WO2023136333A1 - Photosensitive resin composition, photosensitive resin laminate, and resist pattern formation method - Google Patents

Photosensitive resin composition, photosensitive resin laminate, and resist pattern formation method Download PDF

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Publication number
WO2023136333A1
WO2023136333A1 PCT/JP2023/000842 JP2023000842W WO2023136333A1 WO 2023136333 A1 WO2023136333 A1 WO 2023136333A1 JP 2023000842 W JP2023000842 W JP 2023000842W WO 2023136333 A1 WO2023136333 A1 WO 2023136333A1
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WIPO (PCT)
Prior art keywords
photosensitive resin
component
resin composition
mass
composition according
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PCT/JP2023/000842
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French (fr)
Japanese (ja)
Inventor
大介 宇野
隆覚 櫻井
秀昭 西本
裕樹 松尾
Original Assignee
旭化成株式会社
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Priority to JP2023574094A priority Critical patent/JPWO2023136333A1/ja
Priority to KR1020247012316A priority patent/KR20240054400A/en
Publication of WO2023136333A1 publication Critical patent/WO2023136333A1/en

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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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/092—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by backside coating or layers, by lubricating-slip layers or means, by oxygen barrier layers or by stripping-release layers or means
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/061—Etching masks
    • H05K3/064—Photoresists

Definitions

  • the present invention relates to a photosensitive resin composition, a photosensitive resin laminate, and a method for forming a resist pattern.
  • photolithography for example, a photosensitive resin laminate having a support and a photosensitive resin layer is laminated on a substrate from the photosensitive resin layer side (opposite side to the support). By exposing and developing such a photosensitive resin layer, a resist pattern can be formed on the substrate, and the substrate can be etched after plating if necessary.
  • Patent Literature 1 discloses a photosensitive resin composition containing an alkali-soluble polymer having an inorganic value (I value) of a predetermined value or less.
  • a photosensitive resin composition having low hydrophobicity may have excellent solubility in a developer (excellent developability).
  • Patent Document 2 discloses an addition product of a carboxyl group-containing resin and an unsaturated compound having an ⁇ , ⁇ -unsaturated double bond and an epoxy group, and having an acid value of 50 to 200.
  • a photosensitive resin composition is disclosed that includes an alkali-soluble polymer.
  • the carboxyl group-containing resin is produced from comonomer components such as 36 parts by mass of acrylic acid, 43 parts by mass of methacrylic acid, and 10 parts by mass of methyl methacrylate.
  • the photosensitive resin compositions of Patent Documents 1 and 2 have room for improvement from the viewpoint of achieving both the developability of the photosensitive resin layer and the resolution of the resulting resist pattern. That is, as one method for achieving high resolution, it is conceivable to improve the hydrophobicity of the photosensitive resin layer, but if the hydrophobicity of the photosensitive resin layer is improved, the solubility in the developer decreases. Therefore, development time tended to be long. In addition, due to the recent demand for high resolution, provision of a photosensitive resin composition having a photosensitive resin layer capable of improving adhesion to a substrate has been awaited.
  • an object of the present invention is to provide a photosensitive resin composition capable of improving various properties by controlling the type and ratio of at least the acid comonomer component among the comonomer components of the alkali-soluble polymer. It is in.
  • Another object of the present invention is to provide a photosensitive resin laminate comprising a photosensitive resin layer obtained from such a photosensitive resin composition, and a method for forming a resist pattern realized using the same. .
  • the component (A) contains at least the following comonomer components: (a) methacrylic acid or acrylic acid, (b) a carboxylic acid different from the acid selected as component (a); and (c) a compound having an aromatic or alicyclic structure, has a structural unit derived from In the component (A),
  • the mass ratio (a1) of structural units derived from the component (a); a mass ratio (b1) of structural units derived from the component (b); ratio (the mass ratio (a1)/the mass ratio (b1)) is 1/10 to 10, a photosensitive resin composition.
  • the photosensitive resin composition according to item 10 wherein the ratio of the styrene-derived structural unit in the component (A) is 45 to 95% by mass.
  • Component (A) 10 to 90% by mass
  • the (B) component 5 to 70% by mass
  • the (C) component 0.01 to 20% by mass
  • the photosensitive resin composition according to any one of items 1 to 11, comprising: [13] 13.
  • the relationship between the mass average of the mass ratio (a1) and the mass average of the mass ratio (b1) (mass average of mass ratio (a1) / mass average of mass ratio (b1)) is 1/10 to 10 14.
  • the photosensitive resin composition according to item 13. At least one of the alkali-soluble polymers contained in the component (A), 15.
  • the component (B) contains a compound having a bisphenol A structure and/or a hydrogenated bisphenol A structure.
  • HABI hexaarylbiimidazole
  • the mass ratio (a1) of structural units derived from the component (a); a mass ratio (b1) of structural units derived from the component (b); The mass ratio (c1) of the structural unit derived from the component (c) is represented by the following formulas (1) to (3): 10 ⁇ (a1)+(b1) ⁇ 50 (1) 0.5 ⁇ (a1)/(b1) ⁇ 8.0 (2) 30 ⁇ (c1) ⁇ 80 (3)
  • the photosensitive resin composition according to any one of items 1 to 21, which satisfies [23]
  • the component (A) contains a plurality of alkali-soluble polymers, At least one of the alkali-soluble polymers contained in component (A) has structural units derived from components (a) to (c), and 23.
  • the photosensitive resin composition according to item 22 wherein the mass ratios (a1), (b1), and (c1) satisfy the formulas (1) to (3).
  • a photosensitive resin laminate comprising a support and a photosensitive resin layer obtained from the photosensitive resin composition according to any one of items 1 to 24. [26] 26.
  • the photosensitive resin laminate according to item 25 comprising a protective film on the side of the photosensitive resin layer opposite to the support.
  • the photosensitive resin composition of the present invention it is possible to improve the developability of the photosensitive resin layer by controlling the type and ratio of at least the acid comonomer component among the comonomer components of the alkali-soluble polymer. can.
  • the photosensitive resin composition of the present invention it is possible to improve the adhesion of the photosensitive resin layer to the substrate and the resolution of the resist pattern.
  • this embodiment An embodiment of the present invention (hereinafter abbreviated as "this embodiment") will be described below.
  • the present invention is not limited to this embodiment, and various modifications can be made within the scope of the gist of the present invention.
  • the numerical range described using "-" includes the numerical values described before and after "-”.
  • the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described in stages. can be done.
  • the upper limit value or lower limit value described in a certain numerical range can be replaced with the values shown in the examples.
  • (meth)acrylic means acrylic or methacrylic
  • (meth)acryloyl means acryloyl or methacryloyl
  • (meth)acrylate means acrylate or methacrylate
  • the photosensitive resin composition according to this embodiment is Ingredients for: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, including.
  • the above (A) to (C) are also simply referred to as "(A) component” to "(C) component".
  • the (A) component is at least the following comonomer component: (a) methacrylic acid or acrylic acid, (b) a carboxylic acid different from the acid selected as component (a) above; and (c) a structural unit derived from a compound having an aromatic structure or an alicyclic structure.
  • (a) and (b) are also referred to simply as "(a) acid comonomer component” and “(b) acid comonomer component”, and (c) is referred to simply as "(c) comonomer component”.
  • comonomer component also called
  • the component (A) (a) mass ratio (a1) of structural units derived from the acid comonomer component; (b) the mass ratio (b1) of structural units derived from the acid comonomer component;
  • the ratio of (mass ratio (a1)/mass ratio (b1)) is 1/10 to 10.
  • “1/10” here is, for example, "0.1".
  • a plurality of acid comonomer components are used in combination as the comonomer component of the alkali-soluble polymer, and the plurality of acid comonomer components and other comonomer components are also used in combination.
  • the type and content ratio of at least the acid comonomer component are controlled.
  • a photosensitive resin composition it is possible to improve various properties (developability of the photosensitive resin layer, adhesion of the photosensitive resin layer to the substrate, resolution of the resist pattern, etc.).
  • comonomer components of the alkali-soluble polymer a plurality of acid comonomer components are used in combination, and the plurality of acid comonomer components and other aromatic or alicyclic structures are combined. It can also be used in combination with a comonomer component having.
  • the present inventors have found that controlling the type and content ratio of at least the acid comonomer component leads to improvement in various performances, and based on such an idea, the present embodiment is proposed. It is a thing.
  • the ratio of comonomer components having other aromatic or alicyclic structures can also be controlled. It is easy to improve the adhesion to the substrate and the resolution of the resist pattern).
  • Each component constituting the photosensitive resin composition will be described below.
  • Component (A) is a polymer soluble in an alkaline solution.
  • Component (A) preferably has a carboxyl group, and from the viewpoint of improving developability, preferably has an acid value of 50 to 600 mgKOH/g, and more preferably has an acid value of 100 to 400 mgKOH/g. preferable.
  • the acid value of component (A) may be 60 mgKOH/g or more, 80 mgKOH/g or more, 100 mgKOH/g or more, 500 mgKOH/g or less, or 400 mgKOH/g or less.
  • the (A) component can be thermoplastic.
  • the acid value refers to milligrams of potassium hydroxide required to neutralize 1 g of component (A).
