WO2025005146A1 - 感光性樹脂組成物、感光性樹脂積層体、及びレジストパターンの形成方法等 - Google Patents
感光性樹脂組成物、感光性樹脂積層体、及びレジストパターンの形成方法等 Download PDFInfo
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- WO2025005146A1 WO2025005146A1 PCT/JP2024/023207 JP2024023207W WO2025005146A1 WO 2025005146 A1 WO2025005146 A1 WO 2025005146A1 JP 2024023207 W JP2024023207 W JP 2024023207W WO 2025005146 A1 WO2025005146 A1 WO 2025005146A1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
Definitions
- the present invention relates to a photosensitive resin composition, a photosensitive resin laminate, and a method for forming a resist pattern.
- Photolithography is a method for forming a desired wiring pattern on a substrate by the following steps: First, a coating film obtained using a photosensitive resin composition is formed on the substrate, and then exposed and developed to form a resist pattern; Next, a conductor pattern is formed on the substrate by etching or plating; After that, the resist pattern is removed to form a wiring pattern on the substrate.
- CMOS complementary metal-oxide-semiconductor
- SAP semi-additive process
- Known photosensitive resin compositions include, for example, the photosensitive resin compositions described in Patent Documents 1 to 4.
- the object of the present disclosure is therefore to provide a photosensitive resin composition capable of realizing a photosensitive resin layer having excellent desired properties.
- the object of the present disclosure is to provide a photosensitive resin laminate having a photosensitive resin layer and a roll thereof, and further to provide a method for producing a photosensitive resin composition and a method for forming a resist pattern.
- a photosensitive resin composition comprising: The component (A) and the component (B) both contain an aromatic ring, The ratio of the aromatic rings in the component (A) is 0.0045 mol/g or more, and The ratio of the aromatic rings in the component (B) is 0.0017 mol/g or more,
- the component (A) contains a compound having a hydroxy group as a monomer component
- the component (C) contains a biimidazole compound in an amount of 4.0% by mass or more based on the total solid content of the photosensitive resin composition.
- the component (A) has a proportion of structural units derived from styrene of 51% by mass or more based on the total mass of all monomer components, 2.
- the photosensitive resin composition according to item 1 wherein the component (B) contains 70 mass% or more of a compound having a bisphenol A skeleton based on the total amount of the component (B).
- [3] 3.
- the photosensitive resin composition according to item 1 or 2 wherein the component (A) has a proportion of structural units derived from styrene of 55 mass% or more based on the total mass of all monomer components.
- a photosensitive resin layer having a thickness of 25 ⁇ m obtained by using the photosensitive resin composition has a transmittance of 45% or more at a wavelength of 365 nm.
- the transmittance is 60% or more.
- a photosensitive resin layer comprising the photosensitive resin composition according to any one of items 1 to 8;
- a method for producing a photosensitive resin composition comprising: The component (A) and the component (B) both contain an aromatic ring, The component (A) has a ratio of the aromatic rings of 0.0045 mol/g or more, and The component (B) has a ratio of the aromatic rings of 0.0017 mol/g or more.
- a method for producing a photosensitive resin composition [13] 11.
- a method for forming a resist pattern using the photosensitive resin laminate according to item 9 or 10 The following steps: A step of laminating the photosensitive resin laminate on a substrate; a step of exposing the photosensitive resin layer in the laminated photosensitive resin laminate; and a step of developing the photosensitive resin layer after exposure; A method for forming a resist pattern comprising the steps of:
- a photosensitive resin composition comprising: The component (A) and the component (B) both contain an aromatic ring, The ratio of the aromatic rings in the component (A) is 0.0045 mol/g or more, and The ratio of the aromatic rings in the component (B) is 0.0017 mol/g or more. Photosensitive resin composition.
- the component (A) has a proportion of structural units derived from styrene of 51% by mass or more based on the total mass of all monomer components,
- the component (B) contains 70 mass% or more of a compound having a bisphenol A skeleton based on the total amount of the component (B), and Item 1B.
- [6A] The photosensitive resin composition according to any one of items 1A to 5A, wherein a photosensitive resin layer obtained using the photosensitive resin composition has a transmittance of 45% or more at a wavelength of 365 nm in a thickness of 25 ⁇ m.
- [7A] Item 6B.
- [8A] A support film; A photosensitive resin layer comprising the photosensitive resin composition according to any one of Items 1A to 7A; A photosensitive resin laminate comprising: [9A] Item 8B.
- the photosensitive resin laminate according to Item 8A wherein the photosensitive resin layer has a transmittance of 45% or more at a wavelength of 365 nm at a thickness of 25 ⁇ m.
- [11A] The following components: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, A method for producing a photosensitive resin composition, comprising: The component (A) and the component (B) both contain an aromatic ring, The component (A) has a ratio of the aromatic rings of 0.0045 mol/g or more, and The component (B) has a ratio of the aromatic rings of 0.0017 mol/g or more. A method for producing a photosensitive resin composition.
- a method for forming a resist pattern using the photosensitive resin laminate according to Item 8A or 9A The following steps: A step of laminating the photosensitive resin laminate on a substrate; a step of exposing the photosensitive resin layer in the laminated photosensitive resin laminate; and a step of developing the photosensitive resin layer after exposure; A method for forming a resist pattern comprising the steps of:
- the present invention can provide a photosensitive resin composition capable of realizing a photosensitive resin layer having excellent desired properties.
- the present invention can also provide a photosensitive resin laminate having a photosensitive resin layer and a roll thereof, as well as a method for producing a photosensitive resin composition and a method for forming a resist pattern.
- the present embodiment an embodiment of the present invention (hereinafter, abbreviated as "the present embodiment”) will be described.
- the present invention is not limited to the present embodiment, and can be practiced with various modifications within the scope of the gist of the present invention.
- the upper and lower limits of each numerical range may be arbitrarily combined, and may be replaced with values described in the examples.
- (meth)acrylic acid means acrylic acid or methacrylic acid
- (meth)acryloyl group means acryloyl group or methacryloyl group
- (meth)acrylate” means “acrylate” or "methacrylate”.
- various numerical values, characteristics, etc. may be measured in accordance with the methods described in the examples.
- the present embodiment comprises the following components: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, A photosensitive resin composition comprising: The component (A) and the component (B) both contain an aromatic ring, The ratio of the aromatic rings in the component (A) is 0.0045 mol/g or more, and The ratio of the aromatic rings in the component (B) is 0.0017 mol/g or more. It is a photosensitive resin composition.
- the photosensitive resin composition of the present embodiment is
- the component (A) contains a compound having a hydroxy group as a monomer component
- the component (C) contains a biimidazole compound in an amount of 4.0 based on the total solid content of the photosensitive resin composition. Contains % by mass or more.
- the present inventors have focused on the incorporation of aromatic rings in a predetermined proportion or more in each of component (A) and component (B).
- the composition may remain on the resist pattern obtained. Therefore, in order to remove such residues (development residues), the resist pattern formed after development may be subjected to plasma treatment.
- the aromatic rings contained in the (A) component and the (B) component each contribute to improving the chemical stability of the photosensitive resin layer, and thus improve the plasma resistance.
- the proportion of aromatic rings in component (A) may be 0.0082 mol/g or less, and the proportion of aromatic rings in component (B) may be 0.0056 mol/g or less.
- the component (A) has a proportion of structural units derived from styrene of 51% by mass or more based on the total mass of all monomer components
- the component (B) contains 70 mass% or more of a compound having a bisphenol A skeleton based on the total amount of the component (B).
- a photosensitive resin composition that satisfies the above conditions is likely to exhibit the effects of this embodiment.
- the compounds containing aromatic rings compounds having styrene and bisphenol A type skeletons are easy to suitably improve plasma resistance.
- compounds having styrene and bisphenol A type skeletons they can be easily introduced into the photosensitive resin composition as components (A) and (B), respectively.
- the photosensitive resin composition when the proportion of aromatic rings increases, the resin viscosity tends to increase, and the radical polymerization efficiency tends to decrease. In this case, it is possible to compound a large amount of biimidazole-based compounds, that is, to suppress the decrease in sensitivity.
- the photosensitive resin layer 25 ⁇ m thick obtained by exposing the photosensitive resin composition to light preferably has a transmittance of 45% or more at a wavelength of 365 nm, and more preferably has a transmittance of 60% or more, which makes it easier to achieve good adhesion (adhesion between the photosensitive resin layer and the substrate).
- the combination of the sensitizer and a relatively large amount of the biimidazole compound makes it easy to prevent a decrease in sensitivity.
- the amount of the sensitizer is reduced, it is advantageous for improving the transmittance, and it is easy to realize a design in which the amount of the biimidazole compound is increased by the amount of the reduced sensitizer.
- the photosensitive resin composition of the present embodiment has a wide range of composition design of this kind, that is, it is possible to achieve both sensitivity and adhesion.
- Component (A), component (B), and component (C) may each be used alone or in combination of two or more.
- the photosensitive resin composition contains components other than components (A), (B), and (C), such other components may also be used alone or in combination of two or more.
- the component (A) is an alkali-soluble polymer.
- the component (A) preferably has a carboxyl group, and from the viewpoint of favorably expressing alkali solubility, preferably has an acid value of 50 to 600 mgKOH/g.
- the acid value of the component (A) may be 60 mgKOH/g or more, or 80 mgKOH/g or more, and may be 500 mgKOH/g or less, or 400 mgKOH/g or less.
- the (A) component preferably has a repeating unit containing at least one type selected from the "first monomers” described below, and more preferably has a repeating unit containing both at least one type selected from the "first monomers” and at least one type selected from the "second monomers” described below.
- the ratio of the monomer components in the component (A) is a copolymerization ratio when only one type of alkali-soluble polymer is contained as the component (A), and is a weighted average of the copolymerization ratios when two or more types of alkali-soluble polymers are used as the component (A), with the content ratio of each alkali-soluble polymer being the weight.
- the ratio of aromatic rings is 0.0045 mol/g or more. It is preferable to make the ratio of aromatic rings 0.0045 mol/g or more from the viewpoint of improving plasma resistance, and from the same viewpoint, it is more preferable to make it 0.0050 mol/g or more, even more preferable to make it 0.0053 mol/g or more, particularly preferable to make it 0.0058 mol/g or more, even more preferable to make it 0.0063 mol/g or more, and most preferable to make it 0.0067 mol/g or more.
- the aromatic ring may be derived from the first monomer, may be derived from the second monomer, or may be derived from both the first and second monomers. However, in order to easily realize the desired component (A), it is preferable that the proportion of the aromatic ring is derived from at least the second monomer.
- the proportion of aromatic rings in component (A) can be calculated by taking the weighted average of the proportion of aromatic rings contained in each monomer component in component (A) based on the content of each monomer component in component (A).
- the proportion of aromatic rings contained in each monomer component in component (A) can be calculated by (number of aromatic rings contained in one monomer molecule/molecular weight of monomer).
- the component (A) may have a proportion of structural units derived from styrene of 40 mass % or more based on the total mass of all monomer components.
- the (A) component preferably has a ratio of structural units derived from styrene of 51% by mass or more based on the total mass of all monomer components. This makes it easier to achieve the effects of this embodiment. From the same viewpoint, the ratio of structural units derived from styrene is more preferably 52% by mass or more, 55% by mass or more, or 60% by mass or more, and even more preferably 65% by mass or more.
- the ratio of structural units derived from styrene may be 85% by mass or less.
