,000, 20,000 to 50,000, or 30,000 to 40,000.
（Ａ）成分の数平均分子量（Ｍｎ）は、下記の範囲であってよい。（Ａ）成分の数平均分子量は、優れた感度、現像性、追従性、解像性及び密着性を得やすい観点から、５０００以上、１００００以上、１２０００以上、１５０００以上、又は、１６０００以上であってよい。（Ａ）成分の数平均分子量は、更に優れた感度、現像性及び追従性を得やすい観点から、１６５００以上であってよい。（Ａ）成分の数平均分子量は、優れた感度、現像性、追従性、解像性及び密着性を得やすい観点から、５００００以下、４００００以下、３５０００以下、３００００以下、２５０００以下、２００００以下、１８０００以下、１７０００以下、又は、１６５００以下であってよい。（Ａ）成分の数平均分子量は、更に優れた解像性を得やすい観点から、１６０００以下であってよい。これらの観点から、（Ａ）成分の数平均分子量は、５０００～５００００、１００００～２５０００、又は、１５０００～２００００であってよい。
The number average molecular weight (Mn) of component (A) may be within the following range. The number average molecular weight of component (A) is 5000 or more, 10000 or more, 12000 or more, 15000 or more, or 16000 or more from the viewpoint of easily obtaining excellent sensitivity, developability, followability, resolution and adhesion. you can The number average molecular weight of component (A) may be 16,500 or more from the viewpoint of easily obtaining even better sensitivity, developability, and followability. The number average molecular weight of component (A) is 50,000 or less, 40,000 or less, 35,000 or less, 30,000 or less, 25,000 or less, 20,000 or less, from the viewpoint of easily obtaining excellent sensitivity, developability, followability, resolution, and adhesion. It may be 18000 or less, 17000 or less, or 16500 or less. The number average molecular weight of component (A) may be 16,000 or less from the viewpoint of easily obtaining even better resolution. From these viewpoints, the number average molecular weight of component (A) may be 5,000 to 50,000, 10,000 to 25,000, or 15,000 to 20,000.
（Ａ）成分の分散度（重量平均分子量／数平均分子量）は、下記の範囲であってよい。（Ａ）成分の分散度は、優れた感度、現像性、追従性、解像性及び密着性を得やすい観点から、１．００以上、１．５０以上、１．８０以上、２．００以上、２．１０以上、又は、２．１２以上であってよい。（Ａ）成分の分散度は、更に優れた解像性を得やすい観点から、２．１５以上、又は、２．１８以上であってよい。（Ａ）成分の分散度は、優れた感度、現像性、追従性、解像性及び密着性を得やすい観点から、３．００以下、２．８０以下、２．５０以下、２．３０以下、又は、２．２０以下であってよい。（Ａ）成分の分散度は、更に優れた感度、現像性及び追従性を得やすい観点から、２．１８以下、又は、２．１５以下であってよい。これらの観点から、（Ａ）成分の分散度は、１．００～３．００であってよい。
The degree of dispersion (weight average molecular weight/number average molecular weight) of component (A) may be within the following range. The dispersion degree of component (A) is 1.00 or more, 1.50 or more, 1.80 or more, 2.00 or more from the viewpoint of easily obtaining excellent sensitivity, developability, followability, resolution and adhesion. , 2.10 or greater, or 2.12 or greater. The dispersity of component (A) may be 2.15 or more, or 2.18 or more from the viewpoint of easily obtaining even better resolution. The degree of dispersion of component (A) is 3.00 or less, 2.80 or less, 2.50 or less, 2.30 or less from the viewpoint of easily obtaining excellent sensitivity, developability, followability, resolution and adhesion. , or less than or equal to 2.20. The degree of dispersion of component (A) may be 2.18 or less, or 2.15 or less from the viewpoint of easily obtaining even better sensitivity, developability and followability. From these points of view, the component (A) may have a dispersity of 1.00 to 3.00.
重量平均分子量及び数平均分子量は、例えば、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により標準ポリスチレンの検量線を用いて測定することができる。より具体的には、実施例に記載の条件で測定することができる。分子量の低い化合物について、上述の重量平均分子量及び数平均分子量の測定方法で測定困難な場合には、他の方法で分子量を測定し、その平均値を算出することもできる。
The weight average molecular weight and number average molecular weight can be measured, for example, by gel permeation chromatography (GPC) using a standard polystyrene calibration curve. More specifically, it can be measured under the conditions described in Examples. If it is difficult to measure a compound having a low molecular weight by the above weight average molecular weight and number average molecular weight measurement methods, the molecular weight can be measured by another method and the average value can be calculated.
（Ａ）成分の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、感光性フィルムの全量、又は、感光性樹脂組成物の全量（固形分全量）を基準として下記の範囲であってよい。（Ａ）成分の含有量は、フィルムの成形性に優れる観点から、１０質量％以上、２０質量％以上、３０質量％以上、４０質量％以上、４５質量％以上、又は、５０質量％以上であってよい。（Ａ）成分の含有量は、９０質量％以下、８０質量％以下、７５質量％以下、７０質量％以下、６５質量％以下、６０質量％以下、又は、５５質量％以下であってよい。これらの観点から、（Ａ）成分の含有量は、１０～９０質量％であってよい。
The content of component (A) is 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 easily obtaining excellent followability, resolution and adhesion. may be in the range of The content of component (A) is 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 45% by mass or more, or 50% by mass or more from the viewpoint of excellent film formability. It's okay. The content of component (A) may be 90% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, or 55% by mass or less. From these points of view, the content of component (A) may be 10 to 90% by mass.
（Ａ）成分の含有量は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して下記の範囲であってよい。（Ａ）成分の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、１０質量部以上、２０質量部以上、３０質量部以上、４０質量部以上、４５質量部以上、５０質量部以上、５５質量部以上、又は、５６質量部以上であってよい。（Ａ）成分の含有量は、優れた現像性を得やすい観点から、５７質量部以上、又は、５８質量部以上であってよい。（Ａ）成分の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、９０質量部以下、８０質量部以下、７５質量部以下、７０質量部以下、６５質量部以下、６０質量部以下、又は、５９質量部以下であってよい。（Ａ）成分の含有量は、更に優れた追従性を得やすい観点、及び、優れた感度を得やすい観点から、５８質量部以下、５７質量部以下、又は、５６質量部以下であってよい。これらの観点から、（Ａ）成分の含有量は、１０～９０質量部、又は、４０～７０質量部であってよい。
The content of component (A) may be within the following range with respect to the total amount of 100 parts by mass of components (A) and (B). The content of component (A) is 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, or 45 parts by mass or more from the viewpoint of easily obtaining excellent followability, resolution and adhesion. , 50 parts by mass or more, 55 parts by mass or more, or 56 parts by mass or more. The content of component (A) may be 57 parts by mass or more, or 58 parts by mass or more from the viewpoint of easily obtaining excellent developability. The content of component (A) is 90 parts by mass or less, 80 parts by mass or less, 75 parts by mass or less, 70 parts by mass or less, or 65 parts by mass or less from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. , 60 parts by mass or less, or 59 parts by mass or less. The content of component (A) may be 58 parts by mass or less, 57 parts by mass or less, or 56 parts by mass or less from the viewpoint of easily obtaining excellent followability and from the viewpoint of easily obtaining excellent sensitivity. . From these viewpoints, the content of component (A) may be 10 to 90 parts by mass, or 40 to 70 parts by mass.
本実施形態に係る感光性フィルム及び感光性樹脂組成物において、フェノール性水酸基を有する樹脂の含有量は、感光性フィルムの全量、又は、感光性樹脂組成物の全量（固形分全量）を基準として、３０質量％以下、３０質量％未満、２０質量％以下、１０質量％以下、５質量％以下、１質量％以下、又は、０．１質量％以下であってよい。本実施形態に係る感光性フィルム及び感光性樹脂組成物は、フェノール性水酸基を有する樹脂を含有しなくてよい（上述の含有量が実質的に０質量％であってよい）。
In the photosensitive film and photosensitive resin composition according to the present embodiment, the content of the resin having a phenolic hydroxyl group is based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content). , 30% by mass or less, less than 30% by mass, 20% by mass or less, 10% by mass or less, 5% by mass or less, 1% by mass or less, or 0.1% by mass or less. The photosensitive film and photosensitive resin composition according to the present embodiment may not contain a resin having a phenolic hydroxyl group (the above content may be substantially 0% by mass).
本実施形態に係る感光性フィルム及び感光性樹脂組成物は、（Ｂ）成分として光重合性化合物（ピラゾリン化合物に該当する化合物を除く）を含有する。光重合性化合物は、光により重合する化合物である。（Ｂ）成分は、エチレン性不飽和結合を有する化合物であってよく、（メタ）アクリロイル基を有する化合物（（メタ）アクリル酸化合物）であってよい。
The photosensitive film and photosensitive resin composition according to the present embodiment contain photopolymerizable compounds (excluding compounds corresponding to pyrazoline compounds) as the (B) component. A photopolymerizable compound is a compound that is polymerized by light. The component (B) may be a compound having an ethylenically unsaturated bond and may be a compound ((meth)acrylic acid compound) having a (meth)acryloyl group.
（Ｂ）成分としては、ビスフェノールＡ型（メタ）アクリル酸化合物（ポリオキシアルキレン基を有する（メタ）アクリル酸化合物を除く）、ＥＯ変性ジ（メタ）アクリレート、ＰＯ変性ジ（メタ）アクリレート、ＥＯ・ＰＯ変性ジ（メタ）アクリレート、ポリアルキレングリコールジ（メタ）アクリレート（ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート等）、ＥＯ変性ポリアルキレングリコールジ（メタ）アクリレート、ＰＯ変性ポリアルキレングリコールジ（メタ）アクリレート、ＥＯ・ＰＯ変性ポリアルキレングリコールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ＥＯ変性トリメチロールプロパントリ（メタ）アクリレート、ＰＯ変性トリメチロールプロパントリ（メタ）アクリレート、ＥＯ・ＰＯ変性トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、ＥＯ変性ペンタエリスリトールテトラ（メタ）アクリレート、ＰＯ変性ペンタエリスリトールテトラ（メタ）アクリレート、ＥＯ・ＰＯ変性ペンタエリスリトールテトラ（メタ）アクリレート、ＥＯ変性ジペンタエリスリトールヘキサ（メタ）アクリレート、ＰＯ変性ジペンタエリスリトールヘキサ（メタ）アクリレート、ＥＯ・ＰＯ変性ジペンタエリスリトールヘキサ（メタ）アクリレート、ノニルフェノキシポリエチレンオキシアクリレート、フタル酸系化合物、（メタ）アクリル酸アルキル、分子内に少なくとも１つのカチオン重合可能な環状エーテル基を有する光重合性化合物（オキセタン化合物等）などが挙げられる。「ＥＯ変性」とは、ポリオキシエチレン基を有する化合物であることを意味する。「ＰＯ変性」とは、ポリオキシプロピレン基を有する化合物であることを意味する。「ＥＯ・ＰＯ変性」とは、ポリオキシエチレン基及び／又は（ポリ）オキシプロピレン基を有する化合物であることを意味する。
Component (B) includes bisphenol A type (meth)acrylic acid compounds (excluding (meth)acrylic acid compounds having a polyoxyalkylene group), EO-modified di(meth)acrylates, PO-modified di(meth)acrylates, EO・ PO-modified di(meth)acrylate, polyalkylene glycol di(meth)acrylate (polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc.), EO-modified polyalkylene glycol di(meth)acrylate, PO-modified poly Alkylene glycol di(meth)acrylate, EO/PO-modified polyalkylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO/PO-modified trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, EO-modified pentaerythritol tetra(meth)acrylate Acrylate, PO-modified pentaerythritol tetra(meth)acrylate, EO/PO-modified pentaerythritol tetra(meth)acrylate, EO-modified dipentaerythritol hexa(meth)acrylate, PO-modified dipentaerythritol hexa(meth)acrylate, EO/PO-modified Dipentaerythritol hexa(meth)acrylate, nonylphenoxypolyethyleneoxyacrylate, phthalic acid compounds, alkyl (meth)acrylates, photopolymerizable compounds having at least one cationic polymerizable cyclic ether group in the molecule (oxetane compounds, etc.) ) and the like. "EO-modified" means a compound having a polyoxyethylene group. "PO-modified" means a compound having a polyoxypropylene group. “EO/PO-modified” means a compound having a polyoxyethylene group and/or a (poly)oxypropylene group.
（Ｂ）成分は、優れた追従性、解像性及び密着性を得やすい観点から、ビスフェノールＡ型（メタ）アクリル酸化合物を含んでよい。ビスフェノールＡ型（メタ）アクリル酸化合物としては、２，２－ビス（４－（（メタ）アクリロキシポリエトキシ）フェニル）プロパン（２，２－ビス（４－（（メタ）アクリロキシペンタエトキシ）フェニル）プロパン等）、２，２－ビス（４－（（メタ）アクリロキシポリプロポキシ）フェニル）プロパン、２，２－ビス（４－（（メタ）アクリロキシポリブトキシ）フェニル）プロパン、２，２－ビス（４－（（メタ）アクリロキシポリエトキシポリプロポキシ）フェニル）プロパンなどが挙げられる。（Ｂ）成分は、優れた追従性、解像性及び密着性を得やすい観点から、２，２－ビス（４－（（メタ）アクリロキシポリエトキシ）フェニル）プロパンを含んでよく、２，２－ビス（４－（（メタ）アクリロキシペンタエトキシ）フェニル）プロパンを含んでよい。
The (B) component may contain a bisphenol A type (meth)acrylic acid compound from the viewpoint of easily obtaining excellent conformability, resolution and adhesion. As the bisphenol A type (meth)acrylic acid compound, 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane (2,2-bis(4-((meth)acryloxypentaethoxy) phenyl)propane, etc.), 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolybutoxy)phenyl)propane, 2, 2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane and the like. Component (B) may contain 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane from the viewpoint of easily obtaining excellent followability, resolution and adhesion. 2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane may be included.
ビスフェノールＡ型（メタ）アクリル酸化合物の分子量は、優れた追従性、解像性及び密着性を得やすい観点から、下記の範囲であってよい。分子量は、１００以上、２００以上、３００以上、４００以上、４５０以上、５００以上、６００以上、７００以上、又は、８００以上であってよい。分子量は、１００００以下、１００００未満、８０００以下、６０００以下、５０００以下、３０００以下、２０００以下、１５００以下、１０００以下、９００以下、８００以下、７００以下、６００以下、又は、５００以下であってよい。これらの観点から、分子量は、１００～１００００であってよい。
The molecular weight of the bisphenol A type (meth)acrylic acid compound may be within the following range from the viewpoint of easily obtaining excellent conformability, resolution and adhesion. The molecular weight may be 100 or greater, 200 or greater, 300 or greater, 400 or greater, 450 or greater, 500 or greater, 600 or greater, 700 or greater, or 800 or greater. 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 less, or 500 or less. . From these points of view, the molecular weight may range from 100 to 10,000.
ビスフェノールＡ型（メタ）アクリル酸化合物の含有量は、（Ｂ）成分の全質量を基準として下記の範囲であってよい。ビスフェノールＡ型（メタ）アクリル酸化合物の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、５０質量％以上、５０質量％超、６０質量％以上、７０質量％以上、又は、７５質量％以上であってよい。ビスフェノールＡ型（メタ）アクリル酸化合物の含有量は、更に優れた追従性を得やすい観点、及び、優れた感度を得やすい観点から、８０質量％以上、８５質量％以上、又は、９０質量％以上であってよい。ビスフェノールＡ型（メタ）アクリル酸化合物の含有量は、１００質量％以下であり、優れた追従性、解像性及び密着性を得やすい観点から、１００質量％未満、９９質量％以下、９８質量％以下、９７質量％以下、９５質量％以下、９２質量％以下、又は、９１質量％以下であってよい。ビスフェノールＡ型（メタ）アクリル酸化合物の含有量は、優れた現像性を得やすい観点から、９０質量％以下、８５質量％以下、又は、８０質量％以下であってよい。これらの観点から、ビスフェノールＡ型（メタ）アクリル酸化合物の含有量は、５０～１００質量％であってよい。
The content of the bisphenol A type (meth)acrylic acid compound may be within the following ranges based on the total mass of the component (B). The content of the bisphenol A type (meth)acrylic acid compound is 50% by mass or more, more than 50% by mass, 60% by mass or more, 70% by mass or more from the viewpoint of easily obtaining excellent followability, resolution and adhesion. , or 75% by mass or more. The content of the bisphenol A type (meth)acrylic acid compound is 80% by mass or more, 85% by mass or more, or 90% by mass from the viewpoint of easily obtaining excellent followability and from the viewpoint of easily obtaining excellent sensitivity. or more. The content of the bisphenol A type (meth)acrylic acid compound is 100% by mass or less, and from the viewpoint of easily obtaining excellent followability, resolution and adhesion, it is less than 100% by mass, 99% by mass or less, and 98% by mass. % or less, 97 mass % or less, 95 mass % or less, 92 mass % or less, or 91 mass % or less. The content of the bisphenol A type (meth)acrylic acid compound may be 90% by mass or less, 85% by mass or less, or 80% by mass or less from the viewpoint of easily obtaining excellent developability. From these points of view, the content of the bisphenol A type (meth)acrylic acid compound may be 50 to 100% by mass.
ビスフェノールＡ型（メタ）アクリル酸化合物の含有量は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して下記の範囲であってよい。ビスフェノールＡ型（メタ）アクリル酸化合物の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、１質量部以上、５質量部以上、１０質量部以上、２０質量部以上、２０質量部超、２５質量部以上、２５質量部超、３０質量部以上、又は、３０質量部超であってよい。ビスフェノールＡ型（メタ）アクリル酸化合物の含有量は、更に優れた追従性を得やすい観点、及び、優れた感度を得やすい観点から、３２質量部以上、３５質量部以上、３５質量部超、３８質量部以上、又は、４０質量部以上であってよい。ビスフェノールＡ型（メタ）アクリル酸化合物の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、１００質量部未満、９０質量部以下、８０質量部以下、７０質量部以下、６０質量部以下、５０質量部以下、４５質量部以下、又は、４０質量部以下であってよい。ビスフェノールＡ型（メタ）アクリル酸化合物の含有量は、優れた現像性を得やすい観点から、３８質量部以下、３５質量部以下、３５質量部未満、又は、３２質量部以下であってよい。これらの観点から、ビスフェノールＡ型（メタ）アクリル酸化合物の含有量は、１質量部以上１００質量部未満であってよい。
The content of the bisphenol A type (meth)acrylic acid compound may be within the following range with respect to 100 parts by mass of the total amount of the components (A) and (B). The content of the bisphenol A type (meth)acrylic acid compound is 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, or 20 parts by mass or more from the viewpoint of easily obtaining excellent followability, resolution and adhesion. , more than 20 parts by weight, more than 25 parts by weight, more than 25 parts by weight, more than 30 parts by weight, or more than 30 parts by weight. The content of the bisphenol A type (meth)acrylic acid compound is 32 parts by mass or more, 35 parts by mass or more, more than 35 parts by mass, from the viewpoint of easily obtaining excellent followability and excellent sensitivity. It may be 38 parts by mass or more, or 40 parts by mass or more. The content of the bisphenol A type (meth)acrylic acid compound is less than 100 parts by mass, 90 parts by mass or less, 80 parts by mass or less, or 70 parts by mass or less from the viewpoint of easily obtaining excellent followability, resolution and adhesion. , 60 parts by mass or less, 50 parts by mass or less, 45 parts by mass or less, or 40 parts by mass or less. The content of the bisphenol A type (meth)acrylic acid compound may be 38 parts by mass or less, 35 parts by mass or less, less than 35 parts by mass, or 32 parts by mass or less from the viewpoint of easily obtaining excellent developability. From these points of view, the content of the bisphenol A type (meth)acrylic acid compound may be 1 part by mass or more and less than 100 parts by mass.