  • the weight average molecular weight of component (A) is preferably from 5,000 to 500,000, more preferably from 10,000 to 200,000, even more preferably from 20,000 to 100,000. , 23,000 to 70,000.
  • the weight-average molecular weight of component (A) is at least the above lower limit, it becomes easier to maintain a uniform thickness of the photosensitive resin layered body and to ensure the resistance of the exposed portion to the developing solution.
  • the polydispersity (Mw/Mn) which is the ratio of the weight average molecular weight (Mw) of component (A) to the number average molecular weight (Mn) of component (A), is 1.0 to 6.0.
  • the weight average molecular weight and polydispersity are measured by gel permeation chromatography (GPC) using a polystyrene calibration curve. The weight average molecular weight can be measured, for example, under the following conditions.
  • the content of component (A) in the photosensitive resin composition (based on the total solid content of the photosensitive resin composition.
  • the content of component (A) in the photosensitive resin composition is preferably 10 to It is 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 60% by mass.
  • the content of component (A) is preferably at least the above lower limit.
  • the resist pattern formed by exposure fully exhibits the performance as a resist material, it is preferably not more than the above upper limit.
  • component (A) is at least the following comonomer components: (a) methacrylic acid or acrylic acid, (b) a carboxylic acid different from the acid selected as the (a) acid comonomer component, and (c) a compound having an aromatic or alicyclic structure, obtained by polymerizing Therefore, component (A) has at least structural units derived from each of (a) acid comonomer component, (b) acid comonomer component, and (c) comonomer component.
  • (a) acid comonomer component) (a) the acid comonomer component is methacrylic acid or acrylic acid;
  • methacrylic acid refers to the compound represented by the chemical formula C4H6O2
  • acrylic acid refers to the compound represented by the chemical formula C3H4O2 .
  • the (b) acid comonomer component is a carboxylic acid different from the acid comonomer component selected for (a) the acid comonomer component above.
  • the (b) acid comonomer component may be a carboxylic acid different from methacrylic acid.
  • the (b) acid comonomer component may be a carboxylic acid different from acrylic acid.
  • the (b) acid comonomer component may be a carboxylic acid different from both methacrylic acid and acrylic acid.
  • the acid comonomer component may be a compound having an ethylenically unsaturated bond and may be a compound having a (meth)acryloyl group.
  • the acid comonomer component may be used alone or in combination of two or more.
  • the (b) acid comonomer component can be, for example, acrylic acid when the (a) acid comonomer component is methacrylic acid, or methacrylic acid when the (a) acid comonomer component is acrylic acid.
  • the (b) acid comonomer component can be a carboxylic acid different from both methacrylic acid and acrylic acid, for example.
  • carboxylic acids different from methacrylic acid and acrylic acid include cinnamic acid, crotonic acid, succinic acid half ester, maleic acid half ester, fumaric acid half ester, 4-vinylbenzoic acid, succinic acid, maleic acid, fumaric acid, itaconic acid, and the like.
  • mass ratio (a1) of structural units derived from the acid comonomer component (b) the mass ratio (b1) of structural units derived from the acid comonomer component; (mass ratio (a1)/mass ratio (b1)) is 1/10 to 10 (eg, 10.0).
  • the carboxylic acids that can be selected as the (a) acid comonomer component and (b) the acid comonomer component have different effects on the properties of the photosensitive resin composition and the photosensitive resin layer depending on the type. Therefore, by controlling the type and ratio of at least the acid comonomer component among the comonomer components of the alkali-soluble polymer, various properties of the photosensitive resin layer can be improved.
  • the ratio (mass ratio (a1)/mass ratio (b1)) is preferably 1/8 to 8 (eg, 8.0), and 1/7 to 7.0. is more preferable, 1/5 to 5.0 is more preferable, and 1/4.2 to 4.2 is even more preferable.
  • the acid comonomer component is preferably methacrylic acid. According to this, the contribution of methacrylic acid is obtained, and it becomes easy to realize a photosensitive resin layer excellent in various properties.
  • the (a) acid comonomer component is methacrylic acid and the (b) acid comonomer component is acrylic acid.
  • methacrylic acid and acrylic acid the contribution of methacrylic acid, which is relatively hydrophobic, makes it easier to improve the resolution of the resist pattern, and the contribution of acrylic acid, which has a relatively low glass transition temperature. It becomes easy to aim at the developability improvement by obtaining. Therefore, the contribution of both acids can be preferably obtained, and as a result, various characteristics (developability of the photosensitive resin layer, resolution of the resist pattern, etc.) can be improved.
  • acrylic acid that can be used as component (b) has a lower glass transition temperature (Tg) than methacrylic acid that can be used as component (a). Therefore, for example, when focusing on the case of methacrylic acid and acrylic acid, by controlling the type and content ratio of at least the acid comonomer component, the hydrophobicity of the component (A) as a whole can be secured and the solution can be obtained. Tg can be adjusted to favor image quality improvement.
  • the (a) acid comonomer component is methacrylic acid or acrylic acid
  • the (b) acid comonomer component may contain a carboxylic acid different from both methacrylic acid and acrylic acid. According to this, the contributions of carboxylic acids different from methacrylic acid and acrylic acid can be obtained, and it becomes easy to realize a photosensitive resin layer excellent in various properties.
  • the sum of (a) the mass ratio (a1) of structural units derived from the acid comonomer component and (b) the mass ratio (b1) of the structural units derived from the acid comonomer component is 1 to It is preferably 65% by mass. According to this, it is possible to ensure room for other comonomer components to be included, and it becomes easy to widen the range of composition design according to various uses.
  • the ratio of the constituent units of the comonomer component in the component (A) roughly corresponds to the amount of the comonomer component charged. From the same viewpoint as above, the total is more preferably 5 to 50% by mass, even more preferably 15 to 35% by mass, and particularly preferably 20 to 30% by mass.
  • a comonomer component is one of the comonomer components for obtaining the (A) component, and is a compound having an aromatic structure or an alicyclic structure. (c) By having such a configuration of the comonomer component, it is possible to improve the adhesion of the resist pattern. (c)
  • the comonomer component may be a compound having an ethylenically unsaturated bond or a compound having a (meth)acryloyl group.
  • the comonomer component may be used alone or in combination of two or more.
  • Examples of compounds having an aromatic structure include styrene, styrene derivatives, benzyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, and the like.
  • Examples of styrene derivatives include 4-methylstyrene, 4-hydroxystyrene, 4-methoxystyrene, 4-chlorostyrene, 4-(chloromethyl)styrene and the like.
  • Examples of compounds having an alicyclic structure include groups having one cyclic hydrocarbon group such as cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group, or (meth)acrylic acid esters having groups composed of derivatives thereof. , a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group, an isobornyl group, a group having two or more cyclic hydrocarbons, or a (meth)acrylic acid ester having a group consisting of derivatives thereof.
  • the comonomer component preferably contains styrene and/or benzyl (meth)acrylate, and more preferably contains styrene. This makes it easier to improve the adhesion of the resist pattern even when the development time is prolonged.
  • the content of (c) comonomer component in component (A) is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, even more preferably 40 to 90% by mass, 45 to 80 mass % is even more preferred, and 65 to 80 mass % is particularly preferred. According to this range, it is easy to maintain good alkali solubility, and it is easy to improve the adhesion of the resist pattern.
  • the comonomer component contains styrene, and the styrene content is 45% by mass or more, preferably 50% by mass or more, more preferably 55% by mass, even more preferably 60% by mass or more, and particularly preferably 65% by mass or more; It is preferable that there is one from the viewpoint of facilitating the improvement of the adhesion of the resist pattern.
  • the comonomer component contains styrene, the content of styrene may be 95% by mass or less.
  • the component (A) is composed of (a) methacrylic acid and (b) acrylic acid. It is preferable to contain an acid and (c) styrene as comonomer components, and (a) the mass ratio (a1) of structural units derived from methacrylic acid, and (b) the mass ratio (b1 ) and (c) the mass ratio (c1) of structural units derived from styrene, the following formulas (1) to (3): 10 ⁇ (a1)+(b1) ⁇ 50 (1) 0.5 ⁇ (a1)/(b1) ⁇ 8.0 (2) 30 ⁇ (c1) ⁇ 80 (3) preferably satisfy all Formulas (4) to (6) below: 15 ⁇ (a1)+(b1) ⁇ 35 (4) 1.0 ⁇ (a1)/(b1) ⁇ 6.0 (5) 45 ⁇ (c1) ⁇ 75 (6) It is more preferable to satisfy all Formulas (7) to (9) below: 20 ⁇ (a1)+(
  • the component (A) can further have a structural unit derived from a hydroxyalkyl (meth)acrylic acid ester (also referred to as “(d) comonomer component”) as a comonomer component.
  • a hydroxyalkyl (meth)acrylic acid ester also referred to as “(d) comonomer component”
  • Such compounds have hydroxyl (OH) groups and are therefore highly hydrophilic compared to, for example, methacrylic acid or acrylic acid. Therefore, the component (A) can easily control the developability of the photosensitive resin layer by optional combination with the comonomer component (d).
  • the comonomer component may be used singly or in combination of two or more.
  • hydroxyalkyl (meth)acrylate esters examples include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and hydroxypentyl (meth)acrylate.