- the weight average molecular weight (Mw) of component (A) is preferably 10,000 to 60,000. From the standpoint of achieving both flexibility and resolution of the resist pattern, it is preferable to have a weight average molecular weight of 60,000 or less, and from the same standpoint, it is more preferable to have a weight average molecular weight of 55,000 or less, and even more preferably less than 50,000. From the same viewpoint, the weight average molecular weight is preferably 10,000 or more, more preferably 14,000 or more, and even more preferably 25,000 or more.
- the polydispersity of component (A) is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.
- the molecular weights and polydispersities of the multiple (A) components are selected so that the weighted average values, when the content ratio is treated as the weight, fall within the various ranges.
- the first monomer has a carboxyl group in its molecule.
- the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester.
- (meth)acrylic acid is preferred, and methacrylic acid is more preferred.
- methacrylic acid refers to a compound having the chemical formula C 4 H 6 O 2
- “acrylic acid” refers to a compound having the chemical formula C 3 H 4 O 2 .
- the proportion of the first monomer in component (A) is preferably 10 to 50 mass% based on the total mass of all monomer components.
- a proportion of 10 mass% or more is preferable from the viewpoint of excellent adhesion and resolution, more preferably 15 mass% or more, even more preferably 18 mass% or more, even more preferably 21 mass% or more, particularly preferably 23 mass% or more, and most preferably 24 mass% or more.
- a proportion of 50 mass% or less is preferable from the viewpoint of excellent adhesion and resolution, more preferably 35 mass% or less, even more preferably 30 mass% or less, even more preferably 29 mass% or less, particularly preferably 27 mass% or less, and most preferably 26 mass% or less.
- the second monomer has at least one polymerizable unsaturated group in its molecule.
- the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, pentamethylpiperidyl (meth)acrylate, tetra
- (meth)acrylates such as (meth)acrylate, phenoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, etc.; styrene derivatives such as methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, and styrene trimer; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile.
- the second monomer contains a compound having an aromatic ring.
- the proportion of this compound in component (A) is preferably 45 to 90% by mass, based on the total mass of all monomer components.
- a proportion of 45% by mass or more is preferable from the viewpoint of excellent adhesion and resolution, 50% by mass or more is more preferable, 55% by mass or more is even more preferable, 60% by mass or more is even more preferable, and 65% by mass or more is particularly preferable.
- a proportion of 90% by mass or less is preferable from the viewpoint of excellent developability, and 80% by mass or less is more preferable.
- Examples of compounds having an aromatic ring include styrene, benzyl (meth)acrylate, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, styrene trimer and other styrene derivatives, and 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl (meth)acrylate.
- styrene and benzyl (meth)acrylate are preferred, styrene is more preferred, and compounds containing both styrene and benzyl (meth)acrylate are even more preferred.
- the second monomer may contain a compound having an alicyclic ring.
- the proportion of the compound in component (A) may be 10 to 40 mass % based on the total mass of all monomer components.
- Examples of compounds having an alicyclic ring include (meth)acrylic esters having a group having one cyclic hydrocarbon group, such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group, or a group consisting of a derivative thereof, and also include (meth)acrylic esters having a group having two or more cyclic hydrocarbon groups, such as a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group, or an isobornyl group, or a group consisting of a derivative thereof.
- the second monomer may contain a compound having a hydroxy group.
- the proportion of this compound in component (A) is preferably 1.0 to 25 mass%, more preferably 1 to 10 mass%, and even more preferably 1 to 6 mass%, based on the total mass of all monomer components. Controlling this proportion within the above range is preferable from the viewpoint of excellent adhesion and resolution.
- Examples of compounds having a hydroxy group include hydroxyalkyl (meth)acrylates, specifically 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycerin-based (meth)acrylates (for example, glycerin mono(meth)acrylate). These are relatively easy to obtain. And yet, the developability and adhesion are easy to control, making it easy to realize resist patterns with excellent properties.
- the second monomer may be a compound other than those mentioned above, for example, Examples of the (meth)acrylic acid alkyl esters (linear alkyl esters and cyclic alkyl esters) other than the above, conjugated diene compounds other than the above, polar monomers (amino group-containing monomers, amide group-containing monomers, cyano group-containing monomers, epoxy group-containing monomers, and the like) other than the above, crosslinkable monomers other than the above, and acid anhydrides other than the above are also included.
- the (meth)acrylic acid alkyl esters linear alkyl esters and cyclic alkyl esters
- conjugated diene compounds other than the above
- polar monomers amino group-containing monomers, amide group-containing monomers, cyano group-containing monomers, epoxy group-containing monomers, and the like
- crosslinkable monomers other than the above
- acid anhydrides other than the above
- component (A) is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting one or more of the monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and heating and stirring the solution.
- a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile
- a solvent such as acetone, methyl ethyl ketone, or isopropanol
- the synthesis is carried out while dropping a part of the mixture into the reaction solution, and in other cases, the desired concentration is adjusted by adding more solvent after the reaction is completed.
- living radical polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.
- the content of component (A) may be 10% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more, based on the total solid mass of the photosensitive resin composition. It may also be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less.
- component (A) it is preferable to set the content of component (A) to 90% by mass or less from the viewpoint of controlling the development time. On the other hand, it is preferable to set the content to 10% by mass or more from the viewpoint of improving edge fuse resistance, that is, from the viewpoint of suppressing the exudation of the photosensitive resin layer from the film edge. Note that edge fuse resistance may be particularly required for rolls formed by winding a photosensitive resin laminate.
- the component (B) is a compound having an ethylenically unsaturated bond.
- the ratio of aromatic rings is 0.0017 mol/g or more. It is preferable to make the ratio of aromatic rings 0.0017 mol/g or more from the viewpoint of improving plasma resistance, and from the same viewpoint, it is more preferable to make it 0.0019 mol/g or more, even more preferable to make it 0.0021 mol/g or more, particularly preferable to make it 0.0022 mol/g or more, even more preferable to make it 0.0025 mol/g or more, and most preferable to make it 0.0030 mol/g or more.
- the (B) component preferably contains 61% by mass or more of a compound having a bisphenol A skeleton based on the total amount of the (B) component. This makes it easier to achieve the effects of the present embodiment.
- the ratio of the compound having a bisphenol A skeleton is more preferably 70% by mass or more, 75% by mass or more, or 80% by mass or more, even more preferably 90% by mass or more, and most preferably 100% by mass.
- the concept of "a compound having a bisphenol A skeleton" also includes a compound obtained by hydrogenating a compound having a bisphenol A skeleton, that is, a compound having a hydrogenated bisphenol A skeleton.
- each R 2 is independently a hydrogen atom or a methyl group
- each X 2 O and Y 2 O is independently an oxyethylene group or an oxypropylene group
- each m3, m4, n2 and n3 is independently an integer of 0 to 40
- m3+m4 is 1 to 40
- n2+n3 is 0 to 20.
- Examples of the bisphenol A di(meth)acrylate include bisphenol A di(meth)acrylate represented by the following formula:
- the (B) component preferably contains a compound having two or more ethylenically unsaturated bonds in one molecule.
- the photosensitive resin composition may further contain a compound having three ethylenically unsaturated bonds in one molecule, or may further contain a compound having four, five, or six ethylenically unsaturated bonds in one molecule.
- Component (B) preferably contains a compound containing a (meth)acryloyl group (hereinafter, (meth)acrylate compound), and more preferably contains a bifunctional or higher functional (meth)acrylate compound.
- (meth)acrylate compound a compound having two or more (meth)acryloyl groups in one molecule.
- the (B) component is preferably a (meth)acrylate compound.
- the (meth)acrylate compound may include, for example, a bifunctional (meth)acrylate compound and a trifunctional or higher (meth)acrylate compound, for example, a tetrafunctional, pentafunctional, or hexafunctional (meth)acrylate compound.
- bifunctional (meth)acrylate compounds include alkyl di(meth)acrylate, 1,3-bis(meth)acryloyloxy-2-propanol, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, tricyclodecanol di(meth)acrylate, ethoxylated (hydrogenated) bisphenol A di(meth)acrylate, propoxylated (hydrogenated) bisphenol A di(meth)acrylate, and tetramethylene glycoxylated (hydrogenated) bisphenol A di(meth)acrylate.
- bifunctional (meth)acrylate compounds include, for example, NK Ester (registered trademark) A-HD-N, A-NOD-N, A-DOD-N, A-NPG, 701A, A-200, A-400, A-600, A-1000, APG-200, APG-400, APG-700, A-PTMG65, A-DCP, and ABE.
- NK Ester registered trademark
- A-HD-N A-NOD-N
- A-DOD-N A-NPG
- 701A A-200, A-400, A-600, A-1000, APG-200, APG-400, APG-700, A-PTMG65, A-DCP, and ABE.
- trifunctional or higher (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, pentaerythritol (tri/tetra)(meth)acrylate, ditrimethylolpropane (tetra/penta/hexa)(meth)acrylate, and dipentaerythritol (tetra/penta/hexa)(meth)acrylate.
- examples of trifunctional or higher (meth)acrylate compounds include alkylene oxide-modified tri(meth)acrylate of trimethylolpropane, alkylene oxide-modified tri(meth)acrylate of glycerin, alkylene oxide-modified isocyanuric acid tri(meth)acrylate, alkylene oxide-modified pentaerythritol (tri/tetra)(meth)acrylate, alkylene oxide-modified ditrimethylolpropane (tetra/penta/hexa)(meth)acrylate, and alkylene oxide-modified dipentaerythritol (tetra/penta/hexa)(meth)acrylate.
- NK Ester registered trademark
- A-TMPT A-TMPT-9EO
- AT-20E A-GLY-3E
- A-GLY-9E A-GLY-20E
- A-9300 A-9200YN
- A-TMM-3 A-TMM-3L
- A-TMM-3LM-N A-TMMT
- ATM-35E AD-TMP, A-DPH, and A-955.
- the content of the tri- or higher functional (meth)acrylate compound may be 0 to 50 mass%, 0 to 25 mass%, or 1 to 15 mass%, based on the total amount of component (B).
- compounds that may be contained in component (B) include: Dimethacrylate of polyethylene glycol in which an average of 5 mol of EO is added to each end of bisphenol A (the above-mentioned "FA-321M", product name); Dimethacrylate of polyethylene glycol in which an average of 2 mol of EO is added to each end of bisphenol A; dimethacrylate of polyalkylene glycol in which EO is further added to both ends of polypropylene glycol having an average of 12 PO repeating units per molecule, on average, by 3 mol each; (“EO” is an abbreviation for ethylene oxide, and "PO” is an abbreviation for propylene oxide).
- the content of component (B) is preferably 30% by mass or more, and more preferably 35% by mass or more, based on the total solid mass of the photosensitive resin composition, from the viewpoints of sensitivity, tackiness, and tracking ability. Also, from the viewpoints of edge fuse resistance, tackiness, and resolution, the content is preferably 50% by mass or less, more preferably 45% by mass or less, and more preferably 42% by mass or less.
- the content of component (B) relative to the content of component (A) in the photosensitive resin composition is preferably 1.4 or less, preferably 1.3 or less, preferably 1.2 or less, and preferably 1.1 or less.
- the lower limit is preferably 0.6 or more, preferably 0.7 or more, preferably 0.8 or more, preferably 0.9 or more, and preferably 1.0 or more.