（Ｂ）成分は、優れた追従性、解像性及び密着性を得やすい観点から、ポリオキシアルキレン基（２以上のアルキレン基がエーテル結合で連結した基）を有する（メタ）アクリル酸化合物を含んでよく、ポリオキシエチレン基及びポリオキシプロピレン基からなる群より選ばれる少なくとも一種を有する（メタ）アクリル酸化合物を含んでよい。
Component (B) is a (meth)acrylic acid compound having a polyoxyalkylene group (a group in which two or more alkylene groups are linked by an ether bond) from the viewpoint of easily obtaining excellent followability, resolution and adhesion. It may contain a (meth)acrylic acid compound having at least one selected from the group consisting of a polyoxyethylene group and a polyoxypropylene group.
ポリオキシアルキレン基を有する（メタ）アクリル酸化合物の分子量は、優れた追従性、解像性及び密着性を得やすい観点から、下記の範囲であってよい。分子量は、１００以上、２００以上、３００以上、４００以上、５００以上、６００以上、７００以上、８００以上、９００以上、１０００以上、又は、１１００以上であってよい。分子量は、１００００以下、１００００未満、８０００以下、６０００以下、５０００以下、３０００以下、２０００以下、１５００以下、又は、１２００以下であってよい。これらの観点から、分子量は、１００～１００００であってよい。
The molecular weight of the (meth)acrylic acid compound having a polyoxyalkylene group may be within the following range from the viewpoint of easily obtaining excellent conformability, resolution and adhesion. The molecular weight may be 100 or greater, 200 or greater, 300 or greater, 400 or greater, 500 or greater, 600 or greater, 700 or greater, 800 or greater, 900 or greater, 1000 or greater, or 1100 or greater. The molecular weight may be 10,000 or less, less than 10,000, 8,000 or less, 6,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,500 or less, or 1,200 or less. From these points of view, the molecular weight may range from 100 to 10,000.
ポリオキシアルキレン基を有する（メタ）アクリル酸化合物の含有量は、（Ｂ）成分の全質量を基準として下記の範囲であってよい。ポリオキシアルキレン基を有する（メタ）アクリル酸化合物の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、０質量％を超えてよく、１質量％以上、２質量％以上、３質量％以上、５質量％以上、８質量％以上、又は、９質量％以上であってよい。ポリオキシアルキレン基を有する（メタ）アクリル酸化合物の含有量は、優れた現像性を得やすい観点から、１０質量％以上、１２質量％以上、１５質量％以上、１８質量％以上、２０質量％以上、又は、２３質量％以上であってよい。ポリオキシアルキレン基を有する（メタ）アクリル酸化合物の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、５０質量％以下、５０質量％未満、４０質量％以下、３０質量％以下、又は、２５質量％以下であってよい。ポリオキシアルキレン基を有する（メタ）アクリル酸化合物の含有量は、更に優れた追従性を得やすい観点、及び、優れた感度を得やすい観点から、２３質量％以下、２０質量％以下、１８質量％以下、１５質量％以下、１２質量％以下、又は、１０質量％以下であってよい。これらの観点から、ポリオキシアルキレン基を有する（メタ）アクリル酸化合物の含有量は、０質量％を超え５０質量％以下であってよい。
The content of the (meth)acrylic acid compound having a polyoxyalkylene group may be within the following ranges based on the total mass of component (B). The content of the (meth)acrylic acid compound having a polyoxyalkylene group may exceed 0% by mass, 1% by mass or more, and 2% by mass from the viewpoint of easily obtaining excellent followability, resolution and adhesion. Above, it may be 3% by mass or more, 5% by mass or more, 8% by mass or more, or 9% by mass or more. The content of the (meth)acrylic acid compound having a polyoxyalkylene group is 10% by mass or more, 12% by mass or more, 15% by mass or more, 18% by mass or more, and 20% by mass from the viewpoint of easily obtaining excellent developability. or more, or 23% by mass or more. The content of the (meth)acrylic acid compound having a polyoxyalkylene group is 50% by mass or less, less than 50% by mass, 40% by mass or less, 30% by mass or less, from the viewpoint of easily obtaining excellent followability, resolution and adhesion. % by mass or less, or 25% by mass or less. The content of the (meth)acrylic acid compound having a polyoxyalkylene group is 23% by mass or less, 20% by mass or less, and 18% by mass from the viewpoint of easily obtaining excellent followability and from the viewpoint of easily obtaining excellent sensitivity. % or less, 15 mass % or less, 12 mass % or less, or 10 mass % or less. From these points of view, the content of the (meth)acrylic acid compound having a polyoxyalkylene group may be more than 0% by mass and 50% by mass or less.
ポリオキシアルキレン基を有する（メタ）アクリル酸化合物の含有量は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して下記の範囲であってよい。ポリオキシアルキレン基を有する（メタ）アクリル酸化合物の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、０．１０質量部以上、０．５０質量部以上、１．０質量部以上、１．５質量部以上、２．０質量部以上、２．５質量部以上、３．０質量部以上、３．５質量部以上、又は、４．０質量部以上であってよい。ポリオキシアルキレン基を有する（メタ）アクリル酸化合物の含有量は、優れた現像性を得やすい観点から、４．５質量部以上、５．０質量部以上、６．０質量部以上、７．０質量部以上、８．０質量部以上、８．５質量部以上、９．０質量部以上、又は、９．５質量部以上であってよい。ポリオキシアルキレン基を有する（メタ）アクリル酸化合物の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、５０質量部以下、３０質量部以下、２５質量部以下、２０質量部以下、１８質量部以下、１５質量部以下、１２質量部以下、１０質量部以下、又は、９．５質量部以下であってよい。ポリオキシアルキレン基を有する（メタ）アクリル酸化合物の含有量は、更に優れた追従性を得やすい観点、及び、優れた感度を得やすい観点から、９．０質量部以下、８．５質量部以下、８．０質量部以下、７．０質量部以下、６．０質量部以下、５．０質量部以下、又は、４．０質量部以下であってよい。これらの観点から、ポリオキシアルキレン基を有する（メタ）アクリル酸化合物の含有量は、０．１０～５０質量部であってよい。
The content of the (meth)acrylic acid compound having a polyoxyalkylene group may be within the following range with respect to 100 parts by mass of the total amount of components (A) and (B). The content of the (meth)acrylic acid compound having a polyoxyalkylene group is 0.10 parts by mass or more, 0.50 parts by mass or more, from the viewpoint of easily obtaining excellent followability, resolution and adhesion. 0 parts by mass or more, 1.5 parts by mass or more, 2.0 parts by mass or more, 2.5 parts by mass or more, 3.0 parts by mass or more, 3.5 parts by mass or more, or 4.0 parts by mass or more you can The content of the (meth)acrylic acid compound having a polyoxyalkylene group is 4.5 parts by mass or more, 5.0 parts by mass or more, 6.0 parts by mass or more, from the viewpoint of easily obtaining excellent developability. It may be 0 parts by mass or more, 8.0 parts by mass or more, 8.5 parts by mass or more, 9.0 parts by mass or more, or 9.5 parts by mass or more. The content of the (meth)acrylic acid compound having a polyoxyalkylene group is 50 parts by mass or less, 30 parts by mass or less, 25 parts by mass or less, 20 parts by mass or less, from the viewpoint of easily obtaining excellent followability, resolution and adhesion. It may be no more than 18 parts by mass, no more than 15 parts by mass, no more than 12 parts by mass, no more than 10 parts by mass, or no more than 9.5 parts by mass. The content of the (meth)acrylic acid compound having a polyoxyalkylene group is 9.0 parts by mass or less and 8.5 parts by mass from the viewpoint of easily obtaining excellent followability and from the viewpoint of easily obtaining excellent sensitivity. 8.0 parts by mass or less, 7.0 parts by mass or less, 6.0 parts by mass or less, 5.0 parts by mass or less, or 4.0 parts by mass or less. From these points of view, the content of the (meth)acrylic acid compound having a polyoxyalkylene group may be 0.10 to 50 parts by mass.
（Ｂ）成分が、ビスフェノールＡ型（メタ）アクリル酸化合物と、ポリオキシアルキレン基を有する（メタ）アクリル酸化合物と、を含む場合、ポリオキシアルキレン基を有する（メタ）アクリル酸化合物の含有量は、ビスフェノールＡ型（メタ）アクリル酸化合物１００質量部に対して下記の範囲であってよい。ポリオキシアルキレン基を有する（メタ）アクリル酸化合物の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、１質量部以上、２質量部以上、３質量部以上、５質量部以上、８質量部以上、又は、１０質量部以上であってよい。ポリオキシアルキレン基を有する（メタ）アクリル酸化合物の含有量は、優れた現像性を得やすい観点から、１５質量部以上、２０質量部以上、２５質量部以上、又は、３０質量部以上であってよい。ポリオキシアルキレン基を有する（メタ）アクリル酸化合物の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、１００質量部以下、１００質量部未満、８０質量部以下、５０質量部以下、４５質量部以下、４０質量部以下、３５質量部以下、又は、３０質量部以下であってよい。ポリオキシアルキレン基を有する（メタ）アクリル酸化合物の含有量は、更に優れた追従性を得やすい観点、及び、優れた感度を得やすい観点から、２５質量部以下、２０質量部以下、１５質量部以下、又は、１０質量部以下であってよい。これらの観点から、ポリオキシアルキレン基を有する（メタ）アクリル酸化合物の含有量は、１～１００質量部であってよい。
When the component (B) contains a bisphenol A type (meth)acrylic acid compound and a (meth)acrylic acid compound having a polyoxyalkylene group, the content of the (meth)acrylic acid compound having a polyoxyalkylene group may be in the following range with respect to 100 parts by mass of the bisphenol A type (meth)acrylic acid compound. The content of the (meth)acrylic acid compound having a polyoxyalkylene group is 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 5 parts by mass or more, from the viewpoint of easily obtaining excellent followability, resolution and adhesion. It may be at least 8 parts by mass, or at least 10 parts by mass. The content of the (meth)acrylic acid compound having a polyoxyalkylene group is 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, or 30 parts by mass or more from the viewpoint of easily obtaining excellent developability. you can The content of the (meth)acrylic acid compound having a polyoxyalkylene group is 100 parts by mass or less, less than 100 parts by mass, 80 parts by mass or less, 50 parts by mass or less, from the viewpoint of easily obtaining excellent followability, resolution and adhesion. It may be no more than 45 parts by mass, no more than 40 parts by mass, no more than 35 parts by mass, or no more than 30 parts by mass. The content of the (meth)acrylic acid compound having a polyoxyalkylene group is 25 parts by mass or less, 20 parts by mass or less, and 15 parts by mass from the viewpoint of easily obtaining excellent followability and from the viewpoint of easily obtaining excellent sensitivity. parts or less, or 10 parts by mass or less. From these points of view, the content of the (meth)acrylic acid compound having a polyoxyalkylene group may be 1 to 100 parts by mass.
（Ｂ）成分の含有量は、感光性フィルムの全量、又は、感光性樹脂組成物の全量（固形分全量）を基準として下記の範囲であってよい。（Ｂ）成分の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、１０質量％以上、１５質量％以上、２０質量％以上、２５質量％以上、３０質量％以上、３５質量％以上、又は、３８質量％以上であってよい。（Ｂ）成分の含有量は、更に優れた追従性を得やすい観点、及び、優れた感度を得やすい観点から、４０質量％以上、又は、４１質量％以上であってよい。（Ｂ）成分の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、９０質量％以下、８０質量％以下、７０質量％以下、６５質量％以下、６０質量％以下、５５質量％以下、５０質量％以下、４５質量％以下、又は、４２質量％以下であってよい。（Ｂ）成分の含有量は、優れた現像性を得やすい観点から、４１質量％以下、又は、４０質量％以下であってよい。これらの観点から、（Ｂ）成分の含有量は、１０～９０質量％であってよい。
The content of component (B) may be within the following ranges based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content). The content of component (B) is 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, and 30% by mass or more from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. , 35% by mass or more, or 38% by mass or more. The content of the component (B) may be 40% by mass or more, or 41% by mass or more, from the viewpoint of easily obtaining excellent followability and from the viewpoint of easily obtaining excellent sensitivity. The content of component (B) is 90% by mass or less, 80% by mass or less, 70% by mass or less, 65% by mass or less, or 60% by mass or less from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. , 55 mass % or less, 50 mass % or less, 45 mass % or less, or 42 mass % or less. The content of component (B) may be 41% by mass or less, or 40% by mass or less from the viewpoint of easily obtaining excellent developability. From these viewpoints, the content of component (B) may be 10 to 90% by mass.
（Ｂ）成分の含有量は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して下記の範囲であってよい。（Ｂ）成分の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、１０質量部以上、２０質量部以上、２５質量部以上、３０質量部以上、３５質量部以上、４０質量部以上、又は、４１質量部以上であってよい。（Ｂ）成分の含有量は、更に優れた追従性を得やすい観点、及び、優れた感度を得やすい観点から、４２質量部以上、４３質量部以上、又は、４４質量部以上であってよい。（Ｂ）成分の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、９０質量部以下、８０質量部以下、７０質量部以下、６０質量部以下、５５質量部以下、５０質量部以下、４５質量部以下、又は、４４質量部以下であってよい。（Ｂ）成分の含有量は、優れた現像性を得やすい観点から、４３質量部以下、又は、４２質量部以下であってよい。これらの観点から、（Ｂ）成分の含有量は、１０～９０質量部、又は、３０～６０質量部であってよい。
The content of component (B) may be within the following range with respect to 100 parts by mass of the total amount of components (A) and (B). The content of component (B) is 10 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, or 35 parts by mass or more from the viewpoint of easily obtaining excellent followability, resolution and adhesion. , 40 parts by mass or more, or 41 parts by mass or more. The content of the component (B) may be 42 parts by mass or more, 43 parts by mass or more, or 44 parts by mass or more from the viewpoint of easily obtaining excellent followability and from the viewpoint of easily obtaining excellent sensitivity. . The content of component (B) is 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, or 55 parts by mass or less from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. , 50 parts by mass or less, 45 parts by mass or less, or 44 parts by mass or less. The content of component (B) may be 43 parts by mass or less, or 42 parts by mass or less from the viewpoint of easily obtaining excellent developability. From these viewpoints, the content of component (B) may be 10 to 90 parts by mass, or 30 to 60 parts by mass.
本実施形態に係る感光性フィルム及び感光性樹脂組成物において、エチレン性不飽和基を３つ以上有する化合物、及び、ビスフェノールＡ骨格を有するジ（メタ）アクリレート化合物の合計量は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して、２０質量部以下、２０質量部未満、１０質量部以下、１質量部以下、又は、０．１質量部以下であってよい。本実施形態に係る感光性フィルム及び感光性樹脂組成物は、エチレン性不飽和基を３つ以上有する化合物、及び、ビスフェノールＡ骨格を有するジ（メタ）アクリレート化合物からなる群より選ばれる少なくとも一種を含有しなくてよい（（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して含有量が実質的に０質量部であってよい）。
In the photosensitive film and photosensitive resin composition according to the present embodiment, the total amount of the compound having three or more ethylenically unsaturated groups and the di(meth)acrylate compound having a bisphenol A skeleton is the component (A) It may be 20 parts by mass or less, less than 20 parts by mass, 10 parts by mass or less, 1 part by mass or less, or 0.1 parts by mass or less with respect to 100 parts by mass of the total amount of component (B). The photosensitive film and photosensitive resin composition according to the present embodiment contain at least one compound selected from the group consisting of a compound having three or more ethylenically unsaturated groups and a di(meth)acrylate compound having a bisphenol A skeleton. It may not be contained (the content may be substantially 0 parts by mass with respect to 100 parts by mass of the total amount of components (A) and (B)).
本実施形態に係る感光性フィルム及び感光性樹脂組成物において、エチレン性不飽和基及びイソシアヌル環構造を有する光重合性化合物の含有量は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して、１質量部以下、１質量部未満、０．１質量部以下、０．０１質量部以下、又は、０．００１質量部以下であってよい。本実施形態に係る感光性フィルム及び感光性樹脂組成物は、エチレン性不飽和基及びイソシアヌル環構造を有する光重合性化合物を含有しなくてよい（上述の含有量が実質的に０質量部であってよい）。
In the photosensitive film and photosensitive resin composition according to the present embodiment, the content of the photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric ring structure is 100 parts by mass of the total amount of components (A) and (B). 1 part by mass or less, less than 1 part by mass, 0.1 part by mass or less, 0.01 part by mass or less, or 0.001 part by mass or less. The photosensitive film and photosensitive resin composition according to the present embodiment may not contain a photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric ring structure (the above content is substantially 0 parts by mass. may be).
本実施形態に係る感光性フィルム及び感光性樹脂組成物において、ペンタエリスリトール由来の骨格を有する光重合性化合物、及び、ジペンタエリスリトール由来の骨格を有する光重合性化合物からなる群より選ばれる少なくとも一種の含有量は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して、３質量部以下、３質量部未満、１質量部以下、０．１質量部以下、又は、０．０１質量部以下であってよい。本実施形態に係る感光性フィルム及び感光性樹脂組成物は、ペンタエリスリトール由来の骨格を有する光重合性化合物、及び、ジペンタエリスリトール由来の骨格を有する光重合性化合物からなる群より選ばれる少なくとも一種を含有しなくてもよい（（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して含有量が実質的に０質量部であってよい）。本実施形態に係る感光性フィルム及び感光性樹脂組成物において、ペンタエリスリトール由来の骨格を有する（メタ）アクリル酸化合物、及び、ジペンタエリスリトール由来の骨格を有する（メタ）アクリル酸化合物からなる群より選ばれる少なくとも一種の含有量は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して、３質量部以下、３質量部未満、１質量部以下、０．１質量部以下、又は、０．０１質量部以下であってよい。本実施形態に係る感光性フィルム及び感光性樹脂組成物は、ペンタエリスリトール由来の骨格を有する（メタ）アクリル酸化合物、及び、ジペンタエリスリトール由来の骨格を有する（メタ）アクリル酸化合物からなる群より選ばれる少なくとも一種を含有しなくてもよい（（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して含有量が実質的に０質量部であってよい）。
In the photosensitive film and photosensitive resin composition according to the present embodiment, at least one selected from the group consisting of a photopolymerizable compound having a pentaerythritol-derived skeleton and a photopolymerizable compound having a dipentaerythritol-derived skeleton. The content of is 3 parts by mass or less, less than 3 parts by mass, 1 part by mass or less, 0.1 parts by mass or less, or 0.01 parts by mass with respect to 100 parts by mass of the total amount of components (A) and (B) It may be less than or equal to parts by mass. The photosensitive film and the photosensitive resin composition according to the present embodiment are at least one selected from the group consisting of a photopolymerizable compound having a pentaerythritol-derived skeleton and a photopolymerizable compound having a dipentaerythritol-derived skeleton. may not be contained (the content may be substantially 0 parts by mass with respect to 100 parts by mass of the total amount of components (A) and (B)). In the photosensitive film and photosensitive resin composition according to the present embodiment, from the group consisting of a (meth)acrylic acid compound having a skeleton derived from pentaerythritol and a (meth)acrylic acid compound having a skeleton derived from dipentaerythritol The content of at least one selected is 3 parts by mass or less, less than 3 parts by mass, 1 part by mass or less, 0.1 parts by mass or less, or , 0.01 parts by mass or less. The photosensitive film and the photosensitive resin composition according to the present embodiment are selected from the group consisting of (meth)acrylic acid compounds having a pentaerythritol-derived skeleton and (meth)acrylic acid compounds having a dipentaerythritol-derived skeleton. At least one selected may not be contained (the content may be substantially 0 parts by mass with respect to 100 parts by mass of the total amount of components (A) and (B)).