  • the comonomer component preferably comprises hydroxyethyl methacrylate. According to this, it is easy to obtain and easy to control the developability.
  • the content of (d) comonomer component in component (A) is preferably 1.0 to 50% by mass, more preferably 1.5 to 40% by mass, and 2.0 to 20% by mass. It is even more preferable to have
  • the component (A) is a comonomer component ("another comonomer (also referred to as "component”) can be further used in combination.
  • comonomer components include, for example, (meth)acrylic acid alkyl esters, conjugated diene compounds, polar monomers (excluding hydroxyalkyl (meth)acrylates), crosslinkable monomers, acid anhydrides (e.g., maleic anhydride). etc.
  • (Meth)acrylic acid alkyl ester is a concept that includes both chain alkyl esters and cyclic alkyl esters, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl ( meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth) Acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, n-tetradecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate and the like.
  • conjugated diene compounds include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1, 3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene and the like.
  • Polar monomers include, for example, amino group-containing monomers such as 2-aminoethyl methacrylate; amide group-containing monomers such as (meth)acrylamide and N-methylol(meth)acrylamide; acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, cyano group-containing monomers such as ⁇ -cyanoethyl acrylate; epoxy group-containing monomers such as glycidyl (meth)acrylate and 3,4-epoxycyclohexyl (meth)acrylate; and the like.
  • amino group-containing monomers such as 2-aminoethyl methacrylate
  • amide group-containing monomers such as (meth)acrylamide and N-methylol(meth)acrylamide
  • acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile cyano group-containing monomers such as ⁇ -cyanoethyl acrylate
  • epoxy group-containing monomers
  • crosslinkable monomers examples include trimethylolpropane triacrylate and divinylbenzene.
  • a component can contain several alkali-soluble polymers.
  • the component (A) may be a combination of (A1) an alkali-soluble polymer containing methacrylic acid and styrene and (A2) an alkali-soluble polymer containing acrylic acid and styrene. and (A3) an alkali-soluble polymer containing methacrylic acid and hydroxyethyl methacrylate.
  • the mass average of each of the mass ratio (a1), the mass ratio (b1), and the mass ratio (c1) is, for example, when the component (A) contains an N-type alkali-soluble polymer, the alkali-soluble For the sum of macromolecules,
  • the ratio of the first alkali-soluble polymer (polymer 1) is X1
  • the ratio of the second alkali-soluble polymer (polymer 2) is X2,
  • (b1) (X1 ⁇ b1-1)+(X2 ⁇ b1-2)+..+(XN ⁇ b1-N)
  • (c1) (X1 ⁇ c1-1)+(X2 ⁇ c1-2)+..+(XN ⁇ c1-N) a1-1: mass ratio of component (a) in
  • the ratio ((a1)/(b1)) of the alkali-soluble polymer as a whole may be within the above ratio range, and the ratio of the alkali-soluble polymer alone may not be within the above ratio range.
  • the relationship between the mass average of the mass ratio (a1) and the mass average of the mass ratio (b1) (mass average of the mass ratio (a1) / mass average of the mass ratio (b1)) is 1 /10 to 10 is preferable from the viewpoint that the effect of the present embodiment can be easily exhibited.
  • At least one of the alkali-soluble polymers contained in component (A) has structural units derived from (a) to (b) acid comonomer components and (c) comonomer components, and ratio can be met. That is, when the component (A) is composed of a single alkali-soluble polymer, the alkali-soluble polymer, and when the component (A) is composed of a plurality of alkali-soluble polymers, a plurality of them At least one of the alkali-soluble polymers alone can satisfy the essential requirements required as the component (A) of the present invention.
  • the photosensitive resin composition has constitutional units derived from components (a) to (c) among the alkali-soluble polymers contained in component (A), and the alkali-soluble It is preferable that the proportion of the polymer is 10% by mass or more. Further, when at least one of the alkali-soluble polymers contained in component (A) satisfies the essential requirements for component (A) of the present invention, among the alkali-soluble polymers contained in component (A), the requirements The ratio of the alkali-soluble polymer that satisfies is preferably 10% by mass or more. The proportion of such alkali-soluble polymer may be 30% by mass or more, 40% by mass or more, or 50% by mass or more. The proportion of such alkali-soluble polymer may be 100% by mass or less, or 60% by mass or less.
  • Component (B) is a compound having an ethylenically unsaturated bond in its structure.
  • Component preferably contains a compound having a bisphenol A structure and/or a hydrogenated bisphenol A structure. According to this, the effects of the present invention can be easily achieved.
  • Compounds having a bisphenol A structure and/or a hydrogenated bisphenol A structure may be contained in an amount of 30% by mass or more, 50% by mass or more, 80% by mass or more, and 90% by mass or more of the total amount of component (B).
  • the content of compounds having a bisphenol A structure and/or a hydrogenated bisphenol A structure may be the highest among the contents of each compound of the other components (B).
  • the component (B) includes a compound having one ethylenically unsaturated bond, a compound having two ethylenically unsaturated bonds, a compound having three ethylenically unsaturated bonds, and four ethylenically unsaturated bonds. and compounds having 5 or more ethylenically unsaturated bonds. Different types of these compounds may be used in combination.
  • the component (B) preferably contains 30% by mass or more, 50% by mass or more, 80% by mass or more, 90% by mass or more of a compound having two or more ethylenically unsaturated bonds. According to this, it becomes easy to show the effect by this embodiment.
  • component (B) for example, a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds may be used in combination. Compounds different from each other may be used in combination. Examples of compounds having 3 or more ethylenically unsaturated bonds include compounds having 4 ethylenically unsaturated bonds, 5 ethylenically unsaturated bonds, or 6 ethylenically unsaturated bonds. . Among them, component (B) preferably contains a compound having 3 or more ethylenically unsaturated bonds in one molecule, and a compound having 4 or more ethylenically unsaturated bonds in one molecule. It is also preferred to include
  • the types of compounds that may be contained in component (B) include: dimethacrylate of polyethylene glycol obtained by adding an average of 5 moles of EO (ethylene oxide) to each end of bisphenol A; Hexamethacrylate obtained by adding an average of 13 mol of EO (ethylene oxide) to dipentaerythritol, dimethacrylate of polyethylene glycol obtained by adding an average of 1 mol of EO (ethylene oxide) to each end of bisphenol A; EO (ethylene oxide) modified hydrogenated bisphenol A dimethacrylate, polytetramethylene glycol dimethacrylate, Tetramethacrylate obtained by adding an average of 15 mol of EO (ethylene oxide) to pentaerythritol, poly(propylene glycol) dimethacrylate, EO (ethylene oxide)-modified bisphenol A dimethacrylate, and trimethacrylate obtained by adding an average of 9 mol of EO (ethylene oxide)
  • the content of component (B) in the photosensitive resin composition is preferably 5-70% by mass, more preferably 20-60% by mass, still more preferably 30-50% by mass.
  • the content of component (B) is preferably at least the above lower limit from the viewpoint of suppressing poor curing of the photosensitive resin layer and delay in development time. Moreover, it is preferable that it is below said upper limit from a viewpoint of improving the removability of the cured photosensitive resin layer.
  • Component (C) is a compound capable of generating radicals upon exposure to actinic rays, thereby initiating polymerization of component (B).
  • component (C) examples include hexaarylbiimidazole compounds, N-aryl- ⁇ -amino acid compounds, quinone compounds, aromatic ketone compounds, anthracene derivatives, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, and benzoin ether compounds. , dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-arylamino acid ester compounds, and halogen compounds.
  • hexaarylbiimidazole compounds include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole (alias: 2,2′-bis(2-chlorophenyl)-4,4′,5,5′- tetraphenyl-1,2'-biimidazole), 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2, 4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl) -bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl
  • lophine dimers that is, dimers of 2,4,5-triarylimidazole, for example, 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.
  • 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferable from the viewpoint of high sensitivity, resolution and adhesion.
  • N-aryl- ⁇ -amino acid compounds examples include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. Among them, N-phenylglycine is preferable because of its high sensitizing effect.
  • quinone compounds examples include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloro anthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone, etc. be done.
  • aromatic ketone compounds examples include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4-methoxy-4'-dimethylaminobenzophenone, and the like.
  • the aromatic ketone compound also includes 4,4'-bis(diethylamino)benzophenone from the viewpoint of sensitizing effect and adhesion.
  • anthracene derivative includes both anthracene and compounds derived therefrom.
  • anthracene derivatives include anthracene, 9,10-dialkoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethyl anthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone and the like. From the viewpoint of sensitizing effect and adhesion, 9,10-dibutoxyanthracene and 9,10-diphenylanthracene are preferred, and 9,10-diphenylanthracene is particularly preferred.
  • 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, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1 and the like.
  • examples of commercially available acetophenone compounds include Irgacure series (Ciba Specialty Chemicals: Irgacure-907, Irgacure-369, Irgacure-379, etc.).
  • acylphosphine oxide compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, bis(2,6-dimethoxybenzoyl)-2 , 4,4-trimethyl-pentylphosphine oxide and the like.
  • Commercially available acylphosphine oxide compounds include, for example, 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, methylbenzoin, ethylbenzoin and the like.
  • dialkyl ketal compounds include benzyl dimethyl ketal and benzyl diethyl ketal.