- the number of ethylenically unsaturated bonds per 100 g of solids in the photosensitive resin composition is preferably controlled to 0.1 to 0.3 mol.
- it is easy to prevent the photosensitive resin components from leaching out of the hardened resist pattern in the water washing step after development, which in turn makes it easier to prevent contamination in the water washing step.
- the number of ethylenically unsaturated bonds per 100 g of solid content in the photosensitive resin composition is preferably 0.1 mol or more, more preferably 0.11 mol or more, more preferably 0.12 mol or more, and more preferably 0.13 mol or more. Also, it is preferably 0.3 mol or less, preferably 0.28 mol or less, preferably 0.25 mol or less, preferably 0.22 mol or less, preferably 0.20 mol or less, preferably 0.18 mol or less, and preferably 0.15 mol or less.
- the component (C) is a photopolymerization initiator.
- the photopolymerization initiator generates radicals when exposed to actinic rays, which easily initiates polymerization of a compound having an ethylenically unsaturated bond.
- the (C) component may contain 3.5% by mass or more of a biimidazole-based compound based on the total solid content of the photosensitive resin composition.
- the (C) component preferably contains 4.0% by mass or more of a biimidazole-based compound based on the total solid content of the photosensitive resin composition, more preferably contains 4.2% by mass or more, even more preferably contains 5.0% by mass or more, particularly preferably contains 6.0% by mass or more, and most preferably contains 6.2% by mass or more.
- the content ratio of the biimidazole-based compound may be 10% by mass or less, or 8.0% by mass or less, based on the total solid content of the photosensitive resin composition.
- the component (A) may have a proportion of structural units derived from styrene of 40 mass % or more based on the total mass of all monomer components.
- component (C) examples include biimidazole compounds, N-aryl- ⁇ -amino acid compounds, quinone compounds, aromatic ketone compounds, anthracene derivatives, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-aryl amino acid ester compounds, and halogen compounds.
- the biimidazole compound refers to a compound having a biimidazole structure, and an example thereof is a lophine dimer, that is, a dimer of 2,4,5-triarylimidazole.
- the lophine dimer include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)biimidazole, 2-(p-methoxyphenyl)-4,5-diphenylbiimidazole, 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chloropheny
- component (C) contains a lophine dimer, and among these, it is more preferable that it contains 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer.
- N-aryl- ⁇ -amino acid compounds examples include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among these, N-phenylglycine is preferred due to its high sensitizing effect.
- Quinone compounds include, for example, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.
- Aromatic ketone compounds include, for example, benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], and 4-methoxy-4'-dimethylaminobenzophenone. From the standpoint of sensitizing effect and adhesion, aromatic ketone compounds also include 4,4'-bis(diethylamino)benzophenone.
- anthracene derivatives includes both anthracene and compounds derived therefrom.
- the anthracene derivatives include anthracene, 9,10-dialkoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, and 10-phenyl-9-anthraceneboronic acid. From the viewpoints of sensitization effect and adhesion, 9,10-dibutoxyanthracene and 9,10-diphenylanthracene are preferred, and 9,10-
- acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1.
- acetophenone compounds include the Irgacure series (manufactured by Ciba Specialty Chemicals: Irgacure-907, Irgacure-369, and Irgacure-379, etc.).
- acylphosphine oxide compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide.
- Commercially available acylphosphine oxide compounds include Lucirin TPO (manufactured by BASF) and Irgacure-819 (manufactured by Ciba Specialty Chemicals).
- benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin.
- dialkyl ketal compound examples include benzyl dimethyl ketal and benzyl diethyl ketal.
- thioxanthone compounds examples include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.
- dialkylaminobenzoate compound examples include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.
- oxime ester compounds examples include 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, etc.
- Commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 (all manufactured by Ciba Specialty Chemicals).
- 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine is preferred in terms of sensitivity, resolution, availability, etc.
- ester compounds of N-arylamino acids include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.
- halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, chlorinated triazine compounds, and diaryliodonium compounds.
- tribromomethylphenylsulfone is preferred.
- the content of component (C) in the photosensitive resin composition is preferably 0.01 to 20 mass %, and more preferably 0.5 to 10 mass %, based on the total mass of solids in the photosensitive resin composition.
- the content of the (C) component other than the biimidazole-based compound in the photosensitive resin composition may be 0.001 to 2.0 mass%, or 0.01 to 2.0 mass%, based on the total solid mass in the photosensitive resin composition.
- the upper limit of the content may be 1.0 mass%, preferably 0.1 mass%, more preferably 0.053 mass%, and even more preferably 0.031 mass%.
- the component (C) other than the biimidazole-based compound in the photosensitive resin composition is preferably an N-aryl- ⁇ -amino acid compound, a quinone compound, an aromatic ketone compound, an anthracene derivative, an acetophenone compound, an acylphosphine oxide compound, a benzoin compound, a benzoin ether compound, a dialkyl ketal compound, a thioxanthone compound, a dialkylaminobenzoic acid ester compound, an oxime ester compound, an acridine compound, a pyrazoline derivative, an N-arylamino acid ester compound, or a halogen compound, and among these, an aromatic ketone compound, an anthracene derivative, or a pyrazoline derivative is particularly preferred.
- the (C) component may not contain any other components than the biimidazole-based compound.
- the photosensitive resin composition may contain, if desired, an antioxidant, a stabilizer, a leuco dye, a base dye, a sensitizer, a color-forming dye, a plasticizer, a hindered amine, and the like.
- antioxidants examples include triphenyl phosphite (e.g., ADEKA, product name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (e.g., ADEKA, product name: 2112), tris(mononylphenyl) phosphite (e.g., ADEKA, product name: 1178), and bis(mononylphenyl)-dinonylphenyl phosphite (e.g., ADEKA, product name: 329K).
- triphenyl phosphite e.g., ADEKA, product name: TPP
- tris(2,4-di-tert-butylphenyl) phosphite e.g., ADEKA, product name: 2112
- tris(mononylphenyl) phosphite e.g., ADEKA, product name: 1178
- the content of the antioxidant in the photosensitive resin composition is preferably 0.01 to 0.8% by mass, and more preferably 0.01 to 0.3% by mass, based on the total solid content in the photosensitive resin composition. From the viewpoint of favorably expressing the hue stability of the resist pattern and improving the sensitivity of the photosensitive resin layer, the content of the antioxidant is preferably equal to or greater than the above lower limit. On the other hand, from the viewpoint of favorably expressing the hue stability while suppressing the color development of the resist pattern and improving adhesion, the content of the antioxidant is preferably equal to or less than the above upper limit.
- the stabilizer may be, for example, at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and alkylene oxide compounds having a glycidyl group.
- radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, 4-tert-butylcatechol, phenothiazine, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxyamine aluminum salt (for example, aluminum salt with 3 moles of nitrosophenylhydroxylamine added), and diphenylnitrosamine.
- triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate] or aluminum salt with 3 moles of nitrosophenylhydroxylamine added is preferred.
- benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.
- Benzotriazoles are preferably compounds having a carboxy group, such as 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole, a 1:1 mixture of 1-(2-di-n-butylaminomethyl)-5-carboxylbenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxylbenzotriazole, etc.
- a carboxy group such as 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2
- 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and a 1:1 mixture of 1-(2-di-n-butylaminomethyl)-5-carboxylbenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxylbenzotriazole are preferred.
- alkylene oxide compounds having a glycidyl group examples include neopentyl glycol diglycidyl ether (e.g., Epolight 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (e.g., Epolight 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2-mol adduct diglycidyl ether (e.g., Epolight 3002 manufactured by Kyoeisha Chemical Co., Ltd.), and 1,6-hexanediol diglycidyl ether (e.g., Epolight 1600 manufactured by Kyoeisha Chemical Co., Ltd.).
- neopentyl glycol diglycidyl ether e.g., Epolight 1500NP manufactured by Kyoeisha Chemical Co., Ltd.
- nonaethylene glycol diglycidyl ether e.g., Epolight 400E manufactured by Ky
- the total content of the stabilizer in the photosensitive resin composition is preferably 0.001 to 3 mass %, and more preferably 0.05 to 1 mass %, based on the total solid content in the photosensitive resin composition. From the viewpoint of imparting good storage stability to the photosensitive resin composition, the total content is preferably equal to or greater than the above lower limit, while from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, the total content is preferably equal to or less than the above upper limit.
- base dyes examples include Diamond Green [CAS number (hereinafter the same): 633-03-4] (e.g., Aizen Diamond Green GH, product name, manufactured by Hodogaya Chemical Co., Ltd.), Fuchsin [632-99-5], Methyl Violet [603-47-4], Methyl Green [82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390-60-5] (e.g., Aizen Victoria Pure Blue BOH, product name, manufactured by Hodogaya Chemical Co., Ltd.), Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], Basic Yellow 2 [2465-27-2], etc.
- Diamond Green is preferred from the viewpoint of improving coloring properties, hue stability, and exposure contrast.
- the content of the base dye in the photosensitive resin composition is preferably 0.001 to 3 mass %, more preferably 0.01 to 2 mass %, and even more preferably 0.04 to 1 mass %, based on the total solid mass in the photosensitive resin composition. From the viewpoint of obtaining good coloring properties, the content of the base dye is preferably equal to or greater than the above lower limit, while from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, the content is preferably equal to or less than the above upper limit.
- leuco dyes include tris(4-dimethylamino-2-methylphenyl)methane [leuco crystal violet] and tris(4-dimethylamino-2-methylphenyl)methane [leucomalachite green].
- halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, and hexachloroethane.
- leuco dyes the above-mentioned leuco crystal violet, or what is called diamond green, may be used.
- Additives such as plasticizers include, for example, phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether.
- phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-but
- Examples of the hindered amine compound include 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethyl-1-hydroxypiperidine, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethyl-1-oxypiperidine, 2,2,6,6-tetramethylpiperidyl methacrylate, and 1,2,2,6,6-pentamethylpiperidyl methacrylate.
- the hindered amine compound preferably has a monofunctional polymerizable group, and 2,2,6,6-tetramethylpiperidyl methacrylate and 1,2,2,6,6-pentamethylpiperidyl methacrylate are particularly preferred.
- the ratio of the hindered amine compound to the total solid content mass of the photosensitive resin composition is preferably 0.001 to 10% by mass. From the viewpoint of excellent releasability, this ratio is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.3% by mass or more. On the other hand, from the viewpoint of improving resolution, this ratio is preferably 5% by mass or less, more preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.
- the above hindered amine compound may be used as a repeating unit in the component (A).
- a preparation liquid for producing the photosensitive resin composition can be prepared by adding a solvent to the photosensitive resin composition.
- the solvent include ketones such as acetone and methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol.
- MEK methyl ethyl ketone
- the solvent can be added to the photosensitive resin composition so that the viscosity of the preparation liquid is 500 to 4000 mPa ⁇ sec at 25° C.
- a further aspect of this embodiment is A support film; a photosensitive resin layer obtained by exposing the photosensitive resin composition to light;
- the photosensitive resin laminate comprises:
- the thickness of the photosensitive resin layer is preferably 3 to 100 ⁇ m, with a more preferred upper limit of 50 ⁇ m. The closer the thickness of the photosensitive resin layer is to 3 ⁇ m, the easier it is to improve the resolution, and the closer it is to 100 ⁇ m, the easier it is to improve the film strength, so the thickness can be selected appropriately depending on the application.