本実施形態に係る感光性フィルム及び感光性樹脂組成物において、ビスフェノールＦ型（メタ）アクリル酸化合物の含有量は、（Ｂ）成分の全質量を基準として、５質量％以下、５質量％未満、１質量％以下、１質量％未満、０．１質量％以下、又は、実質的に０質量％であってよい。本実施形態に係る感光性フィルム及び感光性樹脂組成物において、ビスフェノールＦ型（メタ）アクリル酸化合物の含有量は、感光性フィルムの全量、又は、感光性樹脂組成物の全量（固形分全量）を基準として、０．２質量％以下、０．１５質量％以下、０．１５質量％未満、０．１質量％以下、又は、０．０１質量％以下であってよい。本実施形態に係る感光性フィルム及び感光性樹脂組成物は、ビスフェノールＦ型（メタ）アクリル酸化合物を含有しなくてよい（上述の含有量が実質的に０質量％であってよい）。
In the photosensitive film and photosensitive resin composition according to the present embodiment, the content of the bisphenol F-type (meth)acrylic acid compound is 5% by mass or less and less than 5% by mass, based on the total mass of the component (B). , 1% by weight or less, less than 1% by weight, 0.1% by weight or less, or substantially 0% by weight. In the photosensitive film and photosensitive resin composition according to the present embodiment, the content of the bisphenol F-type (meth)acrylic acid compound is the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content). 0.2% by mass or less, 0.15% by mass or less, less than 0.15% by mass, 0.1% by mass or less, or 0.01% by mass or less. The photosensitive film and photosensitive resin composition according to the present embodiment may not contain a bisphenol F-type (meth)acrylic acid compound (the above content may be substantially 0% by mass).
本実施形態に係る感光性フィルム及び感光性樹脂組成物において、２つ以上のオキシラン環を有するエポキシ化合物の含有量は、（Ａ）成分１００質量部に対して、２０質量部以下、２０質量部未満、１０質量部以下、１０質量部未満、１質量部以下、又は、実質的に０質量部であってよい。本実施形態に係る感光性フィルム及び感光性樹脂組成物は、２つ以上のオキシラン環を有するエポキシ化合物を含有しなくてよい（２つ以上のオキシラン環を有するエポキシ化合物の含有量は、感光性フィルムの全量、又は、感光性樹脂組成物の全量（固形分全量）を基準として実質的に０質量％であってよい）。
In the photosensitive film and photosensitive resin composition according to the present embodiment, the content of the epoxy compound having two or more oxirane rings is 20 parts by mass or less and 20 parts by mass with respect to 100 parts by mass of component (A). It may be less than, 10 parts by weight or less, less than 10 parts by weight, 1 part by weight or less, or substantially 0 parts by weight. The photosensitive film and photosensitive resin composition according to the present embodiment may not contain an epoxy compound having two or more oxirane rings (the content of the epoxy compound having two or more oxirane rings is It may be substantially 0% by mass based on the total amount of the film or the total amount of the photosensitive resin composition (the total solid content)).
本実施形態に係る感光性フィルム及び感光性樹脂組成物は、（Ｃ）成分として光重合開始剤（ピラゾリン化合物に該当する化合物を除く）を含有する。
The photosensitive film and photosensitive resin composition according to the present embodiment contain a photopolymerization initiator (excluding compounds corresponding to pyrazoline compounds) as the (C) component.
（Ｃ）成分としては、ヘキサアリールビイミダゾール化合物；ベンゾフェノン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－１－ブタノン、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン、４－（２－ヒドロキシエトキシ）フェニル－２－（ヒドロキシ－２－プロピル）ケトン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノ－プロパノン－１等の芳香族ケトン；アルキルアントラキノン等のキノン化合物；ベンゾインアルキルエーテル等のベンゾインエーテル化合物；ベンゾイン、アルキルベンゾイン等のベンゾイン化合物；ベンジルジメチルケタール等のベンジル誘導体；ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド；ビス（２，６－ジメチルベンゾイル）－２，４，４－トリメチル－ペンチルフォスフィンオキサイド；（２，４，６－トリメチルベンゾイル）エトキシフェニルフォスフィンオキサイドなどが挙げられる。
Component (C) includes hexaarylbiimidazole compounds; 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- Aromatic ketones such as [4-(methylthio)phenyl]-2-morpholino-propanone-1; quinone compounds such as alkylanthraquinone; benzoin ether compounds such as benzoin alkyl ether; benzoin compounds such as benzoin and alkylbenzoin; benzyl derivatives such as; bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; bis(2,6-dimethylbenzoyl)-2,4,4-trimethyl-pentylphosphine oxide; 6-trimethylbenzoyl)ethoxyphenylphosphine oxide and the like.
（Ｃ）成分は、優れた追従性、解像性及び密着性を得やすい観点から、ヘキサアリールビイミダゾール化合物を含んでよい。ヘキサアリールビイミダゾール化合物におけるアリール基は、フェニル基等であってよい。ヘキサアリールビイミダゾール化合物におけるアリール基に結合する水素原子は、ハロゲン原子（塩素原子等）により置換されていてよい。
The (C) component may contain a hexaarylbiimidazole compound from the viewpoint of easily obtaining excellent followability, resolution and adhesion. The aryl group in the hexaarylbiimidazole compound may be a phenyl group or the like. A hydrogen atom bonded to an aryl group in the hexaarylbiimidazole compound may be substituted with a halogen atom (such as a chlorine atom).
ヘキサアリールビイミダゾール化合物は、２，４，５－トリアリールイミダゾール二量体であってよい。２，４，５－トリアリールイミダゾール二量体としては、２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｏ－クロロフェニル）－４，５－ビス－（ｍ－メトキシフェニル）イミダゾール二量体、２－（ｐ－メトキシフェニル）－４，５－ジフェニルイミダゾール二量体等が挙げられる。ヘキサアリールビイミダゾール化合物は、優れた追従性、解像性及び密着性を得やすい観点から、２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾール二量体を含んでよく、２，２’－ビス（ｏ－クロロフェニル）－４，４’，５，５’－テトラフェニル－１，２’－ビイミダゾールを含んでよい。
The hexaarylbiimidazole compound may be a 2,4,5-triarylimidazole dimer. Examples of the 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis-(m- methoxyphenyl)imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, and the like. The hexaarylbiimidazole compound may contain 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer from the viewpoint of easily obtaining excellent followability, resolution and adhesion, and 2,2' -bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.
ヘキサアリールビイミダゾール化合物の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、（Ｃ）成分の全量を基準として、５０質量％以上、５０質量％超、７０質量％以上、９０質量％以上、９５質量％以上、９８質量％以上、９９質量％以上、又は、実質的に１００質量％（（Ｃ）成分が実質的にヘキサアリールビイミダゾール化合物からなる態様）であってよい。
The content of the hexaarylbiimidazole compound is 50% by mass or more, more than 50% by mass, or 70% by mass, based on the total amount of component (C), from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. Above, 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, or substantially 100% by mass (an aspect in which the component (C) is substantially composed of a hexaarylbiimidazole compound) you can
（Ｃ）成分の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、感光性フィルムの全量、又は、感光性樹脂組成物の全量（固形分全量）を基準として下記の範囲であってよい。（Ｃ）成分の含有量は、０．１０質量％以上、０．５０質量％以上、１．０質量％以上、２．０質量％以上、３．０質量％以上、４．０質量％以上、４．５質量％以上、又は、４．７質量％以上であってよい。（Ｃ）成分の含有量は、２０質量％以下、１５質量％以下、１２質量％以下、１０質量％以下、８．０質量％以下、７．０質量％以下、６．０質量％以下、又は、５．０質量％以下であってよい。これらの観点から、（Ｃ）成分の含有量は、０．１０～２０質量％であってよい。
The content of component (C) is 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 easily obtaining excellent followability, resolution and adhesion. may be in the range of The content of component (C) is 0.10% by mass or more, 0.50% by mass or more, 1.0% by mass or more, 2.0% by mass or more, 3.0% by mass or more, 4.0% by mass or more , 4.5% by mass or more, or 4.7% by mass or more. The content of component (C) is 20% by mass or less, 15% by mass or less, 12% by mass or less, 10% by mass or less, 8.0% by mass or less, 7.0% by mass or less, 6.0% by mass or less, Alternatively, it may be 5.0% by mass or less. From these viewpoints, the content of component (C) may be 0.10 to 20% by mass.
（Ｃ）成分の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して下記の範囲であってよい。（Ｃ）成分の含有量は、０．１０質量部以上、０．５０質量部以上、１．０質量部以上、２．０質量部以上、３．０質量部以上、３．５質量部以上、４．０質量部以上、４．５質量部以上、又は、５．０質量部以上であってよい。（Ｃ）成分の含有量は、２０質量部以下、１５質量部以下、１２質量部以下、１０質量部以下、８．０質量部以下、７．０質量部以下、６．０質量部以下、又は、５．５質量部以下であってよい。これらの観点から、（Ｃ）成分の含有量は、０．１０～２０質量部であってよい。
The content of component (C) may be in the following range with respect to 100 parts by mass of the total amount of components (A) and (B), from the viewpoint of easily obtaining excellent followability, resolution and adhesion. . The content of component (C) is 0.10 parts by mass or more, 0.50 parts by mass or more, 1.0 parts by mass or more, 2.0 parts by mass or more, 3.0 parts by mass or more, 3.5 parts by mass or more , 4.0 parts by mass or more, 4.5 parts by mass or more, or 5.0 parts by mass or more. The content of component (C) is 20 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, 10 parts by mass or less, 8.0 parts by mass or less, 7.0 parts by mass or less, 6.0 parts by mass or less, Alternatively, it may be 5.5 parts by mass or less. From these points of view, the content of component (C) may be 0.10 to 20 parts by mass.
本実施形態に係る感光性フィルム及び感光性樹脂組成物は、（Ｄ）成分としてピラゾリン化合物（ピラゾリン環を有する化合物）を含有する。（Ｄ）成分は、増感剤（光増感剤）として用いることができる。（Ｄ）成分の分子量は、１００００未満であってよい。
The photosensitive film and photosensitive resin composition according to the present embodiment contain a pyrazoline compound (a compound having a pyrazoline ring) as component (D). (D) A component can be used as a sensitizer (photosensitizer). The molecular weight of component (D) may be less than 10,000.
ピラゾリン化合物としては、１－ピラゾリン化合物、２－ピラゾリン化合物、及び、３－ピラゾリン化合物が挙げられる。ピラゾリン化合物は、優れた追従性、解像性及び密着性を得やすい観点から、２－ピラゾリン化合物を含んでよい。
Pyrazoline compounds include 1-pyrazoline compounds, 2-pyrazoline compounds, and 3-pyrazoline compounds. The pyrazoline compound may contain a 2-pyrazoline compound from the viewpoint of easily obtaining excellent followability, resolution and adhesion.
ピラゾリン化合物は、ピラゾリン環に結合する置換基を有してよく、ピラゾリン環の１位、３位及び５位からなる群より選ばれる少なくとも一種に結合する置換基を有する化合物を含んでよい。置換基としては、アルキル基（炭素数１～２０のアルキル基（非環状アルキル基）、炭素数５～１２のシクロアルキル基等）、アリール基（フェニル基、アラルキル基（ベンジル基、フェネチル基等）、ベンゾイル基、スチリル基など）、ビニル基、ヒドロキシ基、カルボキシ基、カルボン酸塩基、アルデヒド基、アルコキシ基（無置換のアルコキシ基、又は、置換アルコキシ基（ヒドロキシアルコキシ基等））、カルボニル基、アルコキシカルボニル基、アルカノイル基（炭素数２～１２のアルカノイル基等）、オキシカルボニル基、カルボニルオキシ基、アミノ基、エポキシ基、フリル基、シアノ基、ハロゲノ基（フルオロ基、クロロ基、ブロモ基等）、ニトロ基、アセチル基、スルホニル基、スルホンアミド基などが挙げられる。アリール基のベンゼン環は、置換基を有してよく、置換基としては、アルキル基、アルコキシ基（メトキシ基、エトキシ基、プロポキシ基等）、ハロゲノ基（フルオロ基、クロロ基、ブロモ基等）、スルホンアミド基などが挙げられる。置換基は、アルキルエステル基（例えば炭素数１～６のアルキルエステル基）、アルキルアミノ基（例えば炭素数１～２０のアルキルアミノ基）等であってもよい。
The pyrazoline compound may have a substituent that binds to the pyrazoline ring, and may include compounds that have a substituent that binds to at least one selected from the group consisting of the 1-, 3- and 5-positions of the pyrazoline ring. Examples of substituents include alkyl groups (alkyl groups having 1 to 20 carbon atoms (acyclic alkyl groups), cycloalkyl groups having 5 to 12 carbon atoms, etc.), aryl groups (phenyl groups, aralkyl groups (benzyl group, phenethyl group, etc. ), benzoyl group, styryl group, etc.), vinyl group, hydroxy group, carboxy group, carboxylic acid group, aldehyde group, alkoxy group (unsubstituted alkoxy group or substituted alkoxy group (hydroxyalkoxy group, etc.)), carbonyl group , alkoxycarbonyl group, alkanoyl group (alkanoyl group having 2 to 12 carbon atoms, etc.), oxycarbonyl group, carbonyloxy group, amino group, epoxy group, furyl group, cyano group, halogeno group (fluoro group, chloro group, bromo group etc.), nitro group, acetyl group, sulfonyl group, sulfonamide group and the like. The benzene ring of the aryl group may have a substituent, such as an alkyl group, an alkoxy group (methoxy group, ethoxy group, propoxy group, etc.), a halogeno group (fluoro group, chloro group, bromo group, etc.). , a sulfonamide group, and the like. The substituent may be an alkylester group (eg, an alkylester group having 1 to 6 carbon atoms), an alkylamino group (eg, an alkylamino group having 1 to 20 carbon atoms), or the like.
（Ｄ）成分は、優れた追従性、解像性及び密着性を得やすい観点から、下記一般式（ｄ１）で表される化合物、及び、下記一般式（ｄ２）で表される化合物からなる群より選ばれる少なくとも一種を含んでよく、下記一般式（ｄ１）で表される化合物を含んでよい。
Component (D) consists of a compound represented by the following general formula (d1) and a compound represented by the following general formula (d2) from the viewpoint of easily obtaining excellent followability, resolution and adhesion. It may contain at least one selected from the group, and may contain a compound represented by the following general formula (d1).
式（ｄ１）において、Ｒｄ１１、Ｒｄ１２及びＲｄ１３の少なくとも一つは、アルコキシ基（例えば炭素数１～１０のアルコキシ基）、又は、アルキル基（例えば炭素数１～３のアルキル基）であってよい。Ｒｄ１２及びＲｄ１３からなる群より選ばれる少なくとも一種は、優れた追従性、解像性及び密着性を得やすい観点から、アルコキシ基であってよく、メトキシ基、エトキシ基又はプロポキシ基であってよい。ｄ１１は、優れた追従性、解像性及び密着性を得やすい観点から、０であってよい。ｄ１２及びｄ１３からなる群より選ばれる少なくとも一種は、優れた追従性、解像性及び密着性を得やすい観点から、０、１、２又は３であってよく、１であってよい。ｄ１１、ｄ１２及びｄ１３の総和は、０～６又は１～６であってよい。
In formula (d1), at least one of R d11 , R d12 and R d13 is an alkoxy group (eg, an alkoxy group having 1 to 10 carbon atoms) or an alkyl group (eg, an alkyl group having 1 to 3 carbon atoms). It's okay. At least one selected from the group consisting of R d12 and R d13 may be an alkoxy group, a methoxy group, an ethoxy group or a propoxy group from the viewpoint of easily obtaining excellent followability, resolution and adhesion. good. d11 may be 0 from the viewpoint of easily obtaining excellent followability, resolution and adhesion. At least one selected from the group consisting of d12 and d13 may be 0, 1, 2 or 3, or 1 from the viewpoint of easily obtaining excellent followability, resolution and adhesion. The sum of d11, d12 and d13 may be 0-6 or 1-6.
式（ｄ２）において、Ｒｄ２１は、ハロゲノ基であってよく、フルオロ基、クロロ基、又は、ブロモ基であってよい。Ｒｄ２２は、スルホンアミド基であってよい。ｄ２１及びｄ２２からなる群より選ばれる少なくとも一種は、０、１、２又は３であってよく、１であってよい。
In formula (d2), R d21 may be a halogeno group, a fluoro group, a chloro group, or a bromo group. R d22 may be a sulfonamide group. At least one selected from the group consisting of d21 and d22 may be 0, 1, 2 or 3, and may be 1.
ピラゾリン化合物としては、１－フェニル－３－（４－イソプロピルスチリル）－５－（４－イソプロピルフェニル）－ピラゾリン、１－フェニル－３－（４－ｔｅｒｔ－ブチル－スチリル）－５－（４－ｔｅｒｔ－ブチルフェニル）－ピラゾリン、１－フェニル－３－（４－メトキシスチリル）－５－（４－メトキシフェニル）－ピラゾリン、１－フェニル－３－（３，５－ジメトキシスチリル）－５－（３，５－ジメトキシフェニル）－ピラゾリン、１－フェニル－３－（３，４－ジメトキシスチリル）－５－（３，４－ジメトキシフェニル）－ピラゾリン、１－フェニル－３－（２，６－ジメトキシスチリル）－５－（２，６－ジメトキシフェニル）－ピラゾリン、１－フェニル－３－（２，５－ジメトキシスチリル）－５－（２，５－ジメトキシフェニル）－ピラゾリン、１－フェニル－３－（２，３－ジメトキシスチリル）－５－（２，３－ジメトキシフェニル）－ピラゾリン、１－フェニル－３－（２，４－ジメトキシスチリル）－５－（２，４－ジメトキシフェニル）－ピラゾリン、４－［［３－（４－クロロフェニル）－４，５－ジヒドロ－１Ｈ－ピラゾール］－１－イル］ベンゼンスルホンアミド等が挙げられる。
Examples of pyrazoline compounds include 1-phenyl-3-(4-isopropylstyryl)-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-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,6-dimethoxy styryl)-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-dimethoxyphenyl)-pyrazoline, 4-[[3-(4-chlorophenyl)-4,5-dihydro-1H-pyrazol]-1-yl]benzenesulfonamide and the like.
ピラゾリン化合物は、優れた追従性、解像性及び密着性を得やすい観点から、ピラゾリン環に結合するアリール基を有する化合物（ピラゾリン環に結合する２つ以上（例えば２～３つ）のアリール基を有する化合物等）を含んでよく、ピラゾリン環の１位、３位及び５位からなる群より選ばれる少なくとも一種に結合するアリール基を有する化合物を含んでよく、ピラゾリン環の１位、３位及び５位からなる群より選ばれる少なくとも一種に結合するフェニル基（置換基を有してよいフェニル基）を有する化合物を含んでよく、１－フェニル－３－（４－メトキシスチリル）－５－（４－メトキシフェニル）ピラゾリン、及び、４－［［３－（４－クロロフェニル）－４，５－ジヒドロ－１Ｈ－ピラゾール］－１－イル］ベンゼンスルホンアミドからなる群より選ばれる少なくとも一種を含んでよい。
The pyrazoline compound is a compound having an aryl group bonded to the pyrazoline ring (two or more (eg, 2 to 3) aryl groups bonded to the pyrazoline ring) from the viewpoint of easily obtaining excellent followability, resolution and adhesion. ), 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 the pyrazoline ring, 1-position of the pyrazoline ring, 3-position and 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 the 5-position, 1-phenyl-3-(4-methoxystyryl)-5- (4-Methoxyphenyl)pyrazoline and at least one selected from the group consisting of 4-[[3-(4-chlorophenyl)-4,5-dihydro-1H-pyrazol]-1-yl]benzenesulfonamide OK.