  • Thioxanthone compounds include, for example, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.
  • dialkylaminobenzoic acid ester compounds 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, and the like.
  • Commercially available oxime ester compounds include, for example, CGI-325, Irgacure-OXE01, and Irgacure-OXE02 (all manufactured by Ciba Specialty Chemicals).
  • the acridine compound is preferably 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine in terms of sensitivity, resolution, availability, etc.
  • 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl -3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline and 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline are preferred .
  • Ester compounds of N-arylamino acids include, for example, methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, and N-phenylglycine.
  • Halogen compounds include, for example, 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, diallyliodonium compounds, and the like. be done. Among them, tribromomethylphenylsulfone is preferred.
  • the content of component (C) in the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.5 to 10% by mass.
  • the component (C) contains a lophine dimer.
  • the content of the lophine dimer in the photosensitive resin composition is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass.
  • component (C) it is preferable to use an anthracene derivative and a hexaarylbiimidazole compound in combination.
  • the content of component (C) (eg, anthracene derivative) in the photosensitive resin composition is preferably 0.5% by mass or less, and is 0.01% by mass to 0.4% by mass.
  • the content of the hexaarylbiimidazole compound in the photosensitive resin composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.
  • component (D) component: leuco dye The component (D) can be blended in the photosensitive resin composition of the present embodiment in order to impart color developability to unexposed areas and excellent peeling properties.
  • Component (D) includes, for example, leuco crystal violet (tris[4-(dimethylamino)phenyl]methane), 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, and the like. Among them, leuco crystal violet is preferred.
  • the content of component (D) in the photosensitive resin composition is preferably 0.01 to 2% by mass, more preferably 0.1 to 1.0% by mass, based on the total mass of the solid content of the photosensitive resin composition. More preferably, it is 5% by mass.
  • the photosensitive resin composition may optionally contain base dyes (dyes other than component (D)), antioxidants, stabilizers, sensitizers, plasticizers, and the like.
  • base dyes dye other than component (D)
  • antioxidants antioxidants, stabilizers, sensitizers, plasticizers, and the like.
  • Other components are components other than the above (A) to (D).
  • base dyes examples include Basic Green 1 [CAS number (hereinafter the same): 633-03-4] (for example, Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Industry), 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] (for example, Aizen Victoria Pure Blue BOH, trade name, manufactured by Hodogaya Chemical Industry), Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], Basic Yellow 2 [2465-27-2], and the like.
  • Basic Green 1 is preferable from the viewpoint of improving colorability, hue stability, and exposure contrast. These can be used individually by 1 type or in combination of 2 or more types.
  • the content of the base dye in the photosensitive resin composition is preferably 0.001 to 3% by mass, more preferably 0.01 to 2% by mass, and still more preferably 0.04 to 1% by mass. .
  • the content of the base dye is preferably at least the above lower limit from the viewpoint of obtaining good coloring properties, and on the other hand, from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, it is preferably at most the above upper limit. preferable.
  • Antioxidants include, for example, triphenyl phosphite (for example, manufactured by ADEKA, trade name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (for example, manufactured by ADEKA, trade name 2112 ), tris(monononylphenyl) phosphite (eg, ADEKA, trade name: 1178), bis(monononylphenyl)-dinonylphenyl phosphite (eg, ADEKA, trade name: 329K), and the like. . These can be used individually by 1 type or in combination of 2 or more types.
  • the content of the antioxidant in the photosensitive resin composition is preferably 0.01-0.8% by mass, more preferably 0.01-0.3% by mass.
  • the content of the antioxidant is preferably at least the above lower limit, from the viewpoint of exhibiting good hue stability of the resist pattern and improving the sensitivity of the photosensitive resin layer. On the other hand, from the viewpoint of exhibiting good hue stability while suppressing the color development of the resist pattern and improving adhesion, it is preferably not more than the above upper limit.
  • the stabilizer can be used from the viewpoint of improving the thermal stability and/or storage stability of the photosensitive resin composition.
  • examples of the stabilizer include at least one of a radical polymerization inhibitor and an alkylene oxide compound having a glycidyl group. These can be used individually by 1 type or in combination of 2 or more types.
  • radical polymerization inhibitors examples include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, 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 to which 3 mol of nitrosophenylhydroxylamine is added), diphenylnitrosamine, and the like.
  • triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate] or an aluminum salt to which 3 mol of nitrosophenylhydroxylamine is added is preferable.
  • These can be used individually by 1 type or in combination of 2 or more types.
  • alkylene oxide compound having a glycidyl group examples include neopentyl glycol diglycidyl ether (e.g. Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (e.g. Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), Bisphenol A-propylene oxide 2 mol adduct diglycidyl ether (eg Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), 1,6-hexanediol diglycidyl ether (eg Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.), etc. . These can be used individually by 1 type or in combination of 2 or more types.
  • neopentyl glycol diglycidyl ether e.g. Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.
  • the total content of the radical polymerization inhibitor and the alkylene oxide compound having a glycidyl group in the photosensitive resin composition is preferably 0.001 to 3% by mass, more preferably 0.05 to 1% by mass. is.
  • the total content is preferably at least the above lower limit from the viewpoint of imparting good storage stability to the photosensitive resin composition, and on the other hand, from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, the above upper limit is preferably less than or equal to
  • a photosensitive resin composition preparation liquid By adding a solvent to the photosensitive resin composition, a photosensitive resin composition preparation liquid can be prepared.
  • Suitable solvents include, for example, ketones such as acetone and methyl ethyl ketone (MEK); alcohols such as methanol, ethanol, and isopropyl alcohol. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition prepared liquid is 500 to 4000 mPa ⁇ sec at 25°C.
  • a photosensitive resin layer and, in turn, a photosensitive resin laminate can be obtained using a photosensitive resin composition or a photosensitive resin composition preparation.
  • a photosensitive resin laminate has, for example, a support (support film) and a photosensitive resin layer laminated on the support. If necessary, the photosensitive resin laminate may have a protective film on the side opposite to the support.
  • the photosensitive resin laminate is preferably a dry film resist or a transfer film, more preferably a dry film resist, from the viewpoint that the effect of the present invention can be remarkably exhibited.
  • the support is desirably transparent through which the light emitted from the exposure light source is transmitted.
  • a support is preferably a plastic film, and specific examples include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, and vinylidene chloride copolymer film. film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film and the like. These films may be stretched if necessary.
  • the haze of the support is preferably 5 or less.
  • the thickness of the support is preferably 10 to 30 ⁇ m in consideration of the function of maintaining the strength, although a thinner support is advantageous in terms of image formation and economic efficiency.
  • the photosensitive resin layer described above can contain or consist of a photosensitive resin composition.
  • the film thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 3 to 100 ⁇ m, more preferably 10 to 50 ⁇ m, still more preferably 15 to 50 ⁇ m. As the thickness of the photosensitive resin layer approaches 3 ⁇ m, the resolution improves, and as the thickness approaches 100 ⁇ m, the film strength improves.
  • An important property of the protective film used for the photosensitive resin laminate is to have appropriate adhesion.
  • the adhesive strength of the protective film to the photosensitive resin layer is sufficiently lower than the adhesive strength of the support to the photosensitive resin layer so that the protective film can be easily peeled off from the photosensitive resin laminate.
  • protective films that can be used include polyethylene films, polypropylene films, polyethylene terephthalate films, and polyester films.
  • the thickness of the protective film is preferably 10-100 ⁇ m, more preferably 10-50 ⁇ m.
  • a release layer can be applied to the surface of the protective film so that the protective film can be suitably peeled off from the photosensitive resin layer.
  • Release layers are classified into, for example, silicone compounds and non-silicone compounds.
  • silicone compound for example, a condensation reaction type silicone resin obtained by reacting both end-silanol polydimethylsiloxane with polymethylhydrogensiloxane or polymethylmethoxysiloxane; dimethylsiloxane/methylvinylsiloxane copolymer or dimethylsiloxane/methylhexenyl addition reaction type silicone resin obtained by reacting a siloxane copolymer with polymethylhydrogensiloxane; UV-curable or electron beam-curable silicone resin obtained by curing acrylic silicone, epoxy group-containing silicone, etc.
  • Epoxy-modified silicone resin silicone epoxy
  • polyester-modified silicone resin silicone polyester
  • acrylic-modified silicone resin silicone acryl
  • phenol-modified silicone resin silicone phenol
  • alkyd-modified silicone resin silicone alkyd
  • melamine-modified silicone resin modified silicone resins such as silicone melamine
  • non-silicone compounds examples include alkyd (or alkyd) resins, long-chain alkyl resins, acrylic resins, and polyolefin resins.
  • the film thickness of the release layer is preferably 0.001 to 2 ⁇ m, more preferably 0.005 to 1 ⁇ m, still more preferably 0.01 to 0.5 ⁇ m.
  • the film thickness is equal to or less than the above upper limit, the appearance of the coating film tends to be good, and the coating film can be sufficiently cured.
  • the film thickness is equal to or greater than the above lower limit, it becomes easier to ensure sufficient releasability.
  • a photosensitive resin laminate can be produced by sequentially laminating a photosensitive resin layer and, if necessary, a protective film on a support.
  • a photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent for dissolving them to produce a photosensitive resin composition preparation liquid (coating liquid).