- the transmittance of the photosensitive resin layer at a wavelength of 365 nm when the layer has a thickness of 25 ⁇ m is preferably 45% or more, more preferably 59% or more, even more preferably 60% or more, particularly preferably 63% or more, and most preferably 78% or more.
- the transmittance of the photosensitive resin layer at a wavelength of 365 nm when the layer is 25 ⁇ m thick can be controlled by, for example, the content and/or type of the photopolymerization initiator.
- the transmittance can be increased by reducing the content of the photopolymerization initiator and/or by using a photopolymerization initiator with a low absorption coefficient at a wavelength of 365 nm.
- the support film is preferably a layer or film for supporting the photosensitive resin layer, and is preferably transparent and transmits actinic rays.
- the film examples include transparent films made of synthetic resins such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate.
- synthetic resins such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate.
- PET polyethylene terephthalate
- a PET film synthesized using a titanium (Ti)-based catalyst it is more preferable to use, as the high-quality film, a PET film synthesized using a titanium (Ti)-based catalyst, a PET film with a small diameter and low content of lubricant, a PET film containing lubricant only on one side of the film, a thin PET film, a PET film with a smoothing treatment applied to at least one side, a PET film with a roughening treatment such as plasma treatment applied to at least one side, etc.
- Ti titanium
- a smoothing treatment applied to at least one side
- a PET film with a roughening treatment such as plasma treatment applied to at least one side
- the thickness of the support film is preferably 5 to 25 ⁇ m, and more preferably 6 to 20 ⁇ m.
- the haze of the support film is preferably 0.01% to 1.5%, more preferably 0.01% to 1.2%, and even more preferably 0.01% to 0.95%, from the viewpoint of improving the parallelism of the light beam irradiated to the photosensitive resin layer, thereby making it easier to obtain high resolution after exposure and development of the photosensitive resin laminate.
- the photosensitive resin laminate may include a protective film in addition to the support film and the photosensitive resin layer.
- the protective film is laminated on the photosensitive resin layer on the side opposite to the support film, and functions as a cover for the photosensitive resin layer.
- the protective film can be easily peeled off from the photosensitive resin layer.
- Preferred examples of the protective film include polyethylene film, polypropylene film, oriented polypropylene film, polyester film, etc.
- a release layer can be applied to the surface of the protective film so that the protective film can be easily peeled off from the photosensitive resin layer.
- Release layers are classified into silicone compounds and non-silicone compounds, for example.
- silicone compounds include condensation reaction type silicone resins obtained by reacting polydimethylsiloxane with silanol ends with polymethylhydrogensiloxane or polymethylmethoxysiloxane; addition reaction type silicone resins obtained by reacting dimethylsiloxane-methylvinylsiloxane copolymer or dimethylsiloxane-methylhexenylsiloxane copolymer with polymethylhydrogensiloxane; ultraviolet-curable or electron-beam-curable silicone resins obtained by curing acrylic silicone and epoxy group-containing silicone with ultraviolet light or electron beam; and modified silicone resins such as epoxy-modified silicone resin (silicone epoxy), polyester-modified silicone resin (silicone polyester), acrylic-modified silicone resin (silicone acrylic), phenol-modified silicone resin (silicone phenol), alkyd-modified silicone resin (silicone alkyd), and melamine-modified silicone resin (silicone melamine).
- silicone resins obtained by reacting polydimethyls
- Non-silicone compounds include, for example, alkyd (or alkyd) resins, long-chain alkyl resins, acrylic resins, and polyolefin resins.
- the thickness of the release layer is preferably 0.001 to 2 ⁇ m, more preferably 0.005 to 1 ⁇ m, and even more preferably 0.01 to 0.5 ⁇ m. If the thickness is equal to or less than the upper limit, the coating appearance is likely to be good, and the coating is likely to be sufficiently cured. On the other hand, if the thickness is equal to or more than the lower limit, sufficient release properties are likely to be ensured.
- the thickness of the protective film is preferably 10 to 100 ⁇ m, more preferably 10 to 50 ⁇ m.
- protective films include Alphan (registered trademark) EM-501, E-200, E-201F, FG-201, and MA-411 (all manufactured by Oji F-Tex Co., Ltd.), Torayfan (registered trademark) KW37, 2578, 2548, 2500, and YM17S, Therapeel (registered trademark) PJ271, PJ111, HP2, PJ101, WZ, MDA, MFA, TK07, BKE, BX8A, and SY (all manufactured by Toray Industries, Inc.), and GF-18, GF-818, and GF-858 (all manufactured by Tamapoly Co., Ltd.).
- the photosensitive resin laminate can be produced by laminating a photosensitive resin layer and, if necessary, a protective film on a support film.
- the production method can be, for example, A step of mixing the photosensitive resin composition with a solvent capable of dissolving the photosensitive resin composition to obtain a photosensitive resin composition preparation liquid (coating liquid); A step of applying the coating liquid onto a support film using a bar coater or a roll coater and drying the coating liquid to form a photosensitive resin layer on the support film; If necessary, a step of laminating a protective film on the photosensitive resin layer; may have the following structure:
- a further aspect of the present embodiment is a photosensitive resin roll formed by winding a photosensitive resin laminate.
- the roll may or may not have a core material.
- the long photosensitive resin laminate may be wound around a core material or without a core material.
- a further aspect of this embodiment is A method for forming a resist pattern using the photosensitive resin laminate, comprising the steps of: The following steps: A step of laminating the photosensitive resin laminate on a substrate (lamination step); a step of exposing the photosensitive resin layer in the laminated photosensitive resin laminate (exposure step); and a step of developing the photosensitive resin layer after exposure (development step);
- the method for forming a resist pattern includes the steps of:
- the photosensitive resin layer is heated and pressed onto the surface of a support (e.g., a substrate) by a laminator, and laminated once or multiple times.
- a support e.g., a substrate
- materials for the substrate include copper, stainless steel (SUS), glass, and indium tin oxide (ITO).
- the heating temperature during lamination is, for example, 40°C to 160°C.
- Heating and pressing can be performed by using a laminator equipped with a roll, or by repeatedly passing the laminate of the substrate and the photosensitive resin layer through the roll several times. Heating and pressing can be performed under a reduced pressure environment as desired.
- the photosensitive resin layer is exposed to active light using an exposure machine.
- the exposure can be performed after peeling off the support film as desired, or can be performed without peeling off the support film.
- the exposure amount is determined by the illuminance of the light source and the exposure time, which may be measured using an actinometer.
- direct imaging exposure may be performed.
- direct imaging exposure exposure is performed directly on the substrate using a drawing device without using a photomask.
- the light source a semiconductor laser or an ultra-high pressure mercury lamp with a wavelength of 350 to 410 nm is used.
- the drawing pattern is controlled by a computer, the exposure amount is determined by the illuminance of the exposure light source and the moving speed of the substrate.
- the light irradiation method used in the exposure step is preferably at least one method selected from the group consisting of a projection exposure method, a proximity exposure method, a contact exposure method, a direct imaging exposure method, and an electron beam direct writing method, and is more preferably a projection exposure method or a direct imaging exposure method.
- a heating step may be provided between the exposure step and the development step.
- the heating temperature is preferably about 30 to about 200°C, more preferably 30 to 150°C, and even more preferably 35 to 120°C.
- heating methods include a heating furnace using hot air, infrared or far infrared rays, as well as a thermostatic bath, a hot plate, a hot air dryer, an infrared dryer, a hot roll, etc.
- the time that elapses from the exposure step to the heating step is preferably 10 to 600 seconds, and more preferably 20 to 300 seconds.
- the time that elapses from the point at which heating is started to the point at which heating is stopped is preferably 1 to 120 seconds, and more preferably 5 to 60 seconds.
- the unexposed portion (non-patterned portion) of the photosensitive resin layer after exposure is removed with a developer using a developing device. If there is a support film on the photosensitive resin layer after exposure, it is peeled off. Then, the exposed portion is developed (removed) using a developer containing an alkaline aqueous solution, thereby obtaining a resist image (resist pattern).
- the alkaline aqueous solution is preferably an aqueous solution of Na 2 CO 3 , K 2 CO 3 , tetramethylammonium hydroxide, or the like.
- the alkaline aqueous solution is selected according to the characteristics of the photosensitive resin layer, and examples thereof include an aqueous solution of Na 2 CO 3 with a concentration of 0.2 to 2 mass %.
- the alkaline aqueous solution may contain a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like.
- the temperature of the developer in the development step is preferably kept within the range of 20 to 40°C.
- the development step preferably includes a step of developing (removing) the exposed portion and then removing the developer contained in the resist pattern with washing water (water washing step).
- the washing water is selected according to the characteristics of the photosensitive resin layer, such as pure water or industrial water, and may contain 0.001 to 1 mass % of a polyvalent metal salt such as MgSO 4 , for example, from the viewpoint of improving the resolution and rectangularity of the resist pattern.
- the temperature of the washing water in the water washing step is preferably kept within the range of 20 to 40°C.
- a step of heating it at 60°C to 300°C may be included.
- the chemical resistance of the resist pattern can be easily improved.
- a heating furnace using hot air, infrared rays, or far infrared rays can be used.
- the method for producing a wiring board comprises the following steps: a conductive pattern forming step of forming a conductive pattern by etching or plating the substrate on which the resist pattern has been formed; and a peeling step of peeling the resist pattern from the substrate; Includes.
- the substrate on which the resist pattern has been formed as described above may be subjected to an etching or plating step (etching or plating step), which makes it easy to form a wiring pattern (conductor pattern) corresponding to the resist pattern on the substrate. That is, a further aspect of this embodiment is a method for manufacturing a conductor pattern.
- the method for manufacturing a conductor pattern involves, for example, using a metal plate or a metal-coated insulating plate as a substrate, forming a resist pattern on the substrate using the method described above, and then manufacturing the desired conductor pattern.
- the exposed portion is developed (removed) to expose the substrate surface (e.g., the copper surface), which is then subjected to an etching or plating process.
- the etching process is carried out, for example, by spraying an etching solution onto the resist pattern and the substrate surface.
- the etching method include acid etching and alkaline etching.
- the etching solution include an aqueous hydrochloric acid solution, an aqueous ferric chloride solution, or a mixture thereof.
- the plating process is carried out according to known plating methods by developing (removing) the exposed areas and then plating the exposed areas with metal (for example, with a copper sulfate plating solution) or solder.
- a step of peeling the resist pattern from the substrate may be performed using an aqueous solution having a stronger alkalinity than the developer, thereby obtaining a wiring substrate (e.g., a printed wiring substrate) having a desired conductive pattern.
- the alkaline aqueous solution for stripping may be, for example, an aqueous solution of 2 to 5% by mass of NaOH or KOH, or an organic amine stripping solution.
- a small amount of a water-soluble solvent may be mixed into the stripping solution.
- An example of the water-soluble solvent is alcohol.
- the temperature of the stripping solution in the stripping process is preferably within the range of 40 to 70°C.
- the photosensitive resin laminate may be used in the manufacture of printed wiring boards; the manufacture of lead frames for mounting IC chips; precision processing of metal foils such as the manufacture of metal masks; the manufacture of packages such as ball grid arrays (BGA) and chip size packages (CSP); the manufacture of tape substrates such as chip-on-film (COF) and tape automated bonding (TAB); the manufacture of semiconductor bumps; and the manufacture of partitions for flat panel displays such as ITO electrodes, address electrodes, and electromagnetic shields.