（Ｄ）成分の含有量は、感光性フィルムの全量、又は、感光性樹脂組成物の全量（固形分全量）を基準として下記の範囲であってよい。（Ｄ）成分の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、０．０１質量％以上、０．０３質量％以上、０．０５質量％以上、０．０８質量％以上、０．１０質量％以上、０．１０質量％超、０．１２質量％以上、０．１５質量％以上、０．１８質量％以上、又は、０．１９質量％以上であってよい。（Ｄ）成分の含有量は、更に優れた密着性を得やすい観点、及び、優れた感度を得やすい観点から、０．２０質量％以上、０．２３質量％以上、０．２５質量％以上、又は、０．２８質量％以上であってよい。（Ｄ）成分の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、５．０質量％以下、３．０質量％以下、１．０質量％以下、０．８０質量％以下、０．７０質量％以下、０．６０質量％以下、０．５０質量％以下、０．４０質量％以下、０．３５質量％以下、０．３０質量％以下、又は、０．２８質量％以下であってよい。（Ｄ）成分の含有量は、更に優れた追従性を得やすい観点から、０．２５質量％以下、０．２３質量％以下、０．２０質量％以下、又は、０．１９質量％以下であってよい。これらの観点から、（Ｄ）成分の含有量は、０．０１～５．０質量％、又は、０．１０～１．０質量％であってよい。
The content of component (D) may be within the following ranges based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content). The content of component (D) is 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, and 0.08% by mass, from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. % by mass or more, 0.10% by mass or more, more than 0.10% by mass, 0.12% by mass or more, 0.15% by mass or more, 0.18% by mass or more, or 0.19% by mass or more good. The content of the component (D) is 0.20% by mass or more, 0.23% by mass or more, 0.25% by mass or more from the viewpoint of easily obtaining excellent adhesion and from the viewpoint of easily obtaining excellent sensitivity. , or 0.28% by mass or more. The content of component (D) is 5.0% by mass or less, 3.0% by mass or less, 1.0% by mass or less, and 0.80 from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. % by mass or less, 0.70 mass % or less, 0.60 mass % or less, 0.50 mass % or less, 0.40 mass % or less, 0.35 mass % or less, 0.30 mass % or less, or 0. It may be 28% by mass or less. The content of component (D) is 0.25% by mass or less, 0.23% by mass or less, 0.20% by mass or less, or 0.19% by mass or less from the viewpoint of easily obtaining excellent followability. It's okay. From these viewpoints, the content of component (D) may be 0.01 to 5.0% by mass, or 0.10 to 1.0% by mass.
（Ｄ）成分の含有量は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して下記の範囲であってよい。（Ｄ）成分の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、０．０１質量部以上、０．０２質量部以上、０．０２質量部超、０．０３質量部以上、０．０５質量部以上、０．０８質量部以上、０．１０質量部以上、０．１０質量部超、０．１２質量部以上、０．１５質量部以上、０．１８質量部以上、又は、０．２０質量部以上であってよい。（Ｄ）成分の含有量は、更に優れた密着性を得やすい観点、及び、優れた感度を得やすい観点から、０．２１質量部以上、０．２３質量部以上、０．２５質量部以上、０．２８質量部以上、又は、０．３０質量部以上であってよい。（Ｄ）成分の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、５．０質量部以下、３．０質量部以下、１．０質量部以下、０．８０質量部以下、０．７０質量部以下、０．６０質量部以下、０．５０質量部以下、０．４０質量部以下、０．３５質量部以下、又は、０．３０質量部以下であってよい。（Ｄ）成分の含有量は、更に優れた追従性を得やすい観点から、０．２８質量部以下、０．２５質量部以下、０．２３質量部以下、０．２１質量部以下、又は、０．２０質量部以下であってよい。これらの観点から、（Ｄ）成分の含有量は、０．０１～５．０質量部、０．０３～５．０質量部、又は、０．１０～１．０質量部であってよい。
The content of component (D) may be within the following range with respect to the total amount of 100 parts by mass of components (A) and (B). The content of component (D) is 0.01 parts by mass or more, 0.02 parts by mass or more, more than 0.02 parts by mass, and 0.03 from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. parts by mass or more, 0.05 parts by mass or more, 0.08 parts by mass or more, 0.10 parts by mass or more, more than 0.10 parts by mass, 0.12 parts by mass or more, 0.15 parts by mass or more, 0.18 parts by mass parts or more, or 0.20 parts by mass or more. The content of the component (D) is 0.21 parts by mass or more, 0.23 parts by mass or more, and 0.25 parts by mass or more from the viewpoint of easily obtaining excellent adhesion and from the viewpoint of easily obtaining excellent sensitivity. , 0.28 parts by mass or more, or 0.30 parts by mass or more. The content of component (D) is 5.0 parts by mass or less, 3.0 parts by mass or less, 1.0 parts by mass or less, and 0.80 from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. Parts by mass or less, 0.70 parts by mass or less, 0.60 parts by mass or less, 0.50 parts by mass or less, 0.40 parts by mass or less, 0.35 parts by mass or less, or 0.30 parts by mass or less good. The content of component (D) is 0.28 parts by mass or less, 0.25 parts by mass or less, 0.23 parts by mass or less, 0.21 parts by mass or less, or It may be 0.20 parts by mass or less. From these viewpoints, the content of component (D) may be 0.01 to 5.0 parts by mass, 0.03 to 5.0 parts by mass, or 0.10 to 1.0 parts by mass.
（Ｄ）成分の含有量は、（Ａ）成分１００質量部に対して下記の範囲であってよい。（Ｄ）成分の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、０．０１質量部以上、０．０３質量部以上、０．０５質量部以上、０．０８質量部以上、０．１０質量部以上、０．１５質量部以上、０．２０質量部以上、０．２５質量部以上、０．３０質量部以上、０．３５質量部以上、又は、０．３６質量部以上であってよい。（Ｄ）成分の含有量は、更に優れた密着性を得やすい観点、及び、優れた感度を得やすい観点から、０．４０質量部以上、０．４５質量部以上、０．５０質量部以上、又は、０．５４質量部以上であってよい。（Ｄ）成分の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、５．０質量部以下、３．０質量部以下、１．０質量部以下、０．８０質量部以下、０．７０質量部以下、０．６０質量部以下、０．５５質量部以下、又は、０．５４質量部以下であってよい。（Ｄ）成分の含有量は、更に優れた追従性を得やすい観点から、０．５４質量部以下、０．５０質量部以下、０．４５質量部以下、０．４０質量部以下、又は、０．３６質量部以下であってよい。これらの観点から、（Ｄ）成分の含有量は、０．０１～５．０質量部、０．０４～５．０質量部、又は、０．１０～１．０質量部であってよい。
The content of component (D) may be within the following ranges per 100 parts by mass of component (A). The content of component (D) is 0.01 parts by mass or more, 0.03 parts by mass or more, 0.05 parts by mass or more, and 0.08 parts by mass from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. parts by mass or more, 0.10 parts by mass or more, 0.15 parts by mass or more, 0.20 parts by mass or more, 0.25 parts by mass or more, 0.30 parts by mass or more, 0.35 parts by mass or more, or 0. It may be 36 parts by mass or more. The content of the component (D) is 0.40 parts by mass or more, 0.45 parts by mass or more, and 0.50 parts by mass or more from the viewpoint of easily obtaining excellent adhesion and from the viewpoint of easily obtaining excellent sensitivity. , or 0.54 parts by mass or more. The content of component (D) is 5.0 parts by mass or less, 3.0 parts by mass or less, 1.0 parts by mass or less, and 0.80 from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. It may be 0.70 parts by mass or less, 0.60 parts by mass or less, 0.55 parts by mass or less, or 0.54 parts by mass or less. The content of component (D) is 0.54 parts by mass or less, 0.50 parts by mass or less, 0.45 parts by mass or less, 0.40 parts by mass or less, or It may be 0.36 parts by mass or less. From these viewpoints, the content of component (D) may be 0.01 to 5.0 parts by mass, 0.04 to 5.0 parts by mass, or 0.10 to 1.0 parts by mass.
（Ｄ）成分の含有量は、（Ｂ）成分１００質量部に対して下記の範囲であってよい。（Ｄ）成分の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、０．０１質量部以上、０．０３質量部以上、０．０５質量部以上、０．０８質量部以上、０．１０質量部以上、０．１５質量部以上、０．２０質量部以上、０．２５質量部以上、０．３０質量部以上、０．３５質量部以上、０．４０質量部以上、又は、０．４５質量部以上であってよい。（Ｄ）成分の含有量は、更に優れた密着性を得やすい観点、及び、優れた感度を得やすい観点から、０．５０質量部以上、０．５１質量部以上、０．５５質量部以上、０．６０質量部以上、０．６５質量部以上、又は、０．６８質量部以上であってよい。（Ｄ）成分の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、５．０質量部以下、３．０質量部以下、１．０質量部以下、０．８０質量部以下、０．７０質量部以下、又は、０．６８質量部以下であってよい。（Ｄ）成分の含有量は、更に優れた追従性を得やすい観点から、０．６５質量部以下、０．６０質量部以下、０．５５質量部以下、０．５１質量部以下、０．５０質量部以下、又は、０．４５質量部以下であってよい。これらの観点から、（Ｄ）成分の含有量は、０．０１～５．０質量部、０．０５～５．０質量部、又は、０．１０～１．０質量部であってよい。
The content of component (D) may be within the following ranges per 100 parts by mass of component (B). The content of component (D) is 0.01 parts by mass or more, 0.03 parts by mass or more, 0.05 parts by mass or more, and 0.08 parts by mass from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. Parts by mass or more, 0.10 parts by mass or more, 0.15 parts by mass or more, 0.20 parts by mass or more, 0.25 parts by mass or more, 0.30 parts by mass or more, 0.35 parts by mass or more, 0.40 mass parts parts or more, or 0.45 parts by mass or more. The content of component (D) is 0.50 parts by mass or more, 0.51 parts by mass or more, and 0.55 parts by mass or more from the viewpoint of easily obtaining excellent adhesion and from the viewpoint of easily obtaining excellent sensitivity. , 0.60 parts by mass or more, 0.65 parts by mass or more, or 0.68 parts by mass or more. The content of component (D) is 5.0 parts by mass or less, 3.0 parts by mass or less, 1.0 parts by mass or less, and 0.80 from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. It may be 0.70 parts by mass or less, or 0.68 parts by mass or less. The content of component (D) is 0.65 parts by mass or less, 0.60 parts by mass or less, 0.55 parts by mass or less, 0.51 parts by mass or less, 0.65 parts by mass or less, 0.51 parts by mass or less, or 0.60 parts by mass or less, from the viewpoint of easily obtaining excellent followability. It may be 50 parts by mass or less, or 0.45 parts by mass or less. From these viewpoints, the content of component (D) may be 0.01 to 5.0 parts by mass, 0.05 to 5.0 parts by mass, or 0.10 to 1.0 parts by mass.
（Ｄ）成分の含有量は、（Ｃ）成分及び（Ｄ）成分の総量１００質量部に対して下記の範囲であってよい。（Ｄ）成分の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、０．１０質量部以上、０．５０質量部以上、０．８０質量部以上、１．０質量部以上、１．５質量部以上、２．０質量部以上、２．５質量部以上、３．０質量部以上、３．５質量部以上、又は、３．８質量部以上であってよい。（Ｄ）成分の含有量は、更に優れた密着性を得やすい観点、及び、優れた感度を得やすい観点から、４．０質量部以上、４．５質量部以上、５．０質量部以上、５．０質量部超、５．５質量部以上、又は、５．７質量部以上であってよい。（Ｄ）成分の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、２０質量部以下、１５質量部以下、１０質量部以下、９．０質量部以下、８．０質量部以下、７．０質量部以下、６．０質量部以下、又は、５．７質量部以下であってよい。（Ｄ）成分の含有量は、更に優れた追従性を得やすい観点から、５．５質量部以下、５．０質量部以下、５．０質量部未満、４．５質量部以下、４．０質量部以下、又は、３．８質量部以下であってよい。これらの観点から、（Ｄ）成分の含有量は、０．１０～２０質量部、又は、１．０～１０質量部であってよい。
The content of component (D) may be within the following range with respect to 100 parts by mass of the total amount of components (C) and (D). The content of component (D) is 0.10 parts by mass or more, 0.50 parts by mass or more, 0.80 parts by mass or more, and 1.0 part by mass from the viewpoint of easily obtaining excellent followability, resolution and adhesion. Parts by mass or more, 1.5 parts by mass or more, 2.0 parts by mass or more, 2.5 parts by mass or more, 3.0 parts by mass or more, 3.5 parts by mass or more, or 3.8 parts by mass or more good. The content of component (D) is 4.0 parts by mass or more, 4.5 parts by mass or more, and 5.0 parts by mass or more from the viewpoint of easily obtaining excellent adhesion and from the viewpoint of easily obtaining excellent sensitivity. , more than 5.0 parts by mass, 5.5 parts by mass or more, or 5.7 parts by mass or more. The content of component (D) is 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, 9.0 parts by mass or less, from the viewpoint of easily obtaining excellent followability, resolution and adhesion. It may be 0 parts by mass or less, 7.0 parts by mass or less, 6.0 parts by mass or less, or 5.7 parts by mass or less. The content of component (D) is 5.5 parts by mass or less, 5.0 parts by mass or less, less than 5.0 parts by mass, 4.5 parts by mass or less, 4. It may be 0 parts by mass or less, or 3.8 parts by mass or less. From these viewpoints, the content of component (D) may be 0.10 to 20 parts by mass, or 1.0 to 10 parts by mass.
本実施形態に係る感光性フィルム及び感光性樹脂組成物は、重合禁止剤（（Ａ）～（Ｄ）成分のいずれかに該当する化合物を除く）を含有してよく、重合禁止剤を含有しなくてもよい。重合禁止剤は、レジストパターン形成時の未露光部における重合を抑制し、感度の経時安定性及び解像性を向上させやすい。重合禁止剤としては、カテコール化合物（例えば、４－ｔｅｒｔ－ブチルカテコール等のｔｅｒｔ－ブチルカテコール）、ヒンダードアミン（例えば２，２，６，６－テトラメチル－４－ヒドロキシピペリジン－１－オキシル）、４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン－Ｎ－オキシル等が挙げられる。本実施形態に係る感光性フィルム及び感光性樹脂組成物は、感度の優れた経時安定性を得やすい観点から、カテコール化合物を含有してよい。
The photosensitive film and photosensitive resin composition according to the present embodiment may contain a polymerization inhibitor (excluding compounds corresponding to any of the components (A) to (D)), and contains a polymerization inhibitor. It doesn't have to be. A polymerization inhibitor suppresses polymerization in an unexposed area during formation of a resist pattern, and tends to improve stability of sensitivity over time and resolution. Polymerization inhibitors include catechol compounds (eg, tert-butylcatechol such as 4-tert-butylcatechol), hindered amines (eg, 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl), 4 -hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl and the like. The photosensitive film and the photosensitive resin composition according to the present embodiment may contain a catechol compound from the viewpoint of easily obtaining excellent sensitivity and stability over time.
重合禁止剤の含有量は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して下記の範囲であってよい。重合禁止剤の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、０．００１質量部以上、０．００３質量部以上、０．００５質量部以上、０．００８質量部以上、又は、０．０１０質量部以上であってよい。重合禁止剤の含有量は、更に優れた解像性を得やすい観点から、０．０１１質量部以上、０．０１２質量部以上、又は、０．０１５質量部以上であってよい。重合禁止剤の含有量は、優れた追従性、解像性及び密着性を得やすい観点から、０．１００質量部以下、０．０５０質量部以下、０．０４０質量部以下、０．０３０質量部以下、０．０２０質量部以下、又は、０．０１５質量部以下であってよい。重合禁止剤の含有量は、更に優れた追従性を得やすい観点、及び、優れた感度を得やすい観点から、０．０１２質量部以下、０．０１１質量部以下、又は、０．０１０質量部以下であってよい。これらの観点から、重合禁止剤の含有量は、０．００１～０．１００質量部であってよい。重合禁止剤の含有量は、０質量部であってよく、０質量部を超えてよい。
The content of the polymerization inhibitor may be within the following range with respect to the total amount of 100 parts by mass of components (A) and (B). The content of the polymerization inhibitor is 0.001 parts by mass or more, 0.003 parts by mass or more, 0.005 parts by mass or more, and 0.008 parts by mass from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. parts or more, or 0.010 parts by mass or more. The content of the polymerization inhibitor may be 0.011 parts by mass or more, 0.012 parts by mass or more, or 0.015 parts by mass or more from the viewpoint of easily obtaining even better resolution. The content of the polymerization inhibitor is 0.100 parts by mass or less, 0.050 parts by mass or less, 0.040 parts by mass or less, and 0.030 parts by mass from the viewpoint of easily obtaining excellent followability, resolution, and adhesion. parts or less, 0.020 parts by mass or less, or 0.015 parts by mass or less. The content of the polymerization inhibitor is 0.012 parts by mass or less, 0.011 parts by mass or less, or 0.010 parts by mass from the viewpoint of easily obtaining excellent followability and from the viewpoint of easily obtaining excellent sensitivity. may be: From these points of view, the content of the polymerization inhibitor may be 0.001 to 0.100 parts by mass. The content of the polymerization inhibitor may be 0 parts by mass or may exceed 0 parts by mass.
本実施形態に係る感光性樹脂組成物は、有機溶剤を含有してよい。有機溶剤としては、メタノール、エタノール、アセトン、メチルエチルケトン、メチルセロソルブ、エチルセロソルブ、トルエン、Ｎ，Ｎ－ジメチルホルムアミド、プロピレングリコールモノメチルエーテル等が挙げられる。
The photosensitive resin composition according to this embodiment may contain an organic solvent. Organic solvents include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether and the like.
本実施形態に係る感光性フィルム及び感光性樹脂組成物は、上述した成分以外のその他の成分（（Ａ）～（Ｄ）成分のいずれかに該当する化合物を除く）を含有してよい。その他の成分としては、水素供与体（ビス［４－（ジメチルアミノ）フェニル］メタン、ビス［４－（ジエチルアミノ）フェニル］メタン、ロイコクリスタルバイオレット、Ｎ－フェニルグリシン等）、染料（マラカイトグリーン等）、トリブロモフェニルスルホン、ビニル重合体、オキセタン化合物、アントラセン化合物（９，１０－ジブトキシアントラセン等）、ジスチリルベンゼン化合物、ナフタレン化合物、ニトロキシル化合物、メルカプト化合物（メルカプト基を有する化合物。例えばメルカプト基含有水素供与体）、増感剤、光発色剤、熱発色防止剤、可塑剤（ｐ－トルエンスルホンアミド等）、顔料、充填剤、消泡剤、難燃剤、安定剤、密着性付与剤、レベリング剤、剥離促進剤、酸化防止剤、香料、イメージング剤、熱架橋剤、熱ラジカル重合開始剤などが挙げられる。
The photosensitive film and photosensitive resin composition according to the present embodiment may contain other components (excluding compounds corresponding to any of components (A) to (D)) other than the components described above. Other components include hydrogen donors (bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, leuco crystal violet, N-phenylglycine, etc.) and dyes (malachite green, etc.). , tribromophenyl sulfone, vinyl polymers, oxetane compounds, anthracene compounds (9,10-dibutoxyanthracene, etc.), distyrylbenzene compounds, naphthalene compounds, nitroxyl compounds, mercapto compounds (compounds having a mercapto group. For example, mercapto group-containing Hydrogen donor), sensitizer, photocoloring agent, anti-thermocoloring agent, plasticizer (p-toluenesulfonamide, etc.), pigment, filler, antifoaming agent, flame retardant, stabilizer, adhesion imparting agent, leveling agents, release accelerators, antioxidants, perfumes, imaging agents, thermal cross-linking agents, thermal radical polymerization initiators, and the like.