  • the coating solution is applied to the support using a bar coater or roll coater and dried to laminate a photosensitive resin layer on the support.
  • a photosensitive resin laminate can be produced by laminating a protective film on the photosensitive resin layer.
  • the method for forming a resist pattern using the photosensitive resin laminate includes the following steps: Laminating a photosensitive resin laminate on a substrate; A step of exposing the photosensitive resin layer of the laminated photosensitive resin laminate; and a developing step of developing the exposed photosensitive resin layer; , preferably in that order.
  • the lamination process when the photosensitive resin laminate has a protective film, after peeling the protective film from the photosensitive resin laminate, the photosensitive resin layer is heat-pressed onto the substrate surface with a laminator, Laminate once or multiple times.
  • substrate materials include copper, stainless steel (SUS), glass, and indium tin oxide (ITO).
  • the heating temperature during lamination is generally 40 to 160°C.
  • the thermocompression bonding can be performed by using a laminator equipped with rolls or by repeatedly passing the laminate of the substrate and the photosensitive resin layer through rolls several times. Thermocompression bonding can be performed under a reduced pressure environment, if desired.
  • the photosensitive resin layer is exposed to actinic light using an exposure machine. Exposure can be carried out after peeling off the support, if desired. When exposed through a photomask, the amount of exposure is determined by the illuminance of the light source and the exposure time, and may be measured using a photometer. Direct imaging exposure may be performed in the exposure step. In direct imaging exposure, the substrate is directly exposed by a drawing device without using a photomask. As a light source, a semiconductor laser with a wavelength of 350 to 410 nm or an ultra-high pressure mercury lamp is used. When 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 a projection exposure method, a proximity exposure method, a contact exposure method, a direct imaging exposure method, and an electron beam direct drawing method. Alternatively, it is more preferable to carry out by a direct imaging exposure method.
  • the non-exposed area (non-pattern area) of the photosensitive resin layer is dissolved in a developer and removed.
  • the developer contains an alkaline aqueous solution.
  • a resist pattern is obtained by removing an unexposed portion in the development step.
  • a positive photosensitive resin composition is used, a resist pattern is obtained by removing the exposed area.
  • the alkaline aqueous solution it is preferable to use an inorganic alkaline aqueous solution such as Na 2 CO 3 or K 2 CO 3 .
  • the alkaline aqueous solution can be selected according to the properties of the photosensitive resin layer, and is preferably an aqueous Na 2 CO 3 solution with a concentration of 0.2 to 2% by mass.
  • a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like can be mixed in the alkaline aqueous solution.
  • the temperature of the developer in the developing process is preferably kept constant within the range of 18 to 40.degree.
  • a heating step of heating the obtained resist pattern at 100 to 300° C. can be performed. By performing the heating step, it becomes easier to improve the chemical resistance and resolution of the resist pattern.
  • the heating here can be performed using a method such as hot air, infrared rays, or far infrared rays.
  • a wiring pattern corresponding to the resist pattern can be formed on the substrate by forming a resist pattern by the method of forming a resist pattern described above, then performing plating if necessary, and then etching the substrate. .
  • a method of spraying an etchant from above the resist pattern can be adopted.
  • the etching method includes acid etching, alkali etching, and the like.
  • the etchant include aqueous hydrochloric acid, aqueous ferric chloride, and mixtures thereof.
  • Plating can be performed by metal plating (for example, metal plating with a copper sulfate plating solution) or solder plating on the exposed portion by development according to a known plating method.
  • metal plating for example, metal plating with a copper sulfate plating solution
  • solder plating on the exposed portion by development according to a known plating method.
  • the resist pattern can be removed with an aqueous solution (stripping solution) having stronger alkalinity than the developing solution after the plating process when plating is performed, or after the etching process when plating is omitted.
  • the stripping solution is preferably, for example, an aqueous solution of NaOH or KOH or an aqueous solution of an organic amine compound having a concentration of about 2 to 5% by mass and a temperature of about 40°C to 70°C.
  • Substrate surface preparation> The surface of the copper-clad laminate substrate was subjected to surface treatment using a polishing machine and washing with a 10% by mass H 2 SO 4 aqueous solution in order to smooth the surface. A copper clad laminate (substrate) having a thickness of 0.4 mm was obtained on which the copper foil was laminated.
  • Preparation of substrate for evaluation> laminate While peeling off the polyethylene film (protective film) of the photosensitive resin laminate, using a hot roll laminator (Asahi Kasei Electronics Co., Ltd., AL-700), the substrate was preheated to 50 ° C. after leveling as described above. The flexible resin laminate was laminated at a roll temperature of 105°C. Thus, an evaluation substrate was obtained. The air pressure was 0.35 MPa and the lamination speed was 1.5 m/min.
  • Examples 1 to 18 and Comparative Examples 1 to 10 are evaluated using a predetermined drawing pattern for direct imaging (DI) exposure using a direct drawing exposure machine (Oak Manufacturing FDi-3, dominant wavelength 400 nm).
  • the substrate was exposed.
  • Examples 19 and 20 were exposed to i-line monochromatic light using a predetermined mask pattern by a segmented projection exposure apparatus (UX2003 SM-MS04 manufactured by Ushio Inc., using an i-line bandpass filter).
  • the substrate for evaluation was heated using a hot roll laminator (AL-700, manufactured by Asahi Kasei Corp.).
  • the roll temperature was 105° C.
  • the air pressure was 0.30 MPa
  • the lamination speed was 1 m/min.
  • Minimum development time Development was carried out by the above method, and the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve was taken as the shortest development time. A shorter minimum development time (unit: seconds) means better developability. The minimum development time was evaluated according to the following criteria. A: 25 seconds or less B: Over 25 seconds and 30 seconds or less C: Over 30 seconds and 40 seconds or less D: Over 40 seconds
  • Adhesion evaluation For this evaluation, the substrate for evaluation was used after 15 minutes had passed since the photosensitive resin laminate was laminated by the method described in ⁇ Lamination> above. Independent line patterns of various sizes were directly written and exposed to the substrate for evaluation. Thereafter, development was performed by the method described in ⁇ Development> above. The obtained pattern was observed with an optical microscope at a magnification of 100 times, and the adhesion was evaluated according to the following criteria. "Normal formation" means that the resist is neither meandering nor chipped.
  • Press flow rating The photosensitive resin laminate was cut into 2.5 cm squares, the cover film (protective film) was peeled off, and then sandwiched in the center of a 10 cm square PET film. . Thereafter, the protrusion width of the photosensitive resin layer was measured in 4 directions (8 points in total), and the average value was obtained. This test was performed twice, and the average value was used as the value of the press flow test, and the press flow was evaluated according to the following criteria. A: 100 ⁇ m or less B: More than 100 ⁇ m and 150 ⁇ m or less C: More than 150 ⁇ m and 200 ⁇ m or less D: More than 200 ⁇ m
  • Peel strength of support (tackiness): For this evaluation, a substrate for evaluation was prepared by laminating a photosensitive resin laminate on one side by the method described in ⁇ Lamination> above, and left for 24 hours at 23° C. and 50% relative humidity. After that, the 1 inch wide support (PET film in this example) was peeled off 180° at a speed of 100 mm / min, and the strength at that time was measured with Tensilon RTM-500 (manufactured by Toyo Seiki). The peel strength was evaluated by A: Peel strength is less than 3.0 gf D: Peel strength is 3.0 gf or more
  • Peel test In this evaluation, the surface of a 1.6 mm thick copper-clad laminate laminated with a 35 ⁇ m rolled copper foil was smoothed by wet buff roll polishing and used as an evaluation substrate. Polishing was performed twice using Scotch-Brite (registered trademark) HD#600 manufactured by 3M Corporation.
  • a hot roll laminator manufactured by Asahi Kasei Co., Ltd., AL-700 was used to roll the substrate for evaluation after surface preparation. Lamination was performed under conditions of a temperature of 105° C., an air pressure of 0.35 MPa, and a lamination speed of 1.5 m/min. Using an evaluation substrate 15 minutes after lamination, a rectangular pattern of 4 cm ⁇ 6 cm was exposed to the evaluation substrate by the method described in ⁇ Exposure> above, and then developed by the method described in ⁇ Development> above. bottom.
  • the obtained evaluation substrate was cut into a size of 4 cm ⁇ 6 cm, immersed in a stripping solution of R-101 (Mitsubishi Gas Chemical Co., Ltd.) at 50 ° C., and the time until the photosensitive resin layer was completely peeled off from the evaluation substrate. was measured, and using this as the peeling time, the peelability was evaluated according to the following criteria.
  • D Peeling time is more than 25 s

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Abstract

The present invention provides a photosensitive resin composition that has various improved characteristics as a result of the types and proportions of at least the acid comonomer components of the comonomer components of an alkali-soluble polymer being controlled.　According to the present invention, a photosensitive resin composition includes the following components: (A) an alkali-soluble polymer; (B) a compound that has an ethylenically unsaturated bond; (C) and a photopolymerization initiator. The (A) component includes structural units derived from at least the following comonomer components: (a) methacrylic acid or acrylic acid; (b) a carboxylic acid that is different from the acid selected as the (a) component; and (c) a compound that has an aromatic structure or an alicyclic structure. The ratio (mass fraction (a1)/mass fraction (b1)) between the mass fraction (a1) of the structural units of the (A) component that are derived from the (a) component and the mass fraction (b1) of the structural units that are derived from the (b) component is 1/10–10.　