- BGA ball grid arrays
- CSP chip size packages
- COF chip-on-film
- TAB tape automated bonding
- partitions for flat panel displays such as ITO electrodes, address electrodes, and electromagnetic shields.
- the present embodiment will be described with reference to examples and comparative examples.
- the present embodiment is not limited to the following examples.
- the examples and comparative examples were prepared by the following methods, and the physical properties of the examples and comparative examples were measured by the following methods.
- solution (a) was added dropwise to the mixture in the flask at a constant dropping rate over 4 hours, and then stirred at 80°C for 2 hours.
- 0.5 g of azobisisobutyronitrile was dissolved in 50 g of a mixture of 30 g of methyl ethyl ketone and 20 g of ethanol to prepare solution (b).
- the solution (b) was added dropwise to the solution in the flask at a constant dropping rate over 10 minutes, and then the solution in the flask was stirred at 80°C for 3 hours.
- the solution in the flask was then heated to 90° C. over 30 minutes and kept at 90° C.
- Alkali-soluble polymers A-1 to A-12 were obtained by carrying out the same operation while changing the amount of monomers of each copolymerization component in the blending amounts shown in Table 4.
- the weight average molecular weights (Mw) of the obtained alkali-soluble polymers A-1 to A-12 are shown in Table 4.
- the weight average molecular weight was measured by gel permeation chromatography (GPC) and calculated using a calibration curve of standard polystyrene.
- GPC conditions were as follows: (GPC conditions) Pump: JASCO PU-980 Column: 2 columns in total (Shodex KF-80Y/KF-806M) Eluent: tetrahydrofuran Measurement temperature: 40°C Flow rate: 2.05 mL/min Detector: JASCO RI-1530
- Mw weight average molecular weight
- Mn polydispersity
- a 16 ⁇ m-thick polyethylene terephthalate film (QS-68, manufactured by Toray Industries, Inc.) was used as the support film.
- the above-mentioned mixture was uniformly applied to the surface of the film using a bar coater, and then dried in a dryer at 95°C for 3 minutes to form a photosensitive resin layer with a thickness of 25 ⁇ m. This resulted in the production of photosensitive resin laminates (Examples and Comparative Examples).
- a 19 ⁇ m thick polyethylene film (GF-818, manufactured by Tamapoly Co., Ltd.) was attached as a protective film to the surface of the photosensitive resin layer on the side not laminated with the support film.
- GF-818 manufactured by Tamapoly Co., Ltd.
- the transmittance of the photosensitive resin layer at a wavelength of 365 nm was measured using a spectrophotometer U-3010 (manufactured by Hitachi High-Technologies Corporation) with a 16 ⁇ m thick polyethylene terephthalate film (support film, manufactured by Toray Industries, Inc., QS-68) as a reference. The measurement was performed with a slit set to 4 nm and a scan speed set to 600 nm/min.
- ⁇ Evaluation board> A 0.4 mm thick copper-clad laminate laminated with 35 ⁇ m rolled copper foil was prepared. The surface of the substrate was jet scrubbed and polished using an abrasive (Ujiden Chemical Industry Co., Ltd., #400) at a spray pressure of 0.2 MPa. The polished surface of the substrate was washed with a 10 mass% H 2 SO 4 aqueous solution and water in that order. The washed substrate was used as the evaluation substrate.
- the photosensitive resin laminate was laminated onto an evaluation substrate preheated to 50° C. using a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation) at a roll temperature of 105° C.
- the air pressure was 0.35 MPa and the lamination speed was 1.5 m/min.
- ⁇ Exposure> Two hours after lamination, the evaluation substrate was exposed to light using a direct imaging exposure machine (FDi-3, manufactured by Oak Manufacturing Co., Ltd.) using a predetermined imaging pattern for direct imaging (DI) exposure.
- FDi-3 manufactured by Oak Manufacturing Co., Ltd.
- DI direct imaging
- the evaluation substrate 1 minute after exposure was heated for 30 seconds in a constant temperature incubator with airflow (DKM600, manufactured by Yamato Scientific Co., Ltd.) set at 60°C.
- the support film was peeled off from the photosensitive resin layer to expose the photosensitive resin layer. Then, using an alkali developing machine (manufactured by Fuji Kiko Co., Ltd., a dry film developing machine), a 1% by mass Na 2 CO 3 aqueous solution at 30° C. was sprayed onto the photosensitive resin layer for a predetermined time, thereby performing development. After development, the photosensitive resin layer was washed with water by spraying for a predetermined time. The development (spray) time and the water washing (spray) time were both twice the shortest development time. After development, a water washing spray was further performed, and the water washing spray time was twice the shortest development time. At this time, the shortest time required for the photosensitive resin layer in the unexposed portion to completely dissolve was treated as the "shortest development time".
- an alkali developing machine manufactured by Fuji Kiko Co., Ltd., a dry film developing machine
- the arithmetic mean roughness (Ra) of the surface of the photosensitive resin layer was measured using a laser microscope (LEXT OLS4100, manufactured by Olympus Corporation).
- the arithmetic mean roughness (Ra) of the surface was measured at three different points within a reference length of 100 ⁇ m, and the average value of these was calculated. The obtained average value was used as an index of plasma resistance and was evaluated according to the following criteria. If the photosensitive resin layer is damaged by plasma treatment, unevenness may occur on the surface, so a smaller arithmetic mean roughness (Ra) means better plasma resistance. Evaluation criteria: E: Excellent (very good) The arithmetic mean roughness (Ra) is less than 1.5 ⁇ m.
- G Good (good) The arithmetic mean roughness (Ra) is 1.5 ⁇ m or more and less than 3.0 ⁇ m. P: Poor (poor) The arithmetic mean roughness (Ra) is 3.0 ⁇ m or more.