本実施形態に係る感光性フィルム及び感光性樹脂組成物において、熱ラジカル重合開始剤の含有量は、感光性フィルムの全量、又は、感光性樹脂組成物の全量（固形分全量）を基準として、０．５質量％以下、０．５質量％未満、０．１質量％以下、０．０１質量％以下、又は、０．００１質量％以下であってよい。本実施形態に係る感光性フィルム及び感光性樹脂組成物は、熱ラジカル重合開始剤を含有しなくてよい（上述の含有量が実質的に０質量％であってよい）。
In the photosensitive film and photosensitive resin composition according to the present embodiment, the content of the thermal radical polymerization initiator is based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content), It may be 0.5% by mass or less, less than 0.5% by mass, 0.1% by mass or less, 0.01% by mass or less, or 0.001% by mass or less. The photosensitive film and photosensitive resin composition according to the present embodiment may not contain a thermal radical polymerization initiator (the above content may be substantially 0% by mass).
本実施形態に係る感光性フィルム及び感光性樹脂組成物において、ビニル重合体（例えば、エポキシ基を有する側鎖を含むビニル重合体）、及び、オキセタン化合物（例えば、置換基を有していてもよいオキセタン環を２以上有するオキセタン化合物）からなる群より選ばれる少なくとも一種の含有量は、感光性フィルムの全量、又は、感光性樹脂組成物の全量（固形分全量）を基準として、２０質量％以下、２０質量％未満、１０質量％以下、１質量％以下、０．１質量％以下、０．０１質量％以下、又は、０．００１質量％以下であってよい。本実施形態に係る感光性フィルム及び感光性樹脂組成物は、ビニル重合体（例えば、エポキシ基を有する側鎖を含むビニル重合体）、及び、オキセタン化合物（例えば、置換基を有していてもよいオキセタン環を２以上有するオキセタン化合物）からなる群より選ばれる少なくとも一種を含有しなくてよい（上述の含有量が実質的に０質量％であってよい）。
In the photosensitive film and photosensitive resin composition according to the present embodiment, a vinyl polymer (e.g., a vinyl polymer containing a side chain having an epoxy group) and an oxetane compound (e.g., even if it has a substituent The content of at least one selected from the group consisting of oxetane compounds having two or more good oxetane rings is 20% by mass based on the total amount of the photosensitive film or the total amount of the photosensitive resin composition (total solid content). Below, it may be less than 20% by mass, 10% by mass or less, 1% by mass or less, 0.1% by mass or less, 0.01% by mass or less, or 0.001% by mass or less. The photosensitive film and photosensitive resin composition according to the present embodiment include a vinyl polymer (e.g., a vinyl polymer containing a side chain having an epoxy group) and an oxetane compound (e.g., even if it has a substituent oxetane compounds having two or more good oxetane rings) may not be contained (the above content may be substantially 0% by mass).
本実施形態に係る感光性フィルム及び感光性樹脂組成物において、アントラセン化合物、ジスチリルベンゼン化合物及びナフタレン化合物からなる群より選ばれる少なくとも一種の含有量は、感光性フィルムの全量、又は、感光性樹脂組成物の全量（固形分全量）を基準として、０．０１質量％以下、０．０１質量％未満、０．００１質量％以下、又は、０．０００１質量％以下であってよい。本実施形態に係る感光性フィルム及び感光性樹脂組成物は、アントラセン化合物、ジスチリルベンゼン化合物及びナフタレン化合物からなる群より選ばれる少なくとも一種を含有しなくてよい（上述の含有量が実質的に０質量％であってよい）。
In the photosensitive film and photosensitive resin composition according to the present embodiment, the content of at least one selected from the group consisting of anthracene compounds, distyrylbenzene compounds and naphthalene compounds is the total amount of the photosensitive film or the photosensitive resin It may be 0.01% by mass or less, less than 0.01% by mass, 0.001% by mass or less, or 0.0001% by mass or less based on the total amount of the composition (total solid content). The photosensitive film and photosensitive resin composition according to the present embodiment may not contain at least one selected from the group consisting of an anthracene compound, a distyrylbenzene compound and a naphthalene compound (the above content is substantially 0). % by mass).
本実施形態に係る感光性フィルム及び感光性樹脂組成物において、ニトロキシル化合物の含有量は、（Ａ）成分１００質量部、又は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して、０．００５質量部以下、０．００５質量部未満、０．００１質量部以下、又は、０．０００１質量部以下であってよい。本実施形態に係る感光性フィルム及び感光性樹脂組成物は、ニトロキシル化合物を含有しなくてよい（上述の含有量が実質的に０質量部であってよい）。
In the photosensitive film and photosensitive resin composition according to the present embodiment, the content of the nitroxyl compound is based on 100 parts by mass of component (A) or 100 parts by mass of the total amount of components (A) and (B). , 0.005 parts by weight or less, less than 0.005 parts by weight, 0.001 parts by weight or less, or 0.0001 parts by weight or less. The photosensitive film and photosensitive resin composition according to the present embodiment may not contain a nitroxyl compound (the above content may be substantially 0 parts by mass).
本実施形態に係る感光性フィルム及び感光性樹脂組成物において、メルカプト化合物の含有量は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して、０．１質量部以下、０．１質量部未満、０．００１質量部以下、０．００１質量部未満、又は、０．０００１質量部以下であってよい。本実施形態に係る感光性フィルム及び感光性樹脂組成物は、メルカプト化合物を含有しなくてよい（上述の含有量が実質的に０質量部であってよい）。
In the photosensitive film and photosensitive resin composition according to the present embodiment, the content of the mercapto compound is 0.1 part by mass or less, 0.1 part by mass or less with respect to 100 parts by mass as the total amount of components (A) and (B). It may be less than 1 part by weight, 0.001 parts by weight or less, less than 0.001 parts by weight, or 0.0001 parts by weight or less. The photosensitive film and photosensitive resin composition according to the present embodiment may not contain a mercapto compound (the above content may be substantially 0 parts by mass).
＜感光性エレメント＞
本実施形態に係る感光性エレメントは、支持体と、当該支持体上に配置された感光性樹脂層と、を備え、感光性樹脂層が、本実施形態に係る感光性フィルムである。本実施形態に係る感光性エレメントは、感光性樹脂層上に配置された保護層を備えてよい。本実施形態に係る感光性エレメントは、クッション層、接着層、光吸収層、ガスバリア層等を備えてよい。感光性エレメントは、シート状であってよく、巻芯にロール状に巻き取られた感光性エレメントロールの形態であってよい。 <Photosensitive element>
A photosensitive element according to this embodiment includes a support and a photosensitive resin layer disposed on the support, and the photosensitive resin layer is the photosensitive film according to this embodiment. The photosensitive element according to this embodiment may comprise a protective layer disposed on the photosensitive resin layer. The photosensitive element according to this embodiment may comprise a cushion layer, an adhesive layer, a light absorbing layer, a gas barrier layer, and the like. The photosensitive element may be in the form of a sheet, or in the form of a photosensitive element roll wound around a core.
本実施形態に係る感光性エレメントは、支持体と、当該支持体上に配置された感光性樹脂層と、を備え、感光性樹脂層が、本実施形態に係る感光性フィルムである。本実施形態に係る感光性エレメントは、感光性樹脂層上に配置された保護層を備えてよい。本実施形態に係る感光性エレメントは、クッション層、接着層、光吸収層、ガスバリア層等を備えてよい。感光性エレメントは、シート状であってよく、巻芯にロール状に巻き取られた感光性エレメントロールの形態であってよい。 <Photosensitive element>
A photosensitive element according to this embodiment includes a support and a photosensitive resin layer disposed on the support, and the photosensitive resin layer is the photosensitive film according to this embodiment. The photosensitive element according to this embodiment may comprise a protective layer disposed on the photosensitive resin layer. The photosensitive element according to this embodiment may comprise a cushion layer, an adhesive layer, a light absorbing layer, a gas barrier layer, and the like. The photosensitive element may be in the form of a sheet, or in the form of a photosensitive element roll wound around a core.
図１は、感光性エレメントの一例を示す模式断面図である。図１に示すように、感光性エレメント１は、支持体（支持フィルム）２と、支持体２上に配置された感光性樹脂層（感光性フィルム）３と、感光性樹脂層３上に配置された保護層（保護フィルム）４と、を備えている。感光性樹脂層３は、本実施形態に係る感光性樹脂組成物からなる。
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 photosensitive resin layer 3 disposed on the and a protective layer (protective film) 4. The photosensitive resin layer 3 is made of the photosensitive resin composition according to this embodiment.
感光性エレメント１は、例えば、次の手順で得ることができる。まず、支持体２上に感光性樹脂層３を形成する。感光性樹脂層３は、例えば、有機溶剤を含有する感光性樹脂組成物を塗布して形成された塗布層を乾燥することにより形成できる。次いで、感光性樹脂層３上に保護層４を配置する。
The photosensitive element 1 can be obtained, for example, by the following procedure. First, the photosensitive resin layer 3 is formed on the support 2 . The photosensitive resin layer 3 can be formed, for example, by drying a coating layer formed by applying a photosensitive resin composition containing an organic solvent. Next, a protective layer 4 is arranged on the photosensitive resin layer 3 .
支持体及び保護層のそれぞれは、耐熱性及び耐溶剤性を有するポリマーフィルムであってよく、ポリエステルフィルム（ポリエチレンテレフタレートフィルム等）、ポリオレフィンフィルム（ポリエチレンフィルム、ポリプロピレンフィルム等）、炭化水素系ポリマー（ポリオレフィンフィルムを除く）などであってよい。保護層を構成するフィルムの種類と、支持体を構成するフィルムの種類とは、互いに同一であってよく、互いに異なっていてもよい。
Each of the support and the protective layer may be a polymer film having heat resistance and solvent resistance, such as a polyester film (polyethylene terephthalate film, etc.), a polyolefin film (polyethylene film, polypropylene film, etc.), a hydrocarbon-based polymer (polyolefin film, etc.). excluding film). The type of film forming the protective layer and the type of film forming the support may be the same or different.
支持体の厚さは、支持体を感光性樹脂層から剥離する際の支持体の破損を抑制しやすい観点から、１μｍ以上、５μｍ以上、１０μｍ以上、又は、１５μｍ以上であってよい。支持体の厚さは、支持体を介して露光する場合に好適に露光しやすい観点から、１００μｍ以下、５０μｍ以下、３０μｍ以下、又は、２０μｍ以下であってよい。
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 damage to the support when the support is peeled off 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 favorable exposure when exposed through the support.
保護層の厚さは、保護層を剥がしながら感光性樹脂層及び支持体を基材上にラミネートする際の保護層の破損を抑制しやすい観点から、１μｍ以上、５μｍ以上、１０μｍ以上、又は、１５μｍ以上であってよい。保護層の厚さは、生産性が向上しやすい観点から、１００μｍ以下、５０μｍ以下、又は、３０μｍ以下であってよい。
The thickness of the protective layer is 1 μm or more, 5 μm or more, 10 μm or more, or It may be 15 μm or more. 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 easily improving productivity.
＜積層体の製造方法＞
本実施形態に係る積層体の製造方法は、本実施形態に係る感光性フィルム、感光性エレメント又は感光性樹脂組成物を用いて感光性樹脂層を基材（例えば基板）上に配置する配置工程（感光性樹脂層配置工程）と、感光性樹脂層の一部を光硬化させる（露光する）露光工程と、感光性樹脂層の未硬化部（未露光部）の少なくとも一部を除去して硬化物パターンを形成する現像工程と、を備える。本実施形態に係る積層体は、本実施形態に係る積層体の製造方法により得られ、配線基板（例えばプリント配線板）であってよい。本実施形態に係る積層体は、基材と、当該基材上に配置された硬化物パターン（本実施形態に係る硬化物）と、を備える態様であってよい。 <Method for manufacturing laminate>
The method for producing a laminate according to the present embodiment includes an arrangement step of arranging a photosensitive resin layer on a substrate (for example, a substrate) using the photosensitive film, the photosensitive element, or the photosensitive resin composition according to the present embodiment. (Photosensitive resin layer arranging step), an exposure step of photocuring (exposing) a part of the photosensitive resin layer, and removing at least a part of the uncured portion (unexposed portion) of the photosensitive resin layer and a developing step of forming a cured product pattern. The laminate according to this embodiment is obtained by the method for producing a laminate according to this embodiment, and may be a wiring board (for example, a printed wiring board). The laminate according to the present embodiment may be in a mode including a substrate and a cured product pattern (cured product according to the present embodiment) arranged on the substrate.
本実施形態に係る積層体の製造方法は、本実施形態に係る感光性フィルム、感光性エレメント又は感光性樹脂組成物を用いて感光性樹脂層を基材（例えば基板）上に配置する配置工程（感光性樹脂層配置工程）と、感光性樹脂層の一部を光硬化させる（露光する）露光工程と、感光性樹脂層の未硬化部（未露光部）の少なくとも一部を除去して硬化物パターンを形成する現像工程と、を備える。本実施形態に係る積層体は、本実施形態に係る積層体の製造方法により得られ、配線基板（例えばプリント配線板）であってよい。本実施形態に係る積層体は、基材と、当該基材上に配置された硬化物パターン（本実施形態に係る硬化物）と、を備える態様であってよい。 <Method for manufacturing laminate>
The method for producing a laminate according to the present embodiment includes an arrangement step of arranging a photosensitive resin layer on a substrate (for example, a substrate) using the photosensitive film, the photosensitive element, or the photosensitive resin composition according to the present embodiment. (Photosensitive resin layer arranging step), an exposure step of photocuring (exposing) a part of the photosensitive resin layer, and removing at least a part of the uncured portion (unexposed portion) of the photosensitive resin layer and a developing step of forming a cured product pattern. The laminate according to this embodiment is obtained by the method for producing a laminate according to this embodiment, and may be a wiring board (for example, a printed wiring board). The laminate according to the present embodiment may be in a mode including a substrate and a cured product pattern (cured product according to the present embodiment) arranged on the substrate.
基材は、凹部を有してよい。凹部の断面形状（積層方向に直交する断面の形状）は、円状（例えば略真円状）、矩形状、ライン状（直線状）等であってよい。基材の凹部は、有底の凹部であってよい。凹部の直径（例えば最大径）又は深さ（積層方向の長さ）は、下記の範囲であってよい。凹部の直径は、１０μｍ以上、３０μｍ以上、５０μｍ以上、８０μｍ以上、１００μｍ以上、１２０μｍ以上、１５０μｍ以上、１８０μｍ以上、又は、２００μｍ以上であってよい。凹部の直径は、５００μｍ以下、４００μｍ以下、３００μｍ以下、２５０μｍ以下、又は、２００μｍ以下であってよい。これらの観点から、凹部の直径は、１０～５００μｍであってよい。凹部の深さは、１μｍ以上、３μｍ以上、５μｍ以上、６μｍ以上、又は、８μｍ以上であってよい。凹部の深さは、２０μｍ以下、１８μｍ以下、１５μｍ以下、１２μｍ以下、１０μｍ以下、又は、８μｍ以下であってよい。凹部の深さは、１～２０μｍであってよい。
The base material may have recesses. The cross-sectional shape of the concave portion (cross-sectional shape perpendicular to the stacking direction) may be circular (for example, substantially perfect circular), rectangular, linear (linear), or the like. The concave portion of the substrate may be a bottomed concave portion. The diameter (for example, maximum diameter) or depth (length in the stacking direction) of the recess may be within the following ranges. The diameter of the recess may be 10 μm or more, 30 μm or more, 50 μm or more, 80 μm or more, 100 μm or more, 120 μm or more, 150 μm or more, 180 μm or more, or 200 μm or more. The diameter of the recess may be 500 μm or less, 400 μm or less, 300 μm or less, 250 μm or less, or 200 μm or less. From these points of view, the diameter of the recess may be 10 to 500 μm. The depth of the recess may be 1 μm or more, 3 μm or more, 5 μm or more, 6 μm or more, or 8 μm or more. The depth of the recess may be 20 μm or less, 18 μm or less, 15 μm or less, 12 μm or less, 10 μm or less, or 8 μm or less. The depth of the recess may be 1-20 μm.
配置工程では、本実施形態に係る感光性樹脂組成物からなる感光性樹脂層を基材上に配置する。例えば、感光性樹脂層は、感光性エレメントから保護層を除去した後、感光性エレメントの感光性樹脂層を加熱しながら基材に圧着することによって形成してよく、感光性樹脂組成物を基材上に塗布及び乾燥することによって形成してよい。本実施形態に係る積層体の製造方法は、基材が上述の直径（例えば直径５００μｍ以下）の凹部を有し、配置工程において感光性樹脂層の少なくとも一部が凹部内に配置される態様であってよい。
In the placement step, a photosensitive resin layer made of the photosensitive resin composition according to the present embodiment is placed on the substrate. For example, the photosensitive resin layer may be formed by removing the protective layer from the photosensitive element and pressing the photosensitive resin layer of the photosensitive element onto the substrate while heating. It may be formed by coating and drying on the material. In the method for producing a laminate according to the present embodiment, the base material has a concave portion having the above diameter (for example, a diameter of 500 μm or less), and at least a part of the photosensitive resin layer is arranged in the concave portion in the placing step. It's okay.
露光工程では、感光性樹脂層上にマスクを配置した状態で活性光線を照射して、感光性樹脂層におけるマスクが配置された領域以外の領域を露光して光硬化させてよく、マスクを用いずに、ＬＤＩ露光法、ＤＬＰ露光法等の直接描画露光法により活性光線を所望のパターンで照射して感光性樹脂層の一部を露光して光硬化させてよい。活性光線の光源としては、紫外光源又は可視光源を用いてよく、カーボンアーク灯、水銀蒸気アーク灯、高圧水銀灯、キセノンランプ、ガスレーザ（アルゴンレーザ等）、固体レーザ（ＹＡＧレーザ等）、半導体レーザなどが挙げられる。
In the exposure step, an actinic ray is irradiated with a mask placed on the photosensitive resin layer, and a region other than the region where the mask is placed in the photosensitive resin layer may be exposed and photocured. Instead, a part of the photosensitive resin layer may be exposed and photocured by irradiating actinic rays in a desired pattern by a direct drawing exposure method such as an LDI exposure method or a DLP exposure method. As a light source for actinic rays, an ultraviolet light source or a visible light source may be used, such as 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), a semiconductor laser, and the like. is mentioned.
現像工程における現像方法は、例えば、ウェット現像又はドライ現像であってよい。ウェット現像は、感光性樹脂組成物に対応した現像液を用いて、例えば、ディップ方式、パドル方式、スプレー方式、ブラッシング、スラッピング、スクラッビング、揺動浸漬等の方法により行うことができる。現像液は、感光性樹脂組成物の構成に応じて適宜選択され、アルカリ現像液又は有機溶剤現像液であってよい。
The development method in the development process may be, for example, wet development or dry development. Wet development can be carried out by using a developer corresponding to the photosensitive resin composition, for example, by dipping, puddle, spraying, brushing, slapping, scrubbing, rocking immersion, and the like. The developer is appropriately selected according to the constitution of the photosensitive resin composition, and may be an alkaline developer or an organic solvent developer.