Description

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Photosensitive resin composition, photosensitive resin laminate, and method for forming resist pattern
　本発明は、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に関する。 The present invention relates to a photosensitive resin composition, a photosensitive resin laminate, and a method for forming a resist pattern.
　従来、パソコン及び携帯電話等の電子機器に搭載されるプリント配線板は、フォトリソグラフィ法により作製されてきた。フォトリソグラフィ法では、例えば、支持体と、感光性樹脂層と、を有する感光性樹脂積層体が、感光性樹脂層側（支持体とは反対側）から基板に積層される。かかる感光性樹脂層に対して露光及び現像行うことで、基板上にレジストパターンを形成でき、必要によりめっき処理を経た後、基板に対してエッチングを行うことができる。 Conventionally, printed wiring boards mounted on electronic devices such as personal computers and mobile phones have been produced by photolithography. In the photolithography method, for example, a photosensitive resin laminate having a support and a photosensitive resin layer is laminated on a substrate from the photosensitive resin layer side (opposite side to the support). By exposing and developing such a photosensitive resin layer, a resist pattern can be formed on the substrate, and the substrate can be etched after plating if necessary.
　ここで、感光性樹脂層を得るための感光性樹脂組成物について、様々な提案がなされている。例えば、特許文献１には、無機性値（Ｉ値）が所定値以下であるアルカリ可溶性高分子を含む、感光性樹脂組成物が開示されている。この点、疎水性の低い感光性樹脂組成物は、現像液への溶解性に優れる（現像性に優れる）場合がある。 Here, various proposals have been made regarding the photosensitive resin composition for obtaining the photosensitive resin layer. For example, Patent Literature 1 discloses a photosensitive resin composition containing an alkali-soluble polymer having an inorganic value (I value) of a predetermined value or less. In this respect, a photosensitive resin composition having low hydrophobicity may have excellent solubility in a developer (excellent developability).
　また、特許文献２には、カルボキシル基含有樹脂と、α，β－不飽和二重結合及びエポキシ基を有する不飽和化合物と、の付加生成化物であって、その酸価が５０～２００であるアルカリ可溶性高分子を含む、感光性樹脂組成物が開示されている。特許文献２の合成例２において、カルボキシル基含有樹脂は、アクリル酸３６質量部、メタクリル酸４３質量部、及びメタクリル酸メチル１０質量部、等のコモノマー成分から作製されている。 Further, Patent Document 2 discloses an addition product of a carboxyl group-containing resin and an unsaturated compound having an α,β-unsaturated double bond and an epoxy group, and having an acid value of 50 to 200. A photosensitive resin composition is disclosed that includes an alkali-soluble polymer. In Synthesis Example 2 of Patent Document 2, the carboxyl group-containing resin is produced from comonomer components such as 36 parts by mass of acrylic acid, 43 parts by mass of methacrylic acid, and 10 parts by mass of methyl methacrylate.
国際公開第２０１９／２４４７２４号WO2019/244724 特開平８－３３９０８１号公報JP-A-8-339081
　しかしながら、特許文献１及び２の感光性樹脂組成物は、感光性樹脂層の現像性と、得られるレジストパターンの解像性と、を両立する観点で改善の余地があった。すなわち、高解像性のための一つの手法として、感光性樹脂層の疎水性を向上させることが考えられるが、感光性樹脂層の疎水性を向上させると、現像液への溶解性が低下するため、現像時間が長くなる傾向があった。
　また、近年の高解像性への要求から、基板への密着性の向上を図ることができる感光性樹脂層を備える感光性樹脂組成物の提供も待たれていた。 However, the photosensitive resin compositions of Patent Documents 1 and 2 have room for improvement from the viewpoint of achieving both the developability of the photosensitive resin layer and the resolution of the resulting resist pattern. That is, as one method for achieving high resolution, it is conceivable to improve the hydrophobicity of the photosensitive resin layer, but if the hydrophobicity of the photosensitive resin layer is improved, the solubility in the developer decreases. Therefore, development time tended to be long.
In addition, due to the recent demand for high resolution, provision of a photosensitive resin composition having a photosensitive resin layer capable of improving adhesion to a substrate has been awaited.
　本発明は、上記実情に鑑みて提案されたものである。すなわち、本発明の目的は、アルカリ可溶性高分子のコモノマー成分のうち、少なくとも酸コモノマー成分についてその種類及び比率を制御して各種特性の向上を図ることができる、感光性樹脂組成物を提供することにある。また、本発明の目的は、かかる感光性樹脂組成物から得られる感光性樹脂層を備える感光性樹脂積層体、及びそれを用いて実現される、レジストパターンの形成方法、を提供することである。 The present invention has been proposed in view of the above circumstances. That is, an object of the present invention is to provide a photosensitive resin composition capable of improving various properties by controlling the type and ratio of at least the acid comonomer component among the comonomer components of the alkali-soluble polymer. It is in. Another object of the present invention is to provide a photosensitive resin laminate comprising a photosensitive resin layer obtained from such a photosensitive resin composition, and a method for forming a resist pattern realized using the same. .
［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）成分が、少なくとも、下記のコモノマー成分：
　（ａ）メタクリル酸又はアクリル酸、
　（ｂ）前記（ａ）成分として選択された酸とは異なるカルボン酸、及び
　（ｃ）芳香族構造又は脂環式構造を有する化合物、
に由来する構成単位を有し、
　前記（Ａ）成分における、
　前記（ａ）成分に由来する構成単位の質量割合（ａ１）と、
　前記（ｂ）成分に由来する構成単位の質量割合（ｂ１）と、
の比率（前記質量割合（ａ１）／前記質量割合（ｂ１））が、１／１０～１０である、感光性樹脂組成物。
［２］
　前記比率（前記質量割合（ａ１）／前記質量割合（ｂ１））が、１／８～８である、項目１に記載の感光性樹脂組成物。
［３］
　前記（Ａ）成分は、コモノマー成分として、（ｄ）ヒドロキシアルキル（メタ）アクリル酸エステルに由来する構成単位、を更に有する、項目１又は２に記載の感光性樹脂組成物。
［４］
　前記（ｄ）成分は、ヒドロキシエチルメタクリレートである、項目３に記載の感光性樹脂組成物。
［５］
　前記（ａ）成分は、メタクリル酸である、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（ｂ）成分は、アクリル酸である、項目１～５のいずれか１項に記載の感光性樹脂組成物。
［７］
　前記（Ａ）成分における、
　前記（ａ）成分に由来する構成単位の質量割合（ａ１）と、
　前記（ｂ）成分に由来する構成単位の質量割合（ｂ１）と、の合計は、１～６５質量％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（ｃ）成分は、スチレン及び／又はベンジル（メタ）アクリレートを含む、項目１～７のいずれか１項に記載の感光性樹脂組成物。
［９］
　前記（Ａ）成分における、前記（ｃ）成分に由来する構成単位の割合は、１０～９５質量％である、項目１～８のいずれか１項に記載の感光性樹脂組成物。
［１０］
　前記（ｃ）成分は、スチレンを含む、項目８に記載の感光性樹脂組成物。
［１１］
　前記（Ａ）成分における、前記スチレンに由来する構成単位の割合が４５～９５質量％である、項目１０に記載の感光性樹脂組成物。
［１２］
　前記感光性樹脂組成物の固形分総量を基準として、
　前記（Ａ）成分：１０～９０質量％、
　前記（Ｂ）成分：５～７０質量％、及び
　前記（Ｃ）成分：０．０１～２０質量％、
　を含む、項目１～１１のいずれか１項に記載の感光性樹脂組成物。
［１３］
　前記（Ａ）成分は、複数のアルカリ可溶性高分子を含む、項目１～１２のいずれか１項に記載の感光性樹脂組成物。
［１４］
　前記質量割合（ａ１）の質量平均と、前記質量割合（ｂ１）の質量平均と、の関係（質量割合（ａ１）の質量平均／質量割合（ｂ１）の質量平均）が、１／１０～１０である、項目１３に記載の感光性樹脂組成物。
［１５］
　前記（Ａ）成分に含まれるアルカリ可溶性高分子の少なくとも一つは、
　前記（ａ）成分～（ｃ）成分に由来する構成単位を有し、かつ、前記比率を満たす、項目１３又は１４に記載の感光性樹脂組成物。
［１６］
　前記（Ａ）成分に含まれるアルカリ可溶性高分子のうち、
　前記（ａ）成分～（ｃ）成分に由来する構成単位を有し、かつ、
　前記比率を満たすアルカリ可溶性高分子の割合は１０質量％以上である、項目１３～１５のいずれか１項に記載の感光性樹脂組成物。
［１７］
　前記（Ａ）成分の酸価が、５０～６００ｍｇＫＯＨ／ｇである、項目１～１６のいずれか１項に記載の感光性樹脂組成物。
［１８］
　前記（Ｂ）成分は、ビスフェノールＡ構造、及び／又は水添ビスフェノールＡ構造を有する化合物を含む、項目１～１７のいずれか１項に記載の感光性樹脂組成物。
［１９］
　前記（Ｂ）成分は、一分子中に、前記エチレン性不飽和結合を３つ以上有する化合物を含む、項目１～１８のいずれか１項に記載の感光性樹脂組成物。
［２０］
　前記（Ｃ）成分は、ヘキサアリールビイミダゾール（ＨＡＢＩ）化合物を含む、項目１～１９のいずれか１項に記載の感光性樹脂組成物。
［２１］
　（Ｄ）成分として、ロイコ染料を更に含む、項目１～２０のいずれか１項に記載の感光性樹脂組成物。
［２２］
　前記（Ａ）成分における、
　前記（ａ）成分に由来する構成単位の質量割合（ａ１）と、
　前記（ｂ）成分に由来する構成単位の質量割合（ｂ１）と、
　前記（ｃ）成分に由来する構成単位の質量割合（ｃ１）と、が下記式（１）～（３）：
　　１０≦（ａ１）＋（ｂ１）≦５０　・・・　（１）
　　０．５≦（ａ１）／（ｂ１）≦８．０　・・・　（２）
　　３０≦（ｃ１）≦８０　・・・　（３）
を満たす、項目１～２１のいずれか１項に記載の感光性樹脂組成物。
［２３］
　前記（Ａ）成分は、複数のアルカリ可溶性高分子を含み、
　前記（Ａ）成分に含まれるアルカリ可溶性高分子の少なくとも一つは、前記（ａ）成分～（ｃ）成分に由来する構成単位を有し、かつ、
　前記質量割合（ａ１）、（ｂ１）、及び（ｃ１）が、前記式（１）～（３）を満たす、項目２２に記載の感光性樹脂組成物。
［２４］
　前記（Ａ）成分に含まれるアルカリ可溶性高分子のうち、
　前記（ａ）成分～（ｃ）成分に由来する構成単位を有し、かつ、前記質量割合（ａ１）、（ｂ１）、及び（ｃ１）が前記式（１）～（３）を満たすアルカリ可溶性高分子の割合は、１０質量％以上である、項目２３に記載の感光性樹脂組成物。
［２５］
　支持体と、項目１～２４のいずれか１項に記載の感光性樹脂組成物から得られる感光性樹脂層と、を備える、感光性樹脂積層体。
［２６］
　前記感光性樹脂層の、前記支持体とは反対側に、保護フィルムを備える、項目２５に記載の感光性樹脂積層体。
［２７］
　項目２５又は２６に記載の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の感光性樹脂層を露光する工程、及び
　露光した前記感光性樹脂層を現像する工程、
　を有する、レジストパターン形成方法。
［２８］
　前記露光を、ダイレクトイメージング露光によって行う、項目２７に記載のレジストパターン形成方法。 [1]
Ingredients for:
(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) contains at least the following comonomer components:
(a) methacrylic acid or acrylic acid,
(b) a carboxylic acid different from the acid selected as component (a); and (c) a compound having an aromatic or alicyclic structure,
has a structural unit derived from
In the component (A),
The mass ratio (a1) of structural units derived from the component (a);
a mass ratio (b1) of structural units derived from the component (b);
ratio (the mass ratio (a1)/the mass ratio (b1)) is 1/10 to 10, a photosensitive resin composition.
[2]
The photosensitive resin composition according to item 1, wherein the ratio (mass ratio (a1)/mass ratio (b1)) is 1/8 to 8.
[3]
3. The photosensitive resin composition according to item 1 or 2, wherein the component (A) further has (d) a structural unit derived from a hydroxyalkyl (meth)acrylate ester as a comonomer component.
[4]
The photosensitive resin composition according to item 3, wherein the component (d) is hydroxyethyl methacrylate.
[5]
5. The photosensitive resin composition according to any one of items 1 to 4, wherein the component (a) is methacrylic acid.
[6]
The photosensitive resin composition according to any one of items 1 to 5, wherein the component (b) is acrylic acid.
[7]
In the component (A),
The mass ratio (a1) of structural units derived from the component (a);
The photosensitive resin composition according to any one of items 1 to 6, wherein the total mass ratio (b1) of the constituent units derived from component (b) is 1 to 65% by mass.
[8]
The photosensitive resin composition according to any one of items 1 to 7, wherein the component (c) contains styrene and/or benzyl (meth)acrylate.
[9]
9. The photosensitive resin composition according to any one of items 1 to 8, wherein the proportion of structural units derived from component (c) in component (A) is 10 to 95% by mass.
[10]
9. The photosensitive resin composition according to Item 8, wherein the component (c) contains styrene.
[11]
11. The photosensitive resin composition according to item 10, wherein the ratio of the styrene-derived structural unit in the component (A) is 45 to 95% by mass.
[12]
Based on the total solid content of the photosensitive resin composition,
Component (A): 10 to 90% by mass,
The (B) component: 5 to 70% by mass, and the (C) component: 0.01 to 20% by mass,
The photosensitive resin composition according to any one of items 1 to 11, comprising:
[13]
13. The photosensitive resin composition according to any one of items 1 to 12, wherein the component (A) contains a plurality of alkali-soluble polymers.
[14]
The relationship between the mass average of the mass ratio (a1) and the mass average of the mass ratio (b1) (mass average of mass ratio (a1) / mass average of mass ratio (b1)) is 1/10 to 10 14. The photosensitive resin composition according to item 13.
[15]
At least one of the alkali-soluble polymers contained in the component (A),
15. The photosensitive resin composition according to item 13 or 14, which has structural units derived from the components (a) to (c) and satisfies the above ratio.
[16]
Among the alkali-soluble polymers contained in the component (A),
Having structural units derived from the components (a) to (c), and
16. The photosensitive resin composition according to any one of items 13 to 15, wherein the ratio of the alkali-soluble polymer satisfying the ratio is 10% by mass or more.
[17]
17. The photosensitive resin composition according to any one of items 1 to 16, wherein the component (A) has an acid value of 50 to 600 mgKOH/g.
[18]
18. The photosensitive resin composition according to any one of items 1 to 17, wherein the component (B) contains a compound having a bisphenol A structure and/or a hydrogenated bisphenol A structure.
[19]
The photosensitive resin composition according to any one of items 1 to 18, wherein the component (B) contains a compound having three or more ethylenically unsaturated bonds in one molecule.
[20]
20. The photosensitive resin composition according to any one of items 1 to 19, wherein the component (C) contains a hexaarylbiimidazole (HABI) compound.
[21]
21. The photosensitive resin composition according to any one of items 1 to 20, further comprising a leuco dye as component (D).
[22]
In the component (A),
The mass ratio (a1) of structural units derived from the component (a);
a mass ratio (b1) of structural units derived from the component (b);
The mass ratio (c1) of the structural unit derived from the component (c) is represented by the following formulas (1) to (3):
10≦(a1)+(b1)≦50 (1)
0.5≦(a1)/(b1)≦8.0 (2)
30≦(c1)≦80 (3)
The photosensitive resin composition according to any one of items 1 to 21, which satisfies
[23]
The component (A) contains a plurality of alkali-soluble polymers,
At least one of the alkali-soluble polymers contained in component (A) has structural units derived from components (a) to (c), and
23. The photosensitive resin composition according to item 22, wherein the mass ratios (a1), (b1), and (c1) satisfy the formulas (1) to (3).
[24]
Among the alkali-soluble polymers contained in the component (A),
Alkali-soluble having structural units derived from the components (a) to (c), and wherein the mass ratios (a1), (b1), and (c1) satisfy the formulas (1) to (3) 24. The photosensitive resin composition according to item 23, wherein the proportion of the polymer is 10% by mass or more.
[25]
A photosensitive resin laminate comprising a support and a photosensitive resin layer obtained from the photosensitive resin composition according to any one of items 1 to 24.
[26]
26. The photosensitive resin laminate according to item 25, comprising a protective film on the side of the photosensitive resin layer opposite to the support.
[27]
A step of laminating the photosensitive resin laminate according to item 25 or 26 on a substrate;
a step of exposing the photosensitive resin layer of the laminated photosensitive resin laminate, and a step of developing the exposed photosensitive resin layer,
A method of forming a resist pattern, comprising:
[28]
28. The method of forming a resist pattern according to Item 27, wherein the exposure is performed by direct imaging exposure.
　本発明に係る感光性樹脂組成物によれば、アルカリ可溶性高分子のコモノマー成分のうち、少なくとも酸コモノマー成分についてその種類及び比率を制御して、感光性樹脂層の現像性の向上を図ることができる。加えて、本発明に係る感光性樹脂組成物によれば、感光性樹脂層の基板への密着性、及びレジストパターンの解像性の向上も図ることができる。また、本発明によれば、かかる感光性樹脂組成物から得られる感光性樹脂層を備える感光性樹脂積層体、及びそれを用いて実現される、レジストパターンの形成方法を提供することができる。 According to the photosensitive resin composition of the present invention, it is possible to improve the developability of the photosensitive resin layer by controlling the type and ratio of at least the acid comonomer component among the comonomer components of the alkali-soluble polymer. can. In addition, according to the photosensitive resin composition of the present invention, it is possible to improve the adhesion of the photosensitive resin layer to the substrate and the resolution of the resist pattern. Further, according to the present invention, it is possible to provide a photosensitive resin laminate including a photosensitive resin layer obtained from such a photosensitive resin composition, and a method for forming a resist pattern realized using the same.