- ⁇ Sensitivity> In the above-mentioned ⁇ exposure> step, a Stouffer 41-step tablet was used as a mask for exposure, and the exposure dose that resulted in the maximum remaining film step number of 15 steps after subsequent development was determined. Evaluation was performed according to the determined exposure dose based on the following criteria. The smaller the exposure dose value, the higher the sensitivity. Evaluation criteria: E: ⁇ (very good) The exposure amount is less than 160 mJ/ cm2. G: ⁇ (good) The exposure amount is 160 mJ/ cm2 or more and less than 200 mJ/ cm2. P: ⁇ (poor) The exposure amount is 200 mJ/cm2 or more.
- Aromatic rings in component (A) refers to the proportion of aromatic rings in component (A);
- Aromatic rings in component (B) refers to the proportion of aromatic rings in component (B);
- St/(A) component represents the ratio of structural units derived from styrene based on the total mass of all monomer components of (A) component;
- BisA/(B) component] is the ratio of compounds having a bisphenol A skeleton based on the total amount of (B) component;
- Component C-1/composition represents the ratio of the imidazole compound based on the total solid content of the photosensitive resin composition;
- the photosensitive resin laminates of the Examples could be wound up by a conventional method, that is, the laminates could be suitably used to prepare rolls.
- the present invention provides a photosensitive resin composition capable of realizing a photosensitive resin layer having excellent desired characteristics (e.g., plasma resistance).
- the photosensitive resin composition according to the present invention can provide a photosensitive resin laminate having good plasma resistance and, in some cases, good sensitivity and adhesion.
- the present invention can be widely used in industries that form resist patterns.
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Abstract
Description
[1]
以下の成分:
(A)アルカリ可溶性高分子、
(B)エチレン性不飽和結合を有する化合物、及び
(C)光重合開始剤、
を含む、感光性樹脂組成物であって、
前記(A)成分及び前記(B)成分は、ともに芳香環を含有し、
前記(A)成分のうち、前記芳香環の割合が0.0045mol/g以上、かつ、
前記(B)成分のうち、前記芳香環の割合が0.0017mol/g以上であり、
前記(A)成分が、ヒドロキシ基を有する化合物を単量体成分として含有し、
前記(C)成分が、前記感光性樹脂組成物の固形分総量を基準として、ビイミダゾール系化合物を4.0質量%以上含む
感光性樹脂組成物。
[2]
前記(A)成分は、その全単量体成分の合計質量を基準として、スチレンに由来する構成単位の割合が51質量%以上であり、
前記(B)成分は、前記(B)成分の総量を基準として、ビスフェノールA型骨格を有する化合物を70質量%以上含む、項目1に記載の感光性樹脂組成物。
[3]
前記(A)成分は、その全単量体成分の合計質量を基準として、スチレンに由来する構成単位の割合が55質量%以上である、項目1又は2に記載の感光性樹脂組成物。
[4]
前記(B)成分は、前記(B)成分の総量を基準として、ビスフェノールA型骨格を有する化合物を80質量%以上含む、項目1~3のいずれか1項に記載の感光性樹脂組成物。
[5]
前記(C)成分は、前記感光性樹脂組成物の固形分総量を基準として、ビイミダゾール系化合物を5.0質量%以上含む、項目1~4のいずれか1項に記載の感光性樹脂組成物。
[6]
前記(C)成分は、前記感光性樹脂組成物の固形分総量を基準として、ビイミダゾール系化合物を6.0質量%以上含む、項目1~5のいずれか1項のいずれか1項に記載の感光性樹脂組成物。
[7]
前記感光性樹脂組成物を用いて得られる感光性樹脂層25μmにおける、波長365nmの透過率が45%以上である、項目1~6のいずれか1項に記載の感光性樹脂組成物。
[8]
前記透過率が60%以上である、項目7に記載の感光性樹脂組成物。
[9]
支持フィルムと、
項目1~8のいずれか1項に記載の感光性樹脂組成物を含む感光性樹脂層と、
を備える、感光性樹脂積層体。
[10]
前記感光性樹脂層の、厚み25μmにおける波長365nmの透過率が、45%以上である、項目9に記載の感光性樹脂積層体。
[11]
項目9又は10に記載の感光性樹脂積層体を捲回して成る、ロール。
[12]
以下の成分:(A)アルカリ可溶性高分子、
(B)エチレン性不飽和結合を有する化合物、及び
(C)光重合開始剤、
を含む、感光性樹脂組成物の製造方法であって、
前記(A)成分及び前記(B)成分は、ともに芳香環を含有し、
前記(A)成分のうち、前記芳香環の割合が0.0045mol/g以上である該(A)成分を用い、かつ、
前記(B)成分のうち、前記芳香環の割合が0.0017mol/g以上である該(B)成分を用いる、
感光性樹脂組成物の製造方法。
[13]
項目9又は10に記載の感光性樹脂積層体を用いる、レジストパターンの形成方法であって、
以下の工程:
感光性樹脂積層体を基板に積層する工程;
積層した前記感光性樹脂積層体における、前記感光性樹脂層を露光する工程;及び
露光後の前記感光性樹脂層を現像する工程;
を含む、レジストパターンの形成方法。
[1A]
以下の成分:
(A)アルカリ可溶性高分子、
(B)エチレン性不飽和結合を有する化合物、及び
(C)光重合開始剤、
を含む、感光性樹脂組成物であって、
前記(A)成分及び前記(B)成分は、ともに芳香環を含有し、
前記(A)成分のうち、前記芳香環の割合が0.0045mol/g以上、かつ、
前記(B)成分のうち、前記芳香環の割合が0.0017mol/g以上である、
感光性樹脂組成物。
[2A]
前記(A)成分は、その全単量体成分の合計質量を基準として、スチレンに由来する構成単位の割合が51質量%以上であり、
前記(B)成分は、前記(B)成分の総量を基準として、ビスフェノールA型骨格を有する化合物を70質量%以上含み、かつ、
前記(C)成分は、前記感光性樹脂組成物の固形分総量を基準として、ビイミダゾール系化合物を4.0質量%以上含む、項目1Aに記載の感光性樹脂組成物。
[3A]
前記(A)成分は、その全単量体成分の合計質量を基準として、スチレンに由来する構成単位の割合が55質量%以上である、項目1A又は2Aに記載の感光性樹脂組成物。
[4A]
前記(B)成分は、前記(B)成分の総量を基準として、ビスフェノールA型骨格を有する化合物を80質量%以上含む、項目1A~3Aのいずれか1項に記載の感光性樹脂組成物。
[5A]
前記(C)成分は、前記感光性樹脂組成物の固形分総量を基準として、ビイミダゾール系化合物を5.0質量%以上含む、項目1A~4Aのいずれか1項に記載の感光性樹脂組成物。
[6A]
前記感光性樹脂組成物を用いて得られる感光性樹脂層25μmにおける、波長365nmの透過率が45%以上である、項目1A~5Aのいずれか1項に記載の感光性樹脂組成物。
[7A]
前記透過率が60%以上である、項目6Aに記載の感光性樹脂組成物。
[8A]
支持フィルムと、
項目1A~7Aのいずれか1項に記載の感光性樹脂組成物を含む感光性樹脂層と、
を備える、感光性樹脂積層体。
[9A]
前記感光性樹脂層の、厚み25μmにおける波長365nmの透過率が、45%以上である、項目8Aに記載の感光性樹脂積層体。
[10A]
項目8A又は9Aに記載の感光性樹脂積層体を捲回して成る、ロール。
[11A]
以下の成分:(A)アルカリ可溶性高分子、
(B)エチレン性不飽和結合を有する化合物、及び
(C)光重合開始剤、
を含む、感光性樹脂組成物の製造方法であって、
前記(A)成分及び前記(B)成分は、ともに芳香環を含有し、
前記(A)成分のうち、前記芳香環の割合が0.0045mol/g以上である該(A)成分を用い、かつ、
前記(B)成分のうち、前記芳香環の割合が0.0017mol/g以上である該(B)成分を用いる、
感光性樹脂組成物の製造方法。
[12A]
項目8A又は9Aに記載の感光性樹脂積層体を用いる、レジストパターンの形成方法であって、
以下の工程:
感光性樹脂積層体を基板に積層する工程;
積層した前記感光性樹脂積層体における、前記感光性樹脂層を露光する工程;及び
露光後の前記感光性樹脂層を現像する工程;
を含む、レジストパターンの形成方法。
本願明細書中、「(メタ)アクリル酸」は、アクリル酸又はメタクリル酸を意味し、「(メタ)アクリロイル基」は、アクリロイル基又はメタクリロイル基を意味し、また、「(メタ)アクリレート」は、「アクリレート」又は「メタクリレート」を意味する。
本願明細書中、特に断りがない限り、各種の数値、及び特性等は、実施例に記載の手法に準じて測定されてよい。
本実施形態は、以下の成分:
(A)アルカリ可溶性高分子、
(B)エチレン性不飽和結合を有する化合物、及び
(C)光重合開始剤、
を含む、感光性樹脂組成物であって、
前記(A)成分及び前記(B)成分は、ともに芳香環を含有し、
前記(A)成分のうち、前記芳香環の割合が0.0045mol/g以上、かつ、
前記(B)成分のうち、前記芳香環の割合が0.0017mol/g以上である、
感光性樹脂組成物である。
特に、本実施形態の感光性樹脂組成物は、
前記(A)成分が、ヒドロキシ基を有する化合物を単量体成分として含有し、 前記(C)成分が、前記感光性樹脂組成物の固形分総量を基準として、ビイミダゾール系化合物を4.0質量%以上含む。
ここで、感光性樹脂組成物に対する露光、及び現像を経てレジストパターンを形成するとき、得られる該レジストパターン上に、該組成物が残存する場合がある。このため、このような残存物(現像残渣)を除去する目的のもと、現像後に形成されるレジストパターンにプラズマ処理が行われる場合がある。この点、本実施形態において、(A)成分、及び(B)成分にそれぞれ含まれる芳香環が、感光性樹脂層の化学的な安定性の向上に貢献し、ひいては、プラズマ耐性の向上が図られている。
(A)成分のうち、芳香環の割合は、0.0082mol/g以下でよく、また、(B)成分のうち、芳香環の割合は、0.0056mol/g以下でよい。
前記(A)成分は、その全単量体成分の合計質量を基準として、スチレンに由来する構成単位の割合が51質量%以上であり、
前記(B)成分は、前記(B)成分の総量を基準として、ビスフェノールA型骨格を有する化合物を70質量%以上含む、
ことを満たす感光性樹脂組成物は、本実施形態の効果を奏し易い。
芳香環を含む化合物のなかでも、スチレン、及びビスフェノールA型骨格を有する化合物は、プラズマ耐性を好適に向上させ易い。また、スチレン、及びビスフェノールA型骨格を有する化合物を用いることで、それぞれを(A)成分、及び(B)成分として感光性樹脂組成物中に好適に導入し易い。感光性樹脂組成物において、芳香環の割合が多くなると樹脂粘度が上がり易くなるので、ラジカル重合効率が低下し易くなり、この場合、ビイミダゾール系化合物を多く配合すること、すなわち、感度低下の抑止を図ることも可能になる。
増感剤と、比較的多量のビイミダゾール系化合物と、の組み合わせにより、感度の低下を防止し易い。他方、増感剤を低減させれば、透過率の向上に有利であり、また、増感剤を低減させる分、更にビイミダゾール系化合物を増量するような設計を実現し易い。本実施形態の感光性樹脂組成物は、この種の組成設計の幅が広く、すなわち、感度と、密着性と、の両立が可能である。
(A)成分は、カルボキシル基を有することが好ましく、アルカリ可溶性を好適に発現する観点から、50~600mgKOH/gの酸価を有することが好ましい。(A)成分の酸価は、60mgKOH/g以上でよく、80mgKOH/g以上でよく、500mgKOH/g以下でよく、400mgKOH/g以下でよい。