アルカリ現像液は、リチウム、ナトリウム又はカリウムの水酸化物等の水酸化アルカリ；リチウム、ナトリウム、カリウム若しくはアンモニウムの炭酸塩又は重炭酸塩等の炭酸アルカリ；リン酸カリウム、リン酸ナトリウム等のアルカリ金属リン酸塩；ピロリン酸ナトリウム、ピロリン酸カリウム等のアルカリ金属ピロリン酸塩；ホウ砂；メタケイ酸ナトリウム；水酸化テトラメチルアンモニウム；エタノールアミン；エチレンジアミン；ジエチレントリアミン；２－アミノ－２－ヒドロキシメチル－１，３－プロパンジオール；１，３－ジアミノ－２－プロパノール；モルホリンなどの塩基を含む水溶液であってよい。
Alkaline developers include alkali hydroxides such as lithium, sodium or potassium hydroxide; alkali carbonates such as lithium, sodium, potassium or ammonium carbonates or bicarbonates; alkali metals such as potassium phosphate and sodium phosphate. Phosphates; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; borax; sodium metasilicate; tetramethylammonium hydroxide; ethanolamine; ethylenediamine; diethylenetriamine; It may be an aqueous solution containing a base such as 3-propanediol; 1,3-diamino-2-propanol; morpholine.
有機溶剤現像液は、１，１，１－トリクロロエタン、Ｎ－メチルピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、シクロヘキサノン、メチルイソブチルケトン、γ－ブチロラクトン等の有機溶剤を含有してよい。
The organic solvent developer may contain organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methylisobutylketone and γ-butyrolactone.
本実施形態に係る積層体の製造方法は、現像工程の後に、基材における硬化物パターンが形成されていない部分の少なくとも一部に金属層を形成する金属層形成工程を備えてよい。本実施形態に係る積層体は、基材と、当該基材上に配置された硬化物パターン（本実施形態に係る硬化物）と、基材における硬化物パターンが形成されていない部分の少なくとも一部に配置された金属層と、を備える態様であってよい。
The method for producing a laminate according to the present embodiment may include, after the developing step, a metal layer forming step of forming a metal layer on at least part of the portion of the substrate where the cured product pattern is not formed. The laminate according to the present embodiment includes a substrate, a cured product pattern (cured product according to the present embodiment) arranged on the substrate, and at least one part of the substrate where the cured product pattern is not formed. and a metal layer disposed on the part.
金属層形成工程における金属層は、例えば金属銅層であってよい。金属層は、例えば、めっき処理を施すことにより形成できる。めっき処理は、電解めっき処理及び無電解めっき処理の一方又は両方であってよい。
The metal layer in the metal layer forming step may be, for example, a metal copper layer. The metal layer can be formed by plating, for example. The plating treatment may be one or both of electrolytic plating treatment and electroless plating treatment.
本実施形態に係る積層体の製造方法は、現像工程の後に、６０～２５０℃の加熱、又は、０．２～１０Ｊ／ｃｍ２での露光を行うことによりレジストパターンを更に硬化させる工程を備えてよい。
The method for manufacturing a laminate according to the present embodiment includes a step of further curing the resist pattern by heating at 60 to 250° C. or exposing at 0.2 to 10 J/cm 2 after the developing step. you can
本実施形態に係る積層体の製造方法は、金属層形成工程の後に、硬化物パターンを除去する工程を備えてよい。硬化物パターンは、例えば、強アルカリ性水溶液を用いて、浸漬方式、スプレー方式等の現像を行うことにより除去できる。
The method for manufacturing a laminate according to this 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, developing with a strong alkaline aqueous solution by an immersion method, a spray method, or the like.
以下、実施例により本開示を更に具体的に説明するが、本開示はこれらの実施例に限定されるものではない。
The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.
＜バインダーポリマーの合成＞
メタクリル酸２７質量部、メタクリル酸２－ヒドロキシエチル３質量部、メタクリル酸ベンジル２０質量部、スチレン５０質量部、及び、アゾビスイソブチロニトリル０．９質量部を混合することにより溶液（ａ）を調製した。メチルセロソルブ３０質量部及びトルエン２０質量部の混合液５０質量部にアゾビスイソブチロニトリル０．５質量部を溶解することにより溶液（ｂ）を調製した。撹拌機、還流冷却器、温度計、滴下ロート及び窒素ガス導入管を備えるフラスコ内にメチルセロソルブ及びトルエンの混合液（メチルセロソルブ：トルエン＝４５：３８（質量比））を投入した後、フラスコ内に窒素ガスを吹き込みながら撹拌し、８０℃まで昇温させた。一定の滴下速度で溶液（ａ）を上述のフラスコ内に４時間かけて滴下した後、フラスコ内の溶液を８０℃にて２時間撹拌した。次いで、一定の滴下速度で溶液（ｂ）を上述のフラスコ内に１０分間かけて滴下した後、フラスコ内の溶液を８０℃にて３時間撹拌した。さらに、フラスコ内の溶液を１時間かけて９５℃まで昇温させ、９０℃にて２時間保温した後、撹拌を止め、室温（２５℃）まで冷却することによりバインダーポリマーＡ１の溶液を得た。バインダーポリマーＡ１の溶液の不揮発分（固形分）は４９質量％であった。 <Synthesis of binder polymer>
Solution (a) 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 parts by mass of azobisisobutyronitrile was prepared. A solution (b) was prepared by dissolving 0.5 parts by mass of azobisisobutyronitrile in 50 parts by mass of a mixture of 30 parts by mass of methyl cellosolve and 20 parts by mass of toluene. A mixture of methyl cellosolve and toluene (methyl cellosolve: toluene = 45:38 (mass ratio)) was introduced into a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas inlet tube, and then The mixture was stirred while nitrogen gas was blown into it, and the temperature was raised to 80°C. After the solution (a) was dropped into the flask over 4 hours at a constant dropping rate, the solution in the flask was stirred at 80° C. for 2 hours. Next, the solution (b) was added dropwise into the flask over 10 minutes at a constant dropping rate, and then the solution in the flask was stirred at 80° C. for 3 hours. Further, the solution in the flask was heated to 95°C over 1 hour and kept at 90°C for 2 hours, then stirring was stopped and the solution was cooled to room temperature (25°C) to obtain a solution of binder polymer A1. . The non-volatile content (solid content) of the solution of binder polymer A1 was 49% by mass.
メタクリル酸２７質量部、メタクリル酸２－ヒドロキシエチル３質量部、メタクリル酸ベンジル２０質量部、スチレン５０質量部、及び、アゾビスイソブチロニトリル０．９質量部を混合することにより溶液（ａ）を調製した。メチルセロソルブ３０質量部及びトルエン２０質量部の混合液５０質量部にアゾビスイソブチロニトリル０．５質量部を溶解することにより溶液（ｂ）を調製した。撹拌機、還流冷却器、温度計、滴下ロート及び窒素ガス導入管を備えるフラスコ内にメチルセロソルブ及びトルエンの混合液（メチルセロソルブ：トルエン＝４５：３８（質量比））を投入した後、フラスコ内に窒素ガスを吹き込みながら撹拌し、８０℃まで昇温させた。一定の滴下速度で溶液（ａ）を上述のフラスコ内に４時間かけて滴下した後、フラスコ内の溶液を８０℃にて２時間撹拌した。次いで、一定の滴下速度で溶液（ｂ）を上述のフラスコ内に１０分間かけて滴下した後、フラスコ内の溶液を８０℃にて３時間撹拌した。さらに、フラスコ内の溶液を１時間かけて９５℃まで昇温させ、９０℃にて２時間保温した後、撹拌を止め、室温（２５℃）まで冷却することによりバインダーポリマーＡ１の溶液を得た。バインダーポリマーＡ１の溶液の不揮発分（固形分）は４９質量％であった。 <Synthesis of binder polymer>
Solution (a) 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 parts by mass of azobisisobutyronitrile was prepared. A solution (b) was prepared by dissolving 0.5 parts by mass of azobisisobutyronitrile in 50 parts by mass of a mixture of 30 parts by mass of methyl cellosolve and 20 parts by mass of toluene. A mixture of methyl cellosolve and toluene (methyl cellosolve: toluene = 45:38 (mass ratio)) was introduced into a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas inlet tube, and then The mixture was stirred while nitrogen gas was blown into it, and the temperature was raised to 80°C. After the solution (a) was dropped into the flask over 4 hours at a constant dropping rate, the solution in the flask was stirred at 80° C. for 2 hours. Next, the solution (b) was added dropwise into the flask over 10 minutes at a constant dropping rate, and then the solution in the flask was stirred at 80° C. for 3 hours. Further, the solution in the flask was heated to 95°C over 1 hour and kept at 90°C for 2 hours, then stirring was stopped and the solution was cooled to room temperature (25°C) to obtain a solution of binder polymer A1. . The non-volatile content (solid content) of the solution of binder polymer A1 was 49% by mass.
バインダーポリマーＡ１の酸価は１７６ｍｇＫＯＨ／ｇであった。酸価は次の手順で測定した。まず、三角フラスコにバインダーポリマーＡ１を秤量した。次いで、混合溶剤（質量比：トルエン／メタノール＝７０／３０）を加えてバインダーポリマーＡ１を溶解した後、指示薬としてフェノールフタレイン溶液を添加した。そして、０．１ｍｏｌ／Ｌ（Ｎ／１０）水酸化カリウム溶液（アルコール溶液）を用いて滴定することにより酸価を得た。
The acid value of binder polymer A1 was 176 mgKOH/g. The acid value was measured by the following procedure. First, binder polymer A1 was weighed in an Erlenmeyer flask. Next, a mixed solvent (mass ratio: toluene/methanol=70/30) was added to dissolve the binder polymer A1, and then a phenolphthalein solution was added as an indicator. Then, the acid value was obtained by titration with a 0.1 mol/L (N/10) potassium hydroxide solution (alcohol solution).
バインダーポリマーＡ１の重量平均分子量（Ｍｗ）は３５０００であり、数平均分子量（Ｍｎ）は１６０００であった。重量平均分子量及び数平均分子量は、下記条件のゲルパーミエーションクロマトグラフィー法（ＧＰＣ）によって測定し、標準ポリスチレンの検量線を用いて換算することにより導出した。
The binder polymer A1 had a weight average molecular weight (Mw) of 35,000 and a number average molecular weight (Mn) of 16,000. The weight-average molecular weight and number-average molecular weight were measured by gel permeation chromatography (GPC) under the following conditions and derived by conversion using a standard polystyrene calibration curve.
（ＧＰＣ条件）
ポンプ：日立 Ｌ－６０００型（株式会社日立製作所製、商品名）
カラム：以下の計３本（昭和電工マテリアルズ株式会社製、商品名）
Ｇｅｌｐａｃｋ ＧＬ－Ｒ４４０
Ｇｅｌｐａｃｋ ＧＬ－Ｒ４５０
Ｇｅｌｐａｃｋ ＧＬ－Ｒ４００Ｍ
溶離液：テトラヒドロフラン
測定温度：４０℃
注入量：２００μＬ
流量：２．０５ｍＬ／分
検出器：日立 Ｌ－３３００型ＲＩ（株式会社日立製作所製、商品名） (GPC conditions)
Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd., trade name)
Columns: The following three columns (manufactured by Showa Denko Materials Co., Ltd., trade name)
Gelpack GL-R440
Gelpack GL-R450
Gelpack GL-R400M
Eluent: Tetrahydrofuran Measurement temperature: 40°C
Injection volume: 200 μL
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., trade name)
ポンプ：日立 Ｌ－６０００型（株式会社日立製作所製、商品名）
カラム：以下の計３本（昭和電工マテリアルズ株式会社製、商品名）
Ｇｅｌｐａｃｋ ＧＬ－Ｒ４４０
Ｇｅｌｐａｃｋ ＧＬ－Ｒ４５０
Ｇｅｌｐａｃｋ ＧＬ－Ｒ４００Ｍ
溶離液：テトラヒドロフラン
測定温度：４０℃
注入量：２００μＬ
流量：２．０５ｍＬ／分
検出器：日立 Ｌ－３３００型ＲＩ（株式会社日立製作所製、商品名） (GPC conditions)
Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd., trade name)
Columns: The following three columns (manufactured by Showa Denko Materials Co., Ltd., trade name)
Gelpack GL-R440
Gelpack GL-R450
Gelpack GL-R400M
Eluent: Tetrahydrofuran Measurement temperature: 40°C
Injection volume: 200 μL
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., trade name)
溶液（ａ）の調製に用いる単量体をメタクリル酸２７質量部、メタクリル酸２－ヒドロキシエチル５質量部、メタクリル酸ベンジル２３質量部及びスチレン４５質量部に変更したことを除いてバインダーポリマーＡ１と同様に操作することにより、バインダーポリマーＡ２の溶液を得た。バインダーポリマーＡ２の溶液の不揮発分（固形分）は４９質量％であった。バインダーポリマーＡ２の酸価は１７５ｍｇＫＯＨ／ｇであり、重量平均分子量（Ｍｗ）は３５０００であり、数平均分子量（Ｍｎ）は１６５００であった。
Binder polymer A1 and By operating in the same manner, a solution of binder polymer A2 was obtained. The non-volatile content (solid content) of the solution of binder polymer A2 was 49% by mass. The binder polymer A2 had an acid value of 175 mgKOH/g, a weight average molecular weight (Mw) of 35,000, and a number average molecular weight (Mn) of 16,500.
＜感光性樹脂組成物の調製＞
表１に示す各成分と、トルエン１６質量部と、メタノール６質量部と、アセトン１０質量部と、を混合することにより感光性樹脂組成物を調製した。表１は、各成分の配合量（質量部）を示しており、バインダーポリマー及びＦＡ－３２１Ｍ（７０）の配合量は不揮発分の質量（固形分量）である。表１に示す各成分の詳細については下記のとおりである。 <Preparation of photosensitive resin composition>
A photosensitive resin composition was prepared by mixing each component shown in Table 1, 16 parts by mass of toluene, 6 parts by mass of methanol, and 10 parts by mass of acetone. Table 1 shows the amount (parts by mass) of each component, and the amount of the binder polymer and FA-321M (70) is the weight of the non-volatile matter (solid content). Details of each component shown in Table 1 are as follows.
表１に示す各成分と、トルエン１６質量部と、メタノール６質量部と、アセトン１０質量部と、を混合することにより感光性樹脂組成物を調製した。表１は、各成分の配合量（質量部）を示しており、バインダーポリマー及びＦＡ－３２１Ｍ（７０）の配合量は不揮発分の質量（固形分量）である。表１に示す各成分の詳細については下記のとおりである。 <Preparation of photosensitive resin composition>
A photosensitive resin composition was prepared by mixing each component shown in Table 1, 16 parts by mass of toluene, 6 parts by mass of methanol, and 10 parts by mass of acetone. Table 1 shows the amount (parts by mass) of each component, and the amount of the binder polymer and FA-321M (70) is the weight of the non-volatile matter (solid content). Details of each component shown in Table 1 are as follows.
（光重合性化合物）
ＦＡ－３２１Ｍ（７０）：２，２－ビス（４－（メタクリロキシポリエトキシ）フェニル）プロパン（エチレンオキサイド平均１０ｍｏｌ付加物）のプロピレングリコールモノメチルエーテル７０％溶液（ＥＯ変性ビスフェノールＡジメタクリレート、昭和電工マテリアルズ株式会社製、分子量：８０４）
ＢＰ－２ＥＭ：２，２－ビス（４－（メタクリロキシポリエトキシ）フェニル）プロパン（共栄社化学株式会社製、ＥＯ基：５．２（合計値）、分子量：４７８）
ＦＡ－０２４Ｍ：（ＰＯ）（ＥＯ）（ＰＯ）変性ジメタクリレート（昭和電工マテリアルズ株式会社製、エチレンオキサイド平均６ｍｏｌ及びプロピレンオキサイド平均１２ｍｏｌ付加物（合計値）、分子量：１１１４）
３官能モノマー：ＥＯ変性トリメチロールプロパントリメタクリレート（昭和電工マテリアルズ株式会社製、商品名「ＦＡ－１３７Ｍ」、ＥＯ基：２１（合計値）） (Photopolymerizable compound)
FA-321M (70): 2,2-bis(4-(methacryloxypolyethoxy)phenyl)propane (ethylene oxide average 10 mol adduct) propylene glycol monomethyl ether 70% solution (EO-modified bisphenol A dimethacrylate, Showa Denko Materials Co., Ltd., molecular weight: 804)
BP-2EM: 2,2-bis(4-(methacryloxypolyethoxy)phenyl)propane (manufactured by Kyoeisha Chemical Co., Ltd., EO group: 5.2 (total value), molecular weight: 478)
FA-024M: (PO)(EO)(PO)-modified dimethacrylate (manufactured by Showa Denko Materials Co., Ltd., ethylene oxide average 6 mol and propylene oxide average 12 mol adduct (total value), molecular weight: 1114)
Trifunctional monomer: EO-modified trimethylolpropane trimethacrylate (manufactured by Showa Denko Materials Co., Ltd., trade name "FA-137M", EO group: 21 (total value))
ＦＡ－３２１Ｍ（７０）：２，２－ビス（４－（メタクリロキシポリエトキシ）フェニル）プロパン（エチレンオキサイド平均１０ｍｏｌ付加物）のプロピレングリコールモノメチルエーテル７０％溶液（ＥＯ変性ビスフェノールＡジメタクリレート、昭和電工マテリアルズ株式会社製、分子量：８０４）
ＢＰ－２ＥＭ：２，２－ビス（４－（メタクリロキシポリエトキシ）フェニル）プロパン（共栄社化学株式会社製、ＥＯ基：５．２（合計値）、分子量：４７８）
ＦＡ－０２４Ｍ：（ＰＯ）（ＥＯ）（ＰＯ）変性ジメタクリレート（昭和電工マテリアルズ株式会社製、エチレンオキサイド平均６ｍｏｌ及びプロピレンオキサイド平均１２ｍｏｌ付加物（合計値）、分子量：１１１４）
３官能モノマー：ＥＯ変性トリメチロールプロパントリメタクリレート（昭和電工マテリアルズ株式会社製、商品名「ＦＡ－１３７Ｍ」、ＥＯ基：２１（合計値）） (Photopolymerizable compound)
FA-321M (70): 2,2-bis(4-(methacryloxypolyethoxy)phenyl)propane (ethylene oxide average 10 mol adduct) propylene glycol monomethyl ether 70% solution (EO-modified bisphenol A dimethacrylate, Showa Denko Materials Co., Ltd., molecular weight: 804)
BP-2EM: 2,2-bis(4-(methacryloxypolyethoxy)phenyl)propane (manufactured by Kyoeisha Chemical Co., Ltd., EO group: 5.2 (total value), molecular weight: 478)
FA-024M: (PO)(EO)(PO)-modified dimethacrylate (manufactured by Showa Denko Materials Co., Ltd., ethylene oxide average 6 mol and propylene oxide average 12 mol adduct (total value), molecular weight: 1114)
Trifunctional monomer: EO-modified trimethylolpropane trimethacrylate (manufactured by Showa Denko Materials Co., Ltd., trade name "FA-137M", EO group: 21 (total value))
（光重合開始剤）
ＢＣＩＭ：２，２’－ビス（ｏ－クロロフェニル）－４，４’，５，５’－テトラフェニル－１，２’－ビイミダゾール（Ｈａｍｐｆｏｒｄ社製） (Photoinitiator)
BCIM: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Hampford)
ＢＣＩＭ：２，２’－ビス（ｏ－クロロフェニル）－４，４’，５，５’－テトラフェニル－１，２’－ビイミダゾール（Ｈａｍｐｆｏｒｄ社製） (Photoinitiator)
BCIM: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Hampford)
（増感剤）
ＰＺ－５０１Ｄ：１－フェニル－３－（４－メトキシスチリル）－５－（４－メトキシフェニル）－ピラゾリン（株式会社日本化学工業所製）
ジフェニルアントラセン：東京化成工業株式会社製、商品名「９，１０－Ｄｉｐｈｅｎｙｌａｎｔｈｒａｃｅｎｅ」
ジシアノジスチリルベンゼン：４’－（２－シアノスチリル）－３－スチルベンカルボニトリル (sensitizer)
PZ-501D: 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline (manufactured by Nippon Kagaku Kogyosho Co., Ltd.)