　以下、本発明の実施形態（以下、「本実施形態」と略記する。）を説明する。ただし、本発明は、本実施形態に限定されず、その要旨の範囲内で種々変形して実施することができる。本実施形態において、「～」を用いて記載した数値範囲は、「～」の前後に記載された数値をその範囲内に含む。また、本実施形態において、段階的に記載されている数値範囲では、ある数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えることができる。更に、本実施形態において、ある数値範囲で記載された上限値又は下限値は、実施例に示された値に置き換えることもできる。 An embodiment of the present invention (hereinafter abbreviated as "this embodiment") will be described below. However, the present invention is not limited to this embodiment, and various modifications can be made within the scope of the gist of the present invention. In the present embodiment, the numerical range described using "-" includes the numerical values described before and after "-". Further, in the present embodiment, in the numerical ranges described in stages, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described in stages. can be done. Furthermore, in this embodiment, the upper limit value or lower limit value described in a certain numerical range can be replaced with the values shown in the examples.
　本明細書において、「（メタ）アクリル」は、アクリル又はメタクリルを意味し、「（メタ）アクリロイル」は、アクリロイル又はメタクリロイルを意味し、「（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。 As used herein, "(meth)acrylic" means acrylic or methacrylic, "(meth)acryloyl" means acryloyl or methacryloyl, and "(meth)acrylate" means acrylate or methacrylate.
　［感光性樹脂組成物］
　〔概略構成〕
　本実施形態に係る感光性樹脂組成物は、
　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。本明細書では、上記（Ａ）～（Ｃ）を、単に「（Ａ）成分」～「（Ｃ）成分」とも称する。 [Photosensitive resin composition]
[Outline configuration]
The photosensitive resin composition according to this embodiment is
Ingredients for:
(A) an alkali-soluble polymer,
(B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator,
including. In this specification, the above (A) to (C) are also simply referred to as "(A) component" to "(C) component".
　そして、（Ａ）成分が、少なくとも、下記のコモノマー成分：
　（ａ）メタクリル酸又はアクリル酸、
　（ｂ）上記（ａ）成分として選択された酸とは異なるカルボン酸、及び
　（ｃ）芳香族構造又は脂環式構造を有する化合物
に由来する構成単位を有する。本明細書では、上記（ａ）及び（ｂ）を、単に「（ａ）酸コモノマー成分」及び「（ｂ）酸コモノマー成分」とも称し、上記（ｃ）を、単に「（ｃ）コモノマー成分」とも称する。 And the (A) component is at least the following comonomer component:
(a) methacrylic acid or acrylic acid,
(b) a carboxylic acid different from the acid selected as component (a) above; and (c) a structural unit derived from a compound having an aromatic structure or an alicyclic structure. In this specification, (a) and (b) are also referred to simply as "(a) acid comonomer component" and "(b) acid comonomer component", and (c) is referred to simply as "(c) comonomer component". Also called
　ここで、（Ａ）成分における、
　（ａ）酸コモノマー成分に由来する構成単位の質量割合（ａ１）と、
　（ｂ）酸コモノマー成分に由来する構成単位の質量割合（ｂ１）と、
の比率（質量割合（ａ１）／質量割合（ｂ１））が、１／１０～１０である。ここで言う「１／１０」は、例えば「０．１」である。 Here, in the component (A),
(a) mass ratio (a1) of structural units derived from the acid comonomer component;
(b) the mass ratio (b1) of structural units derived from the acid comonomer component;
The ratio of (mass ratio (a1)/mass ratio (b1)) is 1/10 to 10. "1/10" here is, for example, "0.1".
　かかる感光性樹脂組成物では、アルカリ可溶性高分子のコモノマー成分として、複数の酸コモノマー成分が併用され、かつ、それら複数の酸コモノマー成分と、他のコモノマー成分と、もまた併用されている。その上で、少なくとも酸コモノマー成分について、その種類及び含有比率が制御されている。 In such a photosensitive resin composition, a plurality of acid comonomer components are used in combination as the comonomer component of the alkali-soluble polymer, and the plurality of acid comonomer components and other comonomer components are also used in combination. In addition, the type and content ratio of at least the acid comonomer component are controlled.
　このような感光性樹脂組成物によれば、各種特性（感光性樹脂層の現像性、感光性樹脂層の基板への密着性、及びレジストパターンの解像性等）の向上を図ることができる。
　本実施形態の好ましい態様の一つにおいて、アルカリ可溶性高分子のコモノマー成分として、複数の酸コモノマー成分を併用し、かつ、それら複数の酸コモノマー成分と、他の芳香族構造又は脂環式構造を有するコモノマー成分と、もまた併用することができる。その上で、本発明者らは、少なくとも酸コモノマー成分について、その種類及び含有比率を制御することが、各種性能の向上につながることを見出し、このような着想に基づいて本実施形態が提案されたものである。また、本実施形態の好ましい態様の一つにおいて、他の芳香族構造又は脂環式構造を有するコモノマー成分について比率を制御することもでき、この場合、各種特性（例えば、感光性樹脂層の基板への密着性、及びレジストパターンの解像性）の向上を図り易い。
　以下、感光性樹脂組成物を構成する各成分について説明する。 According to such a photosensitive resin composition, it is possible to improve various properties (developability of the photosensitive resin layer, adhesion of the photosensitive resin layer to the substrate, resolution of the resist pattern, etc.). .
In one preferred aspect of the present embodiment, as comonomer components of the alkali-soluble polymer, a plurality of acid comonomer components are used in combination, and the plurality of acid comonomer components and other aromatic or alicyclic structures are combined. It can also be used in combination with a comonomer component having. In addition, the present inventors have found that controlling the type and content ratio of at least the acid comonomer component leads to improvement in various performances, and based on such an idea, the present embodiment is proposed. It is a thing. In one preferred aspect of the present embodiment, the ratio of comonomer components having other aromatic or alicyclic structures can also be controlled. It is easy to improve the adhesion to the substrate and the resolution of the resist pattern).
Each component constituting the photosensitive resin composition will be described below.
　〔（Ａ）成分：アルカリ可溶性高分子〕
　（概略構成）
　（Ａ）成分は、アルカリ性溶液に可溶な高分子である。（Ａ）成分は、カルボキシル基を有することが好ましく、また、現像性向上の観点から、５０～６００ｍｇＫＯＨ／ｇの酸価を有することが好ましく、１００～４００ｍｇＫＯＨ／ｇの酸価を有することがより好ましい。（Ａ）成分のかかる酸価は、６０ｍｇＫＯＨ／ｇ以上でよく、８０ｍｇＫＯＨ／ｇ以上でよく、１００ｍｇＫＯＨ／ｇ以上でよく、５００ｍｇＫＯＨ／ｇ以下でよく、４００ｍｇＫＯＨ／ｇ以下でよい。（Ａ）成分は熱可塑性であることができる。
　上記酸価は、（Ａ）成分１ｇを中和するのに必要な水酸化カリウムのミリグラム数を指す。 [(A) component: alkali-soluble polymer]
(Outline configuration)
Component (A) is a polymer soluble in an alkaline solution. Component (A) preferably has a carboxyl group, and from the viewpoint of improving developability, preferably has an acid value of 50 to 600 mgKOH/g, and more preferably has an acid value of 100 to 400 mgKOH/g. preferable. The acid value of component (A) may be 60 mgKOH/g or more, 80 mgKOH/g or more, 100 mgKOH/g or more, 500 mgKOH/g or less, or 400 mgKOH/g or less. The (A) component can be thermoplastic.
The acid value refers to milligrams of potassium hydroxide required to neutralize 1 g of component (A).
　（Ａ）成分の重量平均分子量は、５，０００～５００，０００であることが好ましく、１０，０００～２００，０００であることがより好ましく、２０，０００～１００，０００であることが更に好ましく、２３，０００～７０，０００であることが特に好ましい。（Ａ）成分の重量平均分子量が上記の下限値以上であることで、感光性樹脂積層体の厚みを均一に維持し易くなり、また、露光部の現像液に対する耐性を確保し易くなる。また、（Ａ）成分の重量平均分子量が上記の上限値以下であることで、感光性樹脂積層体の現像性を維持し易くなる。
　また、（Ａ）成分の重量平均分子量（Ｍｗ）と、（Ａ）成分の数平均分子量（Ｍｎ）と、の比である多分散度（Ｍｗ／Ｍｎ）は、１．０～６．０であることが好ましい。
　上記重量平均分子量及び多分散度は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によりポリスチレンの検量線を用いて測定した重量平均分子量及び多分散度を意味する。該重量平均分子量は、例えば、以下の条件で測定することができる。
　（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
　　Ｇｅｌｐａｃｋ　ＧＬ－Ｒ４２０
　　Ｇｅｌｐａｃｋ　ＧＬ－Ｒ４３０
　　Ｇｅｌｐａｃｋ　ＧＬ－Ｒ４４０（以上、日立化成株式会社製、商品名）
　　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：日立　Ｌ－３３００型ＲＩ（株式会社日立製作所製、商品名） The weight average molecular weight of component (A) is preferably from