また、(A)成分中の単量体成分の割合は、(A)成分として1種のアルカリ可溶性高分子のみを含む場合、共重合比であり、(A)成分として2種以上のアルカリ可溶性高分子が用いられる場合、各アルカリ可溶性高分子の含有比を重みとして、共重合比の加重平均値である。
芳香環は、第一の単量体に由来してもよく、第二の単量体に由来してもよく、第一の単量体、及び第二の単量体の両方に由来してもよい。ただ、所望の(A)成分を実現し易いことから、芳香環の割合は、少なくとも第二の単量体に由来することが好ましい。
(A)成分中の芳香環の割合は、(A)成分中の各単量体成分に含まれる芳香環の割合を、(A)成分中の各単量体成分の含有量の加重平均をとることで算出できる。(A)成分中の各単量体成分に含まれる芳香環の割合は、(単量体1分子中に含まれる芳香環の個数/単量体の分子量)によって算出できる。
ここで、前記(A)成分は、その全単量体成分の合計質量を基準として、スチレンに由来する構成単位の割合が51質量%以上であることが好ましい。これによれば、本実施形態の効果を奏し易い。同様の観点から、スチレンに由来する構成単位の割合が52質量%以上、55質量%以上、また、60質量%以上であることがより好ましく、65%以上であることがさらに好ましい。スチレンに由来する構成単位の割合は、85質量%以下でよい。
同様の観点から、重量平均分子量を10,000以上にすることが好ましく、14,000以上にすることがより好ましく、25,000以上にすることが更に好ましい。
第一の単量体は、その分子中にカルボキシル基を有する。
第一の単量体としては、例えば、(メタ)アクリル酸、フマル酸、ケイ皮酸、クロトン酸、イタコン酸、4-ビニル安息香酸、マレイン酸無水物、マレイン酸半エステルが挙げられる。これらのなかでも、密着性、及び解像性が優れる観点から、(メタ)アクリル酸が好ましく、メタクリル酸がより好ましい。
(メタ)アクリル酸について、「メタクリル酸」は、化学式C4H6O2で表される化合物を意味し、また、「アクリル酸」は、化学式C3H4O2で表される化合物を意味する。
第二の単量体は、その分子中に重合性不飽和基を少なくとも1個有する。
第二の単量体としては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、tert-ブチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、ジシクロペンテニルオキシエチル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ノニルフェノキシポリエチレングリコール(メタ)アクリレート、ペンタメチルピペリジル(メタ)アクリレート、テトラメチルピペリジル(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、エチルカルビトール(メタ)アクリレート、メトキシエチル(メタ)アクリレート、メトキシトリエチレングリコール(メタ)アクリレート、メトキシポリエチレングリコール(メタ)アクリレート、(2-メチル-2-エチル-1,3-ジオキソラン-4-イル)メチル(メタ)アクリレート、環状トリメチロールプロパンホルマール(メタ)アクリレート、3,3,5-トリメチルシクロヘキシル(メタ)アクリレート、等の(メタ)アクリレート類;メチルスチレン、ビニルトルエン、tert-ブトキシスチレン、アセトキシスチレン、スチレンダイマー、及びスチレントリマー等のスチレン誘導体類;酢酸ビニル等のビニルアルコールのエステル類;並びに(メタ)アクリロニトリル等が挙げられる。
上記以外の(メタ)アクリル酸アルキルエステル(鎖状アルキルエステル、及び環状アルキルエステル)、上記以外の共役ジエン化合物、上記以外の極性モノマー(アミノ基含有モノマー、アミド基含有モノマー、シアノ基含有モノマー、及びエポキシ基含有モノマー等)、上記以外の架橋性モノマー、上記以外の酸無水物が挙げられる。
(A)成分の合成は、上記で説明された単数又は複数の単量体を、アセトン、メチルエチルケトン、イソプロパノール等の溶媒で希釈した溶液に、過酸化ベンゾイル、アゾイソブチロニトリル等のラジカル重合開始剤を適量添加し、加熱攪拌することにより行われることが好ましい。混合物の一部を反応液に滴下しながら合成を行う場合もあり、また、反応終了後、更に溶媒を加えて、所望の濃度に調整する場合もある。合成手段としては、溶液重合以外に、リビングラジカル重合、塊状重合、懸濁重合、又は乳化重合を用いてもよい。
(B)成分は、エチレン性不飽和結合を有する化合物である。
(B)成分のうち、芳香環の割合は、0.0017mol/g以上である。芳香環の割合を0.0017mol/g以上にすることはプラズマ耐性を向上させる観点から好ましく、同様の観点から0.0019mol/g以上がより好ましく、0.0021mol/gが更に好ましく、0.0022mol/g以上が特に好ましく、0.0025mol/g以上がさらに好ましく、0.0030mol/g以上が最も好ましい。また、現像性を向上させる観点から0.0056mol/g以下が好ましく、0.0025mol/g以下がさらに好ましく、0.0022mol/g以下がより好ましい。
前記(B)成分は、前記(B)成分の総量を基準として、ビスフェノールA型骨格を有する化合物を61質量%以上含むことが好ましい。これによれば、本実施形態の効果を奏し易い。同様の観点から、ビスフェノールA型骨格を有する化合物の割合が70質量%以上、75質量%以上、また、80質量%以上であることがより好ましく、90質量%以上であることがさらに好ましく、100質量%であることが最も好ましい。
なお、本願明細書中、「ビスフェノールA型骨格を有する化合物」の概念には、ビスフェノールA型骨格を有する化合物を水素化したもの、すなわち、水添ビスフェノールA型骨格を有する化合物も含まれる。
一般式(I)
で表される、ビスフェノールA型ジ(メタ)アクリレートが挙げられる。
ビスフェノールAの両端に、それぞれ平均5molずつのEOを付加したポリエチレングリコ-ルのジメタクリレ-ト(上記「FA-321M」、製品名);
ビスフェノールAの両端に、それぞれ平均2molずつのEOを付加したポリエチレングリコ-ルのジメタクリレート;
POの繰り返し単位を一分子当たり平均12個有するポリプロピレングリコールに、EOを更に両端にそれぞれ平均3molずつ付加したポリアルキレングリコールのジメタクリレート;
が挙げられる(「EO」はエチレンオキサイドの略記であり、また、「PO」はプロピレンオキサイドの略記である)。
上記一般式(I)で表される化合物との関係では、例えば、上記「FA-321M」は、R2=メチル基、X2O=オキシエチレン基、m3+m4=10、n2=n3=0、として表される。
(C)成分は、光重合開始剤である。光重合開始剤は、活性光線によりラジカルを発生し、これにより、エチレン性不飽和結合を有する化合物の重合を開始させ易い。
前記(C)成分は、前記感光性樹脂組成物の固形分総量を基準として、ビイミダゾール系化合物を3.5質量%以上含んでよい。ここで、前記(C)成分は、前記感光性樹脂組成物の固形分総量を基準として、ビイミダゾール系化合物を4.0質量%以上含むことが好ましく、4.2質量%以上含むことがより好ましく、5.0質量%以上含むことがさらに好ましく、6.0%以上含むことが特に好ましく、6.2質量%以上含むことが最も好ましい。これによれば、本実施形態の効果を奏し易い。また、ビイミダゾール系化合物の含有量の割合は、前記感光性樹脂組成物の固形分総量を基準として、10質量%以下でよく、8.0質量%以下でよい。
(A)成分は、その全単量体成分の合計質量を基準として、スチレンに由来する構成単位の割合が40質量%以上であってよい。
ロフィン二量体としては、例えば、2-(o-クロロフェニル)-4,5-ジフェニルビイミダゾール(別名:2,2’-ビス(2-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)、2-(o-クロロフェニル)-4,5-ビス-(m-メトキシフェニル)ビイミダゾール、2-(p-メトキシフェニル)-4,5-ジフェニルビイミダゾール、2,2’,5-トリス-(o-クロロフェニル)-4-(3,4-ジメトキシフェニル)-4’,5’-ジフェニルビイミダゾール、2,4-ビス-(o-クロロフェニル)-5-(3,4-ジメトキシフェニル)-ジフェニルビイミダゾール、2,4,5-トリス-(o-クロロフェニル)-ジフェニルビイミダゾール、2-(o-クロロフェニル)-ビス-4,5-(3,4-ジメトキシフェニル)-ビイミダゾール、2,2’-ビス-(2-フルオロフェニル)-4,4’,5,5’-テトラキス-(3-メトキシフェニル)-ビイミダゾール、2,2’-ビス-(2,3-ジフルオロメチルフェニル)-4,4’,5,5’-テトラキス-(3-メトキシフェニル)-ビイミダゾール、2,2’-ビス-(2,4-ジフルオロフェニル)-4,4’,5,5’-テトラキス-(3-メトキシフェニル)-ビイミダゾール、2,2’-ビス-(2,5-ジフルオロフェニル)-4,4’,5,5’-テトラキス-(3-メトキシフェニル)-ビイミダゾール、2,2’-ビス-(2,6-ジフルオロフェニル)-4,4’,5,5’-テトラキス-(3-メトキシフェニル)-ビイミダゾール、2,2’-ビス-(2,3,4-トリフルオロフェニル)-4,4’,5,5’-テトラキス-(3-メトキシフェニル)-ビイミダゾール、2,2’-ビス-(2,3,5-トリフルオロフェニル)-4,4’,5,5’-テトラキス-(3-メトキシフェニル)-ビイミダゾール、2,2’-ビス-(2,3,6-トリフルオロフェニル)-4,4’,5,5’-テトラキス-(3-メトキシフェニル)-ビイミダゾール、2,2’-ビス-(2,4,5-トリフルオロフェニル)-4,4’,5,5’-テトラキス-(3-メトキシフェニル)-ビイミダゾール、2,2’-ビス-(2,4,6-トリフルオロフェニル)-4,4’,5,5’-テトラキス-(3-メトキシフェニル)-ビイミダゾール、2,2’-ビス-(2,3,4,5-テトラフルオロフェニル)-4,4’,5,5’-テトラキス-(3-メトキシフェニル)-ビイミダゾール、2,2’-ビス-(2,3,4,6-テトラフルオロフェニル)-4,4’,5,5’-テトラキス-(3-メトキシフェニル)-ビイミダゾール、及び2,2’-ビス-(2,3,4,5,6-ペンタフルオロフェニル)-4,4’,5,5’-テトラキス-(3-メトキシフェニル)-ビイミダゾールが挙げられる。
アントラセン誘導体としては、例えば、アントラセン、9,10-ジアルコキシアントラセン、9,10-ジメトキシアントラセン、9,10-ジエトキシアントラセン、9,10-ジブトキシアントラセン、9,10-ジフェニルアントラセン、2-エチルアントラキノン、オクタエチルアントラキノン、1,2-ベンズアントラキノン、2,3-ベンズアントラキノン、2-フェニルアントラキノン、2,3-ジフェニルアントラキノン、1-クロロアントラキノン、10-フェニル-9-アントラセンボロン酸が挙げられる。増感効果及び密着性の観点からは、9,10-ジブトキシアントラセン、9,10-ジフェニルアントラセンが好ましく、特に、9,10-ジフェニルアントラセンが好ましい。
チオキサントン化合物としては、例えば、2,4-ジエチルチオキサントン、2,4-ジイソプロピルチオキサントン、2-クロルチオキサントンが挙げられる。
ジアルキルアミノ安息香酸エステル化合物としては、例えば、ジメチルアミノ安息香酸エチル、ジエチルアミノ安息香酸エチル、エチル-p-ジメチルアミノベンゾエート、2-エチルヘキシル-4-(ジメチルアミノ)ベンゾエートが挙げられる。
なお、これらの化合物については、≪(C)成分:光重合開始剤≫の項目において例示した化合物が参照されてよい。
感光性樹脂組成物は、所望により、酸化防止剤、安定化剤、ロイコ染料、ベース染料、増感剤、発色系染料、可塑剤、ヒンダードアミン等を含むことができる。
架橋反応後の硬化膜の柔軟性が向上し、そして剥離性を向上させる観点で、ヒンダードアミン化合物が単官能重合性基を有することが好ましく、2,2,6,6-テトラメチルピペリジルメタクリレート、1,2,2,6,6-ペンタメチルピペリジルメタクリレートが特に好ましい。
上記ヒンダードアミン化合物は、(A)成分における繰り返し単位として用いられてもよい。
感光性樹脂組成物に溶媒を添加することで、感光性樹脂組成物を作製するための調合液を作製できる。溶媒としては、例えば、アセトン及びメチルエチルケトン(MEK)等のケトン類、メタノール、エタノール、及びイソプロピルアルコール等のアルコール類、が挙げられる。調合液の粘度が25℃で500~4000mPa・secとなるように、感光性樹脂組成物に溶媒を添加することができる。
本実施形態の更なる一態様は、
支持フィルムと、
上記感光性樹脂組成物を露光することで得られる、感光性樹脂層と、
を備える、感光性樹脂積層体である。
感光性樹脂層の膜厚25μmにおける、波長365nmの透過率は、例えば、光重合開始剤の含有量、及び/又は種類によって制御可能である。例えば、光重合開始剤の含有量を減らすこと、及び/又は、波長365nmの吸光係数の低い光重合開始剤を用いることで、該透過率を高め易いる。
支持フィルムは、感光性樹脂層を支持するための層又はフィルムであること、また、活性光線を透過させる透明なものであることが好ましい。
支持フィルムの少なくとも片面に、カレンダー装置等を用いた平滑化処理が施されてよい。
感光性樹脂積層体は、支持フィルムと、感光性樹脂層と、に加え、保護フィルムを備えてよい。保護フィルムは、感光性樹脂層における、支持フィルムとは反対側に積層され、そして、感光性樹脂層のカバーとして機能する。
本実施形態の更なる一態様は、感光性樹脂積層体の作製方法である。
感光性樹脂積層体は、支持フィルムに、感光性樹脂層と、必要により保護フィルムと、を積層することで作製することができる。作製方法は、例えば、