Diphenylanthracene: manufactured by Tokyo Chemical Industry Co., Ltd., trade name “9,10-Diphenylanthracene”
Dicyanodistyrylbenzene: 4'-(2-cyanostyryl)-3-stilbenecarbonitrile
ＰＺ－５０１Ｄ：１－フェニル－３－（４－メトキシスチリル）－５－（４－メトキシフェニル）－ピラゾリン（株式会社日本化学工業所製）
ジフェニルアントラセン：東京化成工業株式会社製、商品名「９，１０－Ｄｉｐｈｅｎｙｌａｎｔｈｒａｃｅｎｅ」
ジシアノジスチリルベンゼン：４’－（２－シアノスチリル）－３－スチルベンカルボニトリル (sensitizer)
PZ-501D: 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline (manufactured by Nippon Kagaku Kogyosho Co., Ltd.)
Diphenylanthracene: manufactured by Tokyo Chemical Industry Co., Ltd., trade name “9,10-Diphenylanthracene”
Dicyanodistyrylbenzene: 4'-(2-cyanostyryl)-3-stilbenecarbonitrile
（その他の成分）
ＴＢＣ：４－ｔｅｒｔ－ブチルカテコール（ＤＩＣ株式会社製、商品名「ＤＩＣ－ＴＢＣ」）
ＬＣＶ：ロイコクリスタルバイオレット（山田化学工業株式会社製）
ＭＫＧ：マラカイトグリーン（大阪有機化学工業株式会社製）
ＳＦ－８０８Ｈ：カルボキシベンゾトリアゾール、５－アミノ－１Ｈ－テトラゾール及びメトキシプロパノールの混合物（サンワ化成株式会社製） (other ingredients)
TBC: 4-tert-butyl catechol (manufactured by DIC Corporation, trade name “DIC-TBC”)
LCV: Leuco Crystal Violet (manufactured by Yamada Chemical Industry Co., Ltd.)
MKG: Malachite Green (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
SF-808H: a mixture of carboxybenzotriazole, 5-amino-1H-tetrazole and methoxypropanol (manufactured by Sanwa Kasei Co., Ltd.)
ＴＢＣ：４－ｔｅｒｔ－ブチルカテコール（ＤＩＣ株式会社製、商品名「ＤＩＣ－ＴＢＣ」）
ＬＣＶ：ロイコクリスタルバイオレット（山田化学工業株式会社製）
ＭＫＧ：マラカイトグリーン（大阪有機化学工業株式会社製）
ＳＦ－８０８Ｈ：カルボキシベンゾトリアゾール、５－アミノ－１Ｈ－テトラゾール及びメトキシプロパノールの混合物（サンワ化成株式会社製） (other ingredients)
TBC: 4-tert-butyl catechol (manufactured by DIC Corporation, trade name “DIC-TBC”)
LCV: Leuco Crystal Violet (manufactured by Yamada Chemical Industry Co., Ltd.)
MKG: Malachite Green (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
SF-808H: a mixture of carboxybenzotriazole, 5-amino-1H-tetrazole and methoxypropanol (manufactured by Sanwa Kasei Co., Ltd.)
＜感光性エレメントの作製＞
支持体として厚さ１６μｍのポリエチレンテレフタレートフィルム（東レ株式会社製、商品名「ＦＢ－４０」）を用意した。厚さが均一になるように上述の感光性樹脂組成物を支持体上に塗布した後、７０℃及び１１０℃の熱風対流式乾燥器で順次乾燥することにより感光性樹脂層（感光性フィルム。乾燥後の１０箇所の平均厚さ：１９μｍ）を形成した。保護層としてポリエチレンフィルム（タマポリ株式会社製、商品名「ＮＦ－１５」）をこの感光性樹脂層に貼り合わせることにより、支持体、感光性樹脂層及び保護層を順に備える感光性エレメントを得た。 <Preparation of photosensitive element>
A polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name “FB-40”) having a thickness of 16 μm was prepared as a support. After coating the above-mentioned photosensitive resin composition on the support so that the thickness becomes uniform, the photosensitive resin composition is sequentially dried in a hot air convection dryer at 70° C. and 110° C. to obtain a photosensitive resin layer (photosensitive film. An average thickness of 10 locations after drying: 19 μm) was formed. A polyethylene film (manufactured by Tamapoly Co., Ltd., trade name "NF-15") was laminated as a protective layer to this photosensitive resin layer to obtain a photosensitive element comprising a support, a photosensitive resin layer and a protective layer in this order. .
支持体として厚さ１６μｍのポリエチレンテレフタレートフィルム（東レ株式会社製、商品名「ＦＢ－４０」）を用意した。厚さが均一になるように上述の感光性樹脂組成物を支持体上に塗布した後、７０℃及び１１０℃の熱風対流式乾燥器で順次乾燥することにより感光性樹脂層（感光性フィルム。乾燥後の１０箇所の平均厚さ：１９μｍ）を形成した。保護層としてポリエチレンフィルム（タマポリ株式会社製、商品名「ＮＦ－１５」）をこの感光性樹脂層に貼り合わせることにより、支持体、感光性樹脂層及び保護層を順に備える感光性エレメントを得た。 <Preparation of photosensitive element>
A polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name “FB-40”) having a thickness of 16 μm was prepared as a support. After coating the above-mentioned photosensitive resin composition on the support so that the thickness becomes uniform, the photosensitive resin composition is sequentially dried in a hot air convection dryer at 70° C. and 110° C. to obtain a photosensitive resin layer (photosensitive film. An average thickness of 10 locations after drying: 19 μm) was formed. A polyethylene film (manufactured by Tamapoly Co., Ltd., trade name "NF-15") was laminated as a protective layer to this photosensitive resin layer to obtain a photosensitive element comprising a support, a photosensitive resin layer and a protective layer in this order. .
＜積層体の作製＞
ガラスエポキシ材の両面に配置された銅箔（厚さ：１８μｍ）を備える銅張積層板（基板、昭和電工マテリアルズ株式会社製、商品名：ＭＣＬ－Ｅ－６７）に対して酸洗及び水洗後、空気流で乾燥することにより基材を得た。次いで、この基材を８０℃に加温した後、保護層を剥離しながら、感光性樹脂層が銅表面に接するように上述の感光性エレメントをラミネートすることにより、基材（銅張積層板）、感光性樹脂層、及び、支持体を順に備える積層体Ａを得た。ラミネートは、１１０℃のヒートロールを用いて、０．４ＭＰａの圧着圧力、１．５ｍ／分のロール速度で行った。 <Production of laminate>
A copper-clad laminate (substrate, manufactured by Showa Denko Materials Co., Ltd., trade name: MCL-E-67) with copper foil (thickness: 18 μm) arranged on both sides of a glass epoxy material is pickled and washed with water. Afterwards, the substrate was obtained by drying with an air stream. Next, after heating this substrate to 80° C., while peeling off the protective layer, the photosensitive element is laminated so that the photosensitive resin layer is in contact with the copper surface, thereby forming a substrate (copper-clad laminate ), a photosensitive resin layer, and a support in this order to obtain a laminate A. Lamination was performed using heat rolls at 110° C. at a pressure of 0.4 MPa and a roll speed of 1.5 m/min.
ガラスエポキシ材の両面に配置された銅箔（厚さ：１８μｍ）を備える銅張積層板（基板、昭和電工マテリアルズ株式会社製、商品名：ＭＣＬ－Ｅ－６７）に対して酸洗及び水洗後、空気流で乾燥することにより基材を得た。次いで、この基材を８０℃に加温した後、保護層を剥離しながら、感光性樹脂層が銅表面に接するように上述の感光性エレメントをラミネートすることにより、基材（銅張積層板）、感光性樹脂層、及び、支持体を順に備える積層体Ａを得た。ラミネートは、１１０℃のヒートロールを用いて、０．４ＭＰａの圧着圧力、１．５ｍ／分のロール速度で行った。 <Production of laminate>
A copper-clad laminate (substrate, manufactured by Showa Denko Materials Co., Ltd., trade name: MCL-E-67) with copper foil (thickness: 18 μm) arranged on both sides of a glass epoxy material is pickled and washed with water. Afterwards, the substrate was obtained by drying with an air stream. Next, after heating this substrate to 80° C., while peeling off the protective layer, the photosensitive element is laminated so that the photosensitive resin layer is in contact with the copper surface, thereby forming a substrate (copper-clad laminate ), a photosensitive resin layer, and a support in this order to obtain a laminate A. Lamination was performed using heat rolls at 110° C. at a pressure of 0.4 MPa and a roll speed of 1.5 m/min.
ガラスエポキシ材の両面に配置された銅箔（厚さ：１８μｍ）を備える銅張積層板（基板、昭和電工マテリアルズ株式会社製、商品名：ＭＣＬ－Ｅ－６７）に対して酸洗及び水洗後、空気流で乾燥することにより基材を得た。次いで、この基材に直径２００μｍ及び深さ８μｍの丸穴（断面形状：略真円）を２５箇所（配列：５×５、隣接する丸穴同士の最短距離：２ｃｍ）に形成した。次いで、この基材における丸穴が形成された面に対して、積層体Ａと同様の手順で上述の感光性エレメントをラミネートすることにより、基材（銅張積層板）、感光性樹脂層、及び、支持体を順に備える積層体Ｂを得た。
A copper-clad laminate (substrate, manufactured by Showa Denko Materials Co., Ltd., trade name: MCL-E-67) with copper foil (thickness: 18 μm) arranged on both sides of a glass epoxy material is pickled and washed with water. Afterwards, the substrate was obtained by drying with an air flow. Next, round holes (cross-sectional shape: substantially perfect circle) having a diameter of 200 μm and a depth of 8 μm were formed in this substrate at 25 locations (arrangement: 5×5, shortest distance between adjacent round holes: 2 cm). Next, by laminating the above-mentioned photosensitive element on the surface of the base material on which the round holes are formed in the same procedure as for the laminate A, the base material (copper-clad laminate), the photosensitive resin layer, Then, a laminate B provided with the support in order was obtained.
＜評価＞
（経時変化前の感度）
上述の積層体Ａの支持体上に４１段ステップタブレット（昭和電工マテリアルズ株式会社製）を載置した後、波長４０５ｎｍの青紫色レーザダイオードを光源とする直描露光機（ビアメカニクス株式会社製、商品名：ＤＥ－１ＵＨ）により、４１段ステップタブレットの現像後の残存段数が１５段となる露光量（照射エネルギー量）で、支持体を介して感光性樹脂層を露光した。このときの露光量（単位：ｍＪ／ｃｍ２）により感度（光感度）を評価した。結果を表１に示す。露光量が少ないほど、感度が良好であることを意味する。 <Evaluation>
(Sensitivity before aging)
After placing a 41-stage step tablet (manufactured by Showa Denko Materials Co., Ltd.) on the support of the laminate A described above, a direct exposure machine (manufactured by Via Mechanics Co., Ltd.) using a blue-violet laser diode with a wavelength of 405 nm as a light source , trade name: DE-1UH), the photosensitive resin layer was exposed through the support at an exposure amount (irradiation energy amount) such that the number of steps remaining after development of the 41-step tablet was 15 steps. The sensitivity (photosensitivity) was evaluated based on the amount of exposure (unit: mJ/cm 2 ) at this time. Table 1 shows the results. It means that the lower the exposure amount, the better the sensitivity.
（経時変化前の感度）
上述の積層体Ａの支持体上に４１段ステップタブレット（昭和電工マテリアルズ株式会社製）を載置した後、波長４０５ｎｍの青紫色レーザダイオードを光源とする直描露光機（ビアメカニクス株式会社製、商品名：ＤＥ－１ＵＨ）により、４１段ステップタブレットの現像後の残存段数が１５段となる露光量（照射エネルギー量）で、支持体を介して感光性樹脂層を露光した。このときの露光量（単位：ｍＪ／ｃｍ２）により感度（光感度）を評価した。結果を表１に示す。露光量が少ないほど、感度が良好であることを意味する。 <Evaluation>
(Sensitivity before aging)
After placing a 41-stage step tablet (manufactured by Showa Denko Materials Co., Ltd.) on the support of the laminate A described above, a direct exposure machine (manufactured by Via Mechanics Co., Ltd.) using a blue-violet laser diode with a wavelength of 405 nm as a light source , trade name: DE-1UH), the photosensitive resin layer was exposed through the support at an exposure amount (irradiation energy amount) such that the number of steps remaining after development of the 41-step tablet was 15 steps. The sensitivity (photosensitivity) was evaluated based on the amount of exposure (unit: mJ/cm 2 ) at this time. Table 1 shows the results. It means that the lower the exposure amount, the better the sensitivity.
（感度の経時安定性）
感光性エレメントを作製した後に室温（２５℃）で７日間及び１４日間保管することにより、感度の経時安定性のための２種の感光性エレメントを得た。７日間保管した感光性エレメントを用いて、上述の積層体Ａと同様の手順で積層体ａ１を得た。１４日間保管した感光性エレメントを用いて、上述の積層体Ａと同様の手順で積層体ａ２を得た。積層体ａ１及び積層体ａ２を用いて、経時変化前の上述の感度の評価と同様に露光量（照射エネルギー量）を取得し、積層体ａ１の露光量及び積層体ａ２の露光量の差分を得た。積層体ａ１の露光量に対する露光量の差分の割合が５％以下の場合を「Ａ」と評価し、割合が５％を超える場合を「Ｂ」と評価した。結果を表１に示す。 (Sensitivity stability over time)
Two types of photosensitive elements for stability of sensitivity over time were obtained by storing the photosensitive elements at room temperature (25° C.) for 7 days and 14 days after they were prepared. Using the photosensitive element stored for 7 days, a laminate a1 was obtained in the same manner as for the laminate A described above. Using the photosensitive element stored for 14 days, a laminate a2 was obtained in the same manner as for the laminate A described above. Using the laminate a1 and the laminate a2, the exposure amount (irradiation energy amount) is obtained in the same manner as in the above sensitivity evaluation before aging, and the difference between the exposure amount of the laminate a1 and the exposure amount of the laminate a2 is calculated. Obtained. A case where the ratio of the difference in the exposure amount to the exposure amount of the laminate a1 was 5% or less was evaluated as "A", and a case where the ratio exceeded 5% was evaluated as "B". Table 1 shows the results.
感光性エレメントを作製した後に室温（２５℃）で７日間及び１４日間保管することにより、感度の経時安定性のための２種の感光性エレメントを得た。７日間保管した感光性エレメントを用いて、上述の積層体Ａと同様の手順で積層体ａ１を得た。１４日間保管した感光性エレメントを用いて、上述の積層体Ａと同様の手順で積層体ａ２を得た。積層体ａ１及び積層体ａ２を用いて、経時変化前の上述の感度の評価と同様に露光量（照射エネルギー量）を取得し、積層体ａ１の露光量及び積層体ａ２の露光量の差分を得た。積層体ａ１の露光量に対する露光量の差分の割合が５％以下の場合を「Ａ」と評価し、割合が５％を超える場合を「Ｂ」と評価した。結果を表１に示す。 (Sensitivity stability over time)
Two types of photosensitive elements for stability of sensitivity over time were obtained by storing the photosensitive elements at room temperature (25° C.) for 7 days and 14 days after they were prepared. Using the photosensitive element stored for 7 days, a laminate a1 was obtained in the same manner as for the laminate A described above. Using the photosensitive element stored for 14 days, a laminate a2 was obtained in the same manner as for the laminate A described above. Using the laminate a1 and the laminate a2, the exposure amount (irradiation energy amount) is obtained in the same manner as in the above sensitivity evaluation before aging, and the difference between the exposure amount of the laminate a1 and the exposure amount of the laminate a2 is calculated. Obtained. A case where the ratio of the difference in the exposure amount to the exposure amount of the laminate a1 was 5% or less was evaluated as "A", and a case where the ratio exceeded 5% was evaluated as "B". Table 1 shows the results.
（最小現像時間）
上述の積層体Ａを正方形状（５ｃｍ×５ｃｍ）に切断した後、支持体を剥離することにより試験片を得た。次に、３０℃の１質量％炭酸ナトリウム水溶液を用いて、試験片における未露光の感光性樹脂層を０．１５ＭＰａの圧力でスプレー現像し、未露光の感光性樹脂層が除去されたことを目視で確認できる最短の時間を最小現像時間（ＭＤ）として得た。ノズルは、フルコーンタイプを使用した。上述の試験片とノズル先端との距離は６ｃｍであり、試験片の中心とノズルの中心とが一致するように配置した。結果を表１に示す。最小現像時間（単位：秒）が短いほど、現像性が良好であることを意味する。 (minimum development time)
After cutting the laminate A into a square (5 cm×5 cm), the support was peeled off to obtain a test piece. Next, the unexposed photosensitive resin layer of the test piece was spray-developed at a pressure of 0.15 MPa using a 1% by weight aqueous sodium carbonate solution at 30° C. to confirm that the unexposed photosensitive resin layer was removed. The shortest visually identifiable time was taken as the minimum development time (MD). A full cone type nozzle was used. The distance between the test piece and the tip of the nozzle was 6 cm, and the center of the test piece was aligned with the center of the nozzle. Table 1 shows the results. A shorter minimum development time (unit: seconds) means better developability.
上述の積層体Ａを正方形状（５ｃｍ×５ｃｍ）に切断した後、支持体を剥離することにより試験片を得た。次に、３０℃の１質量％炭酸ナトリウム水溶液を用いて、試験片における未露光の感光性樹脂層を０．１５ＭＰａの圧力でスプレー現像し、未露光の感光性樹脂層が除去されたことを目視で確認できる最短の時間を最小現像時間（ＭＤ）として得た。ノズルは、フルコーンタイプを使用した。上述の試験片とノズル先端との距離は６ｃｍであり、試験片の中心とノズルの中心とが一致するように配置した。結果を表１に示す。最小現像時間（単位：秒）が短いほど、現像性が良好であることを意味する。 (minimum development time)
After cutting the laminate A into a square (5 cm×5 cm), the support was peeled off to obtain a test piece. Next, the unexposed photosensitive resin layer of the test piece was spray-developed at a pressure of 0.15 MPa using a 1% by weight aqueous sodium carbonate solution at 30° C. to confirm that the unexposed photosensitive resin layer was removed. The shortest visually identifiable time was taken as the minimum development time (MD). A full cone type nozzle was used. The distance between the test piece and the tip of the nozzle was 6 cm, and the center of the test piece was aligned with the center of the nozzle. Table 1 shows the results. A shorter minimum development time (unit: seconds) means better developability.
（解像性）
上述の積層体Ａの支持体上に４１段ステップタブレット（昭和電工マテリアルズ株式会社製）を載置した後、波長４０５ｎｍの青紫色レーザダイオードを光源とする直描露光機（ビアメカニクス株式会社製、商品名：ＤＥ－１ＵＨ）により、ライン幅（Ｌ）／スペース幅（Ｓ）（以下、「Ｌ／Ｓ」と記す。）が３ｘ／ｘ（ｘ＝１～２０、単位：μｍ、１μｍ間隔）である描画パターンを用いて、４１段ステップタブレットの現像後の残存段数が１５段となる露光量（照射エネルギー量）で、支持体を介して感光性樹脂層に対し、Ｏｆｆｓｅｔをかけずに露光（描画）を行った。露光後３分以内に、加熱オーブンを用いて８０℃３０秒間の条件で露光後加熱（ＰＥＢ：Ｐｏｓｔ－Ｅｘｐｏｓｕｒｅ－Ｂａｋｅ）を行った。 (Resolution)
After placing a 41-stage step tablet (manufactured by Showa Denko Materials Co., Ltd.) on the support of the laminate A described above, a direct exposure machine (manufactured by Via Mechanics Co., Ltd.) using a blue-violet laser diode with a wavelength of 405 nm as a light source , product name: DE-1UH), the line width (L) / space width (S) (hereinafter referred to as “L / S”) is 3x / x (x = 1 to 20, unit: μm, 1 μm interval ) is applied to the photosensitive resin layer through the support at an exposure amount (irradiation energy amount) such that the remaining number of steps after development of the 41-step tablet is 15 steps, without offset. Exposure (drawing) was performed. Within 3 minutes after exposure, post-exposure baking (PEB: Post-Exposure-Bake) was performed using a heating oven at 80° C. for 30 seconds.
上述の積層体Ａの支持体上に４１段ステップタブレット（昭和電工マテリアルズ株式会社製）を載置した後、波長４０５ｎｍの青紫色レーザダイオードを光源とする直描露光機（ビアメカニクス株式会社製、商品名：ＤＥ－１ＵＨ）により、ライン幅（Ｌ）／スペース幅（Ｓ）（以下、「Ｌ／Ｓ」と記す。）が３ｘ／ｘ（ｘ＝１～２０、単位：μｍ、１μｍ間隔）である描画パターンを用いて、４１段ステップタブレットの現像後の残存段数が１５段となる露光量（照射エネルギー量）で、支持体を介して感光性樹脂層に対し、Ｏｆｆｓｅｔをかけずに露光（描画）を行った。露光後３分以内に、加熱オーブンを用いて８０℃３０秒間の条件で露光後加熱（ＰＥＢ：Ｐｏｓｔ－Ｅｘｐｏｓｕｒｅ－Ｂａｋｅ）を行った。 (Resolution)
After placing a 41-stage step tablet (manufactured by Showa Denko Materials Co., Ltd.) on the support of the laminate A described above, a direct exposure machine (manufactured by Via Mechanics Co., Ltd.) using a blue-violet laser diode with a wavelength of 405 nm as a light source , product name: DE-1UH), the line width (L) / space width (S) (hereinafter referred to as “L / S”) is 3x / x (x = 1 to 20, unit: μm, 1 μm interval ) is applied to the photosensitive resin layer through the support at an exposure amount (irradiation energy amount) such that the remaining number of steps after development of the 41-step tablet is 15 steps, without offset. Exposure (drawing) was performed. Within 3 minutes after exposure, post-exposure baking (PEB: Post-Exposure-Bake) was performed using a heating oven at 80° C. for 30 seconds.
露光後、積層体Ａから支持体を剥離し、感光性樹脂層を露出させ、１質量％炭酸ナトリウム水溶液を３０℃にて上述の最小現像時間の２倍の時間スプレーすることにより、未露光部を除去した。現像後、スペース部分（未露光部）が残渣なく除去され、且つ、ライン部分（露光部）が蛇行及び欠けを生じることなく形成されたレジストパターンにおけるスペース幅のうちの最小値（単位：μｍ）により解像性を評価した。結果を表１に示す。この数値が小さいほど解像性が良好であることを意味する。
After exposure, the support is peeled off from the laminate A to expose the photosensitive resin layer, and a 1% by weight sodium carbonate aqueous solution is sprayed at 30° C. for twice the minimum development time described above, thereby removing the unexposed area. removed. After development, the minimum value (unit: μm) of the space widths in the resist pattern in which the space portion (unexposed portion) is removed without residue and the line portion (exposed portion) is formed without meandering or chipping. The resolution was evaluated by Table 1 shows the results. A smaller value means better resolution.
（密着性）
上述の積層体Ａの支持体上に４１段ステップタブレット（昭和電工マテリアルズ株式会社製）を載置した後、波長４０５ｎｍの青紫色レーザダイオードを光源とする直描露光機（ビアメカニクス株式会社製、商品名：ＤＥ－１ＵＨ）により、Ｌ／Ｓがｘ／３ｘ（ｘ＝１～２０、単位：μｍ、１μｍ間隔）である描画パターンを用いて、４１段ステップタブレットの現像後の残存段数が１５段となる露光量（照射エネルギー量）で、支持体を介して感光性樹脂層に対し、Ｏｆｆｓｅｔをかけずに露光（描画）を行った。露光後３分以内に、加熱オーブンを用いて８０℃３０秒間の条件で露光後加熱（ＰＥＢ：Ｐｏｓｔ－Ｅｘｐｏｓｕｒｅ－Ｂａｋｅ）を行った。 (Adhesion)
After placing a 41-stage step tablet (manufactured by Showa Denko Materials Co., Ltd.) on the support of the laminate A described above, a direct exposure machine (manufactured by Via Mechanics Co., Ltd.) using a blue-violet laser diode with a wavelength of 405 nm as a light source , product name: DE-1UH), using a drawing pattern with L/S of x/3x (x = 1 to 20, unit: μm, 1 μm interval), the number of remaining steps after development of a 41-step tablet is The photosensitive resin layer was exposed (drawn) through the support with an exposure amount (irradiation energy amount) of 15 stages without applying an offset. Within 3 minutes after exposure, post-exposure baking (PEB: Post-Exposure-Bake) was performed using a heating oven at 80° C. for 30 seconds.
上述の積層体Ａの支持体上に４１段ステップタブレット（昭和電工マテリアルズ株式会社製）を載置した後、波長４０５ｎｍの青紫色レーザダイオードを光源とする直描露光機（ビアメカニクス株式会社製、商品名：ＤＥ－１ＵＨ）により、Ｌ／Ｓがｘ／３ｘ（ｘ＝１～２０、単位：μｍ、１μｍ間隔）である描画パターンを用いて、４１段ステップタブレットの現像後の残存段数が１５段となる露光量（照射エネルギー量）で、支持体を介して感光性樹脂層に対し、Ｏｆｆｓｅｔをかけずに露光（描画）を行った。露光後３分以内に、加熱オーブンを用いて８０℃３０秒間の条件で露光後加熱（ＰＥＢ：Ｐｏｓｔ－Ｅｘｐｏｓｕｒｅ－Ｂａｋｅ）を行った。 (Adhesion)
After placing a 41-stage step tablet (manufactured by Showa Denko Materials Co., Ltd.) on the support of the laminate A described above, a direct exposure machine (manufactured by Via Mechanics Co., Ltd.) using a blue-violet laser diode with a wavelength of 405 nm as a light source , product name: DE-1UH), using a drawing pattern with L/S of x/3x (x = 1 to 20, unit: μm, 1 μm interval), the number of remaining steps after development of a 41-step tablet is The photosensitive resin layer was exposed (drawn) through the support with an exposure amount (irradiation energy amount) of 15 stages without applying an offset. Within 3 minutes after exposure, post-exposure baking (PEB: Post-Exposure-Bake) was performed using a heating oven at 80° C. for 30 seconds.
露光後、積層体Ａから支持体を剥離し、感光性樹脂層を露出させ、１質量％炭酸ナトリウム水溶液を３０℃にて上述の最小現像時間の２倍の時間スプレーすることにより、未露光部を除去した。現像後、スペース部分（未露光部）が残渣なく除去され、且つ、ライン部分（露光部）が蛇行及び欠けを生じることなく形成されたレジストパターンにおけるライン幅のうちの最小値（単位：μｍ）により密着性を評価した。結果を表１に示す。この数値が小さいほど密着性が良好であることを意味する。
After exposure, the support is peeled off from the laminate A to expose the photosensitive resin layer, and a 1% by weight sodium carbonate aqueous solution is sprayed at 30° C. for twice the minimum development time described above, thereby removing the unexposed area. removed. After development, the minimum value (unit: μm) of the line widths in a resist pattern in which space portions (unexposed portions) are removed without residue, and line portions (exposed portions) are formed without meandering or chipping. The adhesion was evaluated by Table 1 shows the results. A smaller value means better adhesion.
（追従性）
光学顕微鏡（キーエンス株式会社、ＶＫ－８５００）を用いて積層体Ｂの支持体側から１０箇所の丸穴を観察した。丸穴と感光性樹脂層の硬化物との間に生じた気泡の面積（Ａｉｒ ｖｏｉｄサイズ、単位：μｍ２）を測定し、１０箇所の丸穴の平均値を算出した。結果を表１に示す。気泡の面積が小さいほど、追従性（丸穴追従性）に優れることを意味する。 (Followability)
Ten round holes were observed from the support side of the laminate B using an optical microscope (Keyence Corporation, VK-8500). The area (air void size, unit: μm 2 ) of air bubbles generated between the round holes and the cured product of the photosensitive resin layer was measured, and the average value of ten round holes was calculated. Table 1 shows the results. The smaller the bubble area, the better the followability (round hole followability).
光学顕微鏡（キーエンス株式会社、ＶＫ－８５００）を用いて積層体Ｂの支持体側から１０箇所の丸穴を観察した。丸穴と感光性樹脂層の硬化物との間に生じた気泡の面積（Ａｉｒ ｖｏｉｄサイズ、単位：μｍ２）を測定し、１０箇所の丸穴の平均値を算出した。結果を表１に示す。気泡の面積が小さいほど、追従性（丸穴追従性）に優れることを意味する。 (Followability)
Ten round holes were observed from the support side of the laminate B using an optical microscope (Keyence Corporation, VK-8500). The area (air void size, unit: μm 2 ) of air bubbles generated between the round holes and the cured product of the photosensitive resin layer was measured, and the average value of ten round holes was calculated. Table 1 shows the results. The smaller the bubble area, the better the followability (round hole followability).
１…感光性エレメント、２…支持体、３…感光性樹脂層、４…保護層。
1... Photosensitive element, 2... Support, 3... Photosensitive resin layer, 4... Protective layer.
Claims (17)
- （Ａ）バインダーポリマーと、（Ｂ）光重合性化合物と、（Ｃ）光重合開始剤と、（Ｄ）ピラゾリン化合物と、を含有し、
厚さが２０μｍ以下である、感光性フィルム。 (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a pyrazoline compound,
A photosensitive film having a thickness of 20 μm or less. - 前記（Ｄ）成分が、ピラゾリン環に結合する２つ以上のアリール基を有する化合物を含む、請求項１に記載の感光性フィルム。 The photosensitive film according to claim 1, wherein the component (D) contains a compound having two or more aryl groups bonded to a pyrazoline ring.
- 前記（Ｄ）成分が、下記一般式（ｄ１）で表される化合物を含む、請求項１又は２に記載の感光性フィルム。
- 前記（Ｄ）成分の含有量が、前記（Ａ）成分及び前記（Ｂ）成分の総量１００質量部に対して０．１０～１．０質量部である、請求項１～３のいずれか一項に記載の感光性フィルム。 4. Any one of claims 1 to 3, wherein the content of component (D) is 0.10 to 1.0 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B). The photosensitive film according to the item.
- 前記（Ｄ）成分の含有量が、前記（Ｃ）成分及び前記（Ｄ）成分の総量１００質量部に対して１．０～１０質量部である、請求項１～４のいずれか一項に記載の感光性フィルム。 The content of the component (D) is 1.0 to 10 parts by mass with respect to 100 parts by mass of the total amount of the component (C) and the component (D), according to any one of claims 1 to 4 A photosensitive film as described.
- 前記（Ａ）成分における（メタ）アクリル酸ヒドロキシアルキルの単量体単位の含有量が、前記（Ａ）成分を構成する単量体単位の全量を基準として０．１０～５．０質量％である、請求項１～５のいずれか一項に記載の感光性フィルム。 The content of the hydroxyalkyl (meth)acrylate monomer units in the component (A) is 0.10 to 5.0% by mass based on the total amount of the monomer units constituting the component (A). A photosensitive film according to any one of claims 1 to 5.
- 前記（Ａ）成分が（メタ）アクリル酸アリール及びスチレン化合物を単量体単位として有する、請求項１～６のいずれか一項に記載の感光性フィルム。 The photosensitive film according to any one of claims 1 to 6, wherein the component (A) has an aryl (meth)acrylate and a styrene compound as monomer units.
- 前記（Ａ）成分におけるスチレン化合物の単量体単位の含有量が、前記（Ａ）成分を構成する単量体単位の全量を基準として４０質量％以上である、請求項１～７のいずれか一項に記載の感光性フィルム。 Any one of claims 1 to 7, wherein the content of the monomer units of the styrene compound in the component (A) is 40% by mass or more based on the total amount of the monomer units constituting the component (A). 1. The photosensitive film according to item 1.
- 前記（Ａ）成分の重量平均分子量が２００００～５００００である、請求項１～８のいずれか一項に記載の感光性フィルム。 The photosensitive film according to any one of claims 1 to 8, wherein the component (A) has a weight average molecular weight of 20,000 to 50,000.
- 前記（Ｂ）成分がビスフェノールＡ型（メタ）アクリル酸化合物を含む、請求項１～９のいずれか一項に記載の感光性フィルム。 The photosensitive film according to any one of claims 1 to 9, wherein the component (B) contains a bisphenol A type (meth)acrylic acid compound.
- 前記ビスフェノールＡ型（メタ）アクリル酸化合物の含有量が、前記（Ａ）成分及び前記（Ｂ）成分の総量１００質量部に対して３０質量部以上である、請求項１０に記載の感光性フィルム。 11. The photosensitive film according to claim 10, wherein the content of the bisphenol A type (meth)acrylic acid compound is 30 parts by mass or more with respect to 100 parts by mass as the total amount of the component (A) and the component (B). .
- 前記（Ｂ）成分が、ポリオキシアルキレン基を有する（メタ）アクリル酸化合物を含む、請求項１～１１のいずれか一項に記載の感光性フィルム。 The photosensitive film according to any one of claims 1 to 11, wherein the component (B) contains a (meth)acrylic acid compound having a polyoxyalkylene group.
- 前記（Ｂ）成分の含有量が、前記（Ａ）成分及び前記（Ｂ）成分の総量１００質量部に対して３０～６０質量部である、請求項１～１２のいずれか一項に記載の感光性フィルム。 The content of the component (B) is 30 to 60 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B), according to any one of claims 1 to 12. photosensitive film.
- カテコール化合物を更に含有する、請求項１～１３のいずれか一項に記載の感光性フィルム。 The photosensitive film according to any one of claims 1 to 13, further containing a catechol compound.
- 支持体と、当該支持体上に配置された感光性樹脂層と、を備え、
前記感光性樹脂層が、請求項１～１４のいずれか一項に記載の感光性フィルムである、感光性エレメント。 comprising a support and a photosensitive resin layer disposed on the support;
A photosensitive element, wherein the photosensitive resin layer is the photosensitive film according to any one of claims 1 to 14. - 請求項１～１４のいずれか一項に記載の感光性フィルム、又は、請求項１５に記載の感光性エレメントを用いて感光性樹脂層を基材上に配置する配置工程と、
前記感光性樹脂層の一部を光硬化させる工程と、
前記感光性樹脂層の未硬化部の少なくとも一部を除去して硬化物パターンを形成する工程と、を備える、積層体の製造方法。 An arrangement step of arranging a photosensitive resin layer on a substrate using the photosensitive film according to any one of claims 1 to 14 or the photosensitive element according to claim 15;
a step of photocuring a portion of the photosensitive resin layer;
and removing at least part of the uncured portion of the photosensitive resin layer to form a cured product pattern. - 前記基材が直径５００μｍ以下の凹部を有し、
前記配置工程において前記感光性樹脂層の少なくとも一部が前記凹部内に配置される、請求項１６に記載の積層体の製造方法。 The substrate has a recess with a diameter of 500 μm or less,
17. The method of manufacturing a laminate according to claim 16, wherein at least part of said photosensitive resin layer is arranged in said recess in said arrangement step.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2021/029189 WO2023012985A1 (en) | 2021-08-05 | 2021-08-05 | Photosensitive film, photosensitive element, and method for producing multilayer body |
| PCT/JP2022/009697 WO2022191125A1 (en) | 2021-03-09 | 2022-03-07 | Photosensitive film, photosensitive element, and production method for layered product |
| EP22767081.7A EP4307049A1 (en) | 2021-03-09 | 2022-03-07 | Photosensitive film, photosensitive element, and production method for layered product |
| US17/922,867 US20230161248A1 (en) | 2021-03-09 | 2022-03-07 | Photosensitive film, photosensitive element, and method for producing laminate |
| KR1020227035580A KR20230154733A (en) | 2021-03-09 | 2022-03-07 | Method for producing photosensitive films, photosensitive elements, and laminates |
| JP2022561676A JPWO2022191125A1 (en) | 2021-03-09 | 2022-03-07 | |
| CN202280003952.1A CN116848461A (en) | 2021-03-09 | 2022-03-07 | Photosensitive film, photosensitive element, and method for producing laminate |
| TW111108374A TW202307564A (en) | 2021-08-05 | 2022-03-08 | Photosensitive film, photosensitive element, and production method for layered product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2021/029189 WO2023012985A1 (en) | 2021-08-05 | 2021-08-05 | Photosensitive film, photosensitive element, and method for producing multilayer body |
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| WO2023012985A1 true WO2023012985A1 (en) | 2023-02-09 |
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| Country | Link |
|---|---|
| CN (1) | CN116848461A (en) |
| TW (1) | TW202307564A (en) |
| WO (1) | WO2023012985A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007122028A (en) * | 2005-09-28 | 2007-05-17 | Asahi Kasei Electronics Co Ltd | Photosensitive resin composition and its laminate |
| JP2017040710A (en) * | 2015-08-18 | 2017-02-23 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, method for forming resist pattern and method for manufacturing printed wiring board |
| JP2019109543A (en) * | 2014-05-23 | 2019-07-04 | 日立化成株式会社 | Method for forming resist pattern, method for manufacturing printed wiring board, photosensitive resin composition for projection exposure, and photosensitive element |
-
2021
- 2021-08-05 WO PCT/JP2021/029189 patent/WO2023012985A1/en unknown
-
2022
- 2022-03-07 CN CN202280003952.1A patent/CN116848461A/en active Pending
- 2022-03-08 TW TW111108374A patent/TW202307564A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007122028A (en) * | 2005-09-28 | 2007-05-17 | Asahi Kasei Electronics Co Ltd | Photosensitive resin composition and its laminate |
| JP2019109543A (en) * | 2014-05-23 | 2019-07-04 | 日立化成株式会社 | Method for forming resist pattern, method for manufacturing printed wiring board, photosensitive resin composition for projection exposure, and photosensitive element |
| JP2017040710A (en) * | 2015-08-18 | 2017-02-23 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, method for forming resist pattern and method for manufacturing printed wiring board |
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| CN116848461A (en) | 2023-10-03 |
| TW202307564A (en) | 2023-02-16 |
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