感光性樹脂組成物を、これらを溶解する溶媒と混ぜ合わせることで、感光性樹脂組成物調合液(塗工液)を得る工程、
塗工液を、バーコーター又はロールコーターを用いて支持フィルムに塗布し、そして乾燥させることで、支持フィルム上に感光性樹脂層を形成する工程、
必要により、感光性樹脂層に保護フィルムをラミネートする工程、
を有することができる。
本実施形態の更なる一態様は、感光性樹脂積層体を捲回して成る、感光性樹脂ロールである。
ロールは、芯材を有しても有さなくてもよい。長尺状の感光性樹脂積層体を、芯材を中心に捲回されてもよく、芯材なしに捲回されてもよい。
本実施形態の更なる一態様は、
上記感光性樹脂積層体を用いる、レジストパターンの形成方法であって、
以下の工程:
感光性樹脂積層体を基板に積層する工程(積層工程);
積層した前記感光性樹脂積層体における、前記感光性樹脂層を露光する工程(露光工程);及び
露光後の前記感光性樹脂層を現像する工程(現像工程);
を含む、レジストパターンの形成方法である。
積層工程では、感光性樹脂積層体から保護フィルムを剥離した後、ラミネーターで感光性樹脂層を支持体(例えば、基板)表面に加熱圧着し、1回又は複数回ラミネートする。基板の材料としては、例えば、銅、ステンレス鋼(SUS)、ガラス、酸化インジウムスズ(ITO)が挙げられる。ラミネート時の加熱温度は、例えば40℃~160℃である。加熱圧着は、ロールを備えたラミネーターを使用すること、又は基板と感光性樹脂層との積層物を数回繰り返してロールに通すこと、等により行なうことができる。加熱圧着は、所望により、減圧環境下で行うことができる。
露光工程では、露光機を用いて、感光性樹脂層を活性光に露光する。露光は、所望により支持フィルムを剥離した後に行うことができ、また、支持フィルムを剥離せずに行うこともできる。フォトマスクを通して露光する場合、露光量は、光源照度及び露光時間により決定され、これらは光量計を用いて測定されてよい。露光工程では、ダイレクトイメージング露光を行なってもよい。ダイレクトイメージング露光においては、フォトマスクを使用せず基板上に直接描画装置によって露光する。光源としては、波長350~410nmの半導体レーザー又は超高圧水銀灯が用いられる。描画パターンがコンピュータによって制御される場合、露光量は、露光光源の照度及び基板の移動速度によって決定される。
現像工程では、露光後の感光性樹脂層における未露光部(非パターン部)を、現像装置を用いて現像液により除去する。露光後、感光性樹脂層上に支持フィルムがある場合、これを剥離する。続いて、アルカリ水溶液を含む現像液を用いて、露光部を現像(除去)し、これにより、レジスト画像(レジストパターン)を得る。
本実施形態に係る感光性樹脂組成物を用いて、配線板を製造することも可能である。
配線板の製造方法は、一態様において、以下の工程:
レジストパターンが形成された基板をエッチング又はめっきして導体パターンを形成する導体パターン形成工程;及び
レジストパターンを基板から剥離する剥離工程;
を含む。
上記のとおりレジストパターンを形成した基板を、必要により、エッチング又はめっきする工程(エッチング又はめっき工程)が行われてよい。これにより、レジストパターンに対応する配線パターン(導体パターン)を基板に形成し易い。
すなわち、本実施形態の更なる一態様は、導体パターンの製造方法である。
上記方法により導体パターンを製造した後、現像液よりも強いアルカリ性を有する水溶液を用いて、レジストパターンを基板から剥離する工程(剥離工程)が行われてよい。これにより、所望の導体パターンを有する配線基板(例えば、プリント配線基板)を得ることができる。
メタクリル酸28g、スチレン52g、2-ヒドロキシエチルメタアクリレート20g(共重合成分)を、アゾビスイソブチロニトリル0.8gとともに混合し、溶液(a)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たフラスコに、メチルエチルケトン200g、及びエタノール100g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、そして80℃まで昇温させた。フラスコ内の上記混合液に、滴下速度を一定にして上記溶液(a)を4時間かけて滴下した後、80℃にて2時間撹拌した。次いで、メチルエチルケトン30g、及びエタノール20gの混合液50gに、アゾビスイソブチロニトリル0.5gを溶解して溶液(b)を調整した。フラスコ内の溶液に、滴下速度を一定にして上記溶液(b)を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。更に、フラスコ内の溶液を30分間かけて90℃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℃)まで冷却した。これにより、アルカリ可溶高分子A―1の溶液を得た。
表4に示される配合量で各共重合成分の単量体の投入量を変更し、そして同様の操作を行うことで、アルカリ可溶性高分子A-1~A-12を得た。得られたアルカリ可溶性高分子A-1~A-12の重量平均分子量(Mw)を表4に示す。
(GPC条件)
ポンプ:日本分光製 PU-980
カラム:以下の計2本
Shodex社製 KF-80Y/KF-806M
溶離液:テトラヒドロフラン
測定温度:40℃
流量:2.05mL/分
検出器:日本分光製 RI-1530
本願明細書中「重量平均分子量(Mw)」「多分散度(Mw/Mn)」は、上記に従い測定される。
<感光性樹脂組成物、及び感光性樹脂積層体等>
表に示す成分(ただし、各成分の数字は、固形分としての配合量(質量部)を示す)、及び溶媒(エタノール)を、固形分が60質量%となるように攪拌、及び混合し、これにより、感光性樹脂組成物(実施例、及び比較例)を含む調合液を得た。なお、表1~3に記載される略号は、表4に記載される名称に対応している。
上記感光性エレメントの保護フィルムを剥離した後、分光光度計U-3010(日立ハイテクノロジーズ株式会社製)を用い、16μm厚のポリエチレンテレフタレートフィルム(支持フィルム、東レ(株)製、QS―68)をリファレンスとして、感光性樹脂層の波長365nmにおける透過率を測定した。なお、測定は、スリットを4nm、スキャン速度を600nm/分に設定して行った。
35μm圧延銅箔を積層した、0.4mm厚の銅張積層板を用意した。そして、研削剤(宇治電化学工業(株)製、#400)を用い、かつ、スプレー圧0.2MPaの条件で、基板の表面をジェットスクラブ研磨した。研磨後の基板の表面を、10質量%H2SO4水溶液、水の順で洗浄した。洗浄後の基板を、評価用基板として用いた。
感光性樹脂積層体から保護フィルムを剥がしながら、50℃に予熱した評価用基板に、ホットロールラミネーター(旭化成(株)社製、AL-700)により、ロール温度105℃で感光性樹脂積層体をラミネートした。エアー圧は0.35MPa、ラミネート速度は1.5m/minであった。
ラミネート後2時間経過した評価用基板に、直接描画露光機((株)オーク製作所製 FDi-3)により露光した。ここで、露光は、所定のダイレクトイメージング(DI)露光用の描画パターンを用いて行った。
ここでは、露光後1分経過した評価用基板を、60℃に設定した送風定温恒温器(ヤマト科学(株)製、DKM600)により、30秒間加熱した。
感光性樹脂層から支持フィルムを剥離し、該感光性樹脂層を露出させた。その後、アルカリ現像機((株)フジ機工製、ドライフィルム用現像機)を用い、30℃の1質量%Na2CO3水溶液を、所定時間に亘って感光性樹脂層にスプレーし、これにより現像を行った。現像後、所定時間に亘って感光性樹脂層をスプレーにより水洗した。現像(スプレー)の時間、及び水洗(スプレー)の時間として、ともに、最短現像時間の2倍の時間を用いた。現像後にも更に水洗スプレーを行い、そして、その水洗スプレーの時間は、最短現像時間の2倍の時間とした。このとき、未露光部分の感光性樹脂層が完全に溶解するのに要する、最も短い時間を「最短現像時間」として扱った。
<プラズマ耐性>
ストーファー41段ステップタブレットにて最高残膜段数が15段となる露光量にて露光し、現像した感光性樹脂層に対して、プラズマエッチング装置(神港精機(株)製 EXAM)を用い、1000秒間に亘り、プラズマ処理を施した。ここでの処理は、出力を133W、O2ガスを40cm3/min、CF4ガスを41cm3/min、圧力を50Paとして行った。
評価基準:
E:◎(著しく良好) 算術平均粗さ(Ra)が1.5μm未満
G:○(良好) 算術平均粗さ(Ra)が1.5μm以上3.0μm未満
P:×(不良) 算術平均粗さ(Ra)が3.0μm以上
上記<露光>工程において、ストーファー41段ステップタブレットをマスクとして露光し、そして、その後に現像したときの最高残膜段数が15段となる露光量を求めた。求めた露光量に応じて、以下の基準で評価した。露光量の値が小さいほど、感度が高いことを意味する。
評価基準:
E:◎(著しく良好) 上記露光量が160mJ/cm2未満
G:○(良好) 上記露光量が160mJ/cm2以上200mJ/cm2未満 P:×(不良) 上記露光量が200mJ/cm2以上
ライン/スペース(L/S)がx/3x{x=1~20(1μm間隔で変化)、単位:μm}であるマスクパターンを用いて評価を行った。すなわち、上記ラミネート後の評価用基板に対して、該マスクパターンを用いてストーファー41段ステップタブレットにて最高残膜段数が15段となる露光量にて露光し、露光した。その後、現像を行うことにより、レジストパターンを形成した。このレジストパターンを、光学顕微鏡にて倍率50倍で観察することで、観察画像を得た。観察画像において、ライン部分(露光部分)が蛇行、及び欠けを生じることなく形成された最小のライン幅を求めた。該ライン幅を密着性の指標として扱い、そしてこれを以下の基準で評価した。密着性の値が小さいほど、密着性が良好であることを意味する。
評価基準:
E:◎(著しく良好) 密着性が6μm未満
G:○(良好) 密着性が6μm以上9μm未満
P:×(不良) 密着性が9μm以上
「(A)成分中の芳香環」は、(A)成分のうち芳香環の割合を;
「(B)成分中の芳香環」は、(B)成分のうち芳香環の割合を;
「St/(A)成分」は、(A)成分の全単量体成分の合計質量を基準とした、スチレンに由来する構成単位の割合を;
「BisA/(B)成分]は、(B)成分の総量を基準とした、ビスフェノールA型骨格を有する化合物の割合を;
「成分C-1/組成物」は、感光性樹脂組成物の固形分総量を基準とした、イミダゾール系化合物の割合を;
それぞれ意味する。
なお、実施例の感光性樹脂積層体は、常法により捲回が可能であった、すなわち、該積層体を用いて好適にロールを作製できた。
Claims (13)
- 以下の成分:
(A)アルカリ可溶性高分子、
(B)エチレン性不飽和結合を有する化合物、及び
(C)光重合開始剤、
を含む、感光性樹脂組成物であって、
前記(A)成分及び前記(B)成分は、ともに芳香環を含有し、
前記(A)成分のうち、前記芳香環の割合が0.0045mol/g以上、かつ、
前記(B)成分のうち、前記芳香環の割合が0.0017mol/g以上であり、
前記(A)成分が、ヒドロキシ基を有する化合物を単量体成分として含有し、
前記(C)成分が、前記感光性樹脂組成物の固形分総量を基準として、ビイミダゾール系化合物を4.0質量%以上含む
感光性樹脂組成物。 - 前記(A)成分は、その全単量体成分の合計質量を基準として、スチレンに由来する構成単位の割合が51質量%以上であり、
前記(B)成分は、前記(B)成分の総量を基準として、ビスフェノールA型骨格を有する化合物を70質量%以上含む、請求項1に記載の感光性樹脂組成物。 - 前記(A)成分は、その全単量体成分の合計質量を基準として、スチレンに由来する構成単位の割合が55質量%以上である、請求項1に記載の感光性樹脂組成物。
- 前記(B)成分は、前記(B)成分の総量を基準として、ビスフェノールA型骨格を有する化合物を80質量%以上含む、請求項3に記載の感光性樹脂組成物。
- 前記(C)成分は、前記感光性樹脂組成物の固形分総量を基準として、ビイミダゾール系化合物を5.0質量%以上含む、請求項1に記載の感光性樹脂組成物。
- 前記(C)成分は、前記感光性樹脂組成物の固形分総量を基準として、ビイミダゾール系化合物を6.0質量%以上含む、請求項1に記載の感光性樹脂組成物。
- 前記感光性樹脂組成物を用いて得られる感光性樹脂層25μmにおける、波長365nmの透過率が45%以上である、請求項1に記載の感光性樹脂組成物。
- 前記透過率が60%以上である、請求項7に記載の感光性樹脂組成物。
- 支持フィルムと、
請求項1~8のいずれか1項に記載の感光性樹脂組成物を含む感光性樹脂層と、
を備える、感光性樹脂積層体。 - 前記感光性樹脂層の、厚み25μmにおける波長365nmの透過率が、45%以上である、請求項9に記載の感光性樹脂積層体。
- 請求項9に記載の感光性樹脂積層体を捲回して成る、ロール。
- 以下の成分:(A)アルカリ可溶性高分子、
(B)エチレン性不飽和結合を有する化合物、及び
(C)光重合開始剤、
を含む、感光性樹脂組成物の製造方法であって、
前記(A)成分及び前記(B)成分は、ともに芳香環を含有し、
前記(A)成分のうち、前記芳香環の割合が0.0045mol/g以上である該(A)成分を用い、かつ、
前記(B)成分のうち、前記芳香環の割合が0.0017mol/g以上である該(B)成分を用いる、
感光性樹脂組成物の製造方法。 - 請求項9に記載の感光性樹脂積層体を用いる、レジストパターンの形成方法であって、
以下の工程:
感光性樹脂積層体を基板に積層する工程;
積層した前記感光性樹脂積層体における、前記感光性樹脂層を露光する工程;及び
露光後の前記感光性樹脂層を現像する工程;
を含む、レジストパターンの形成方法。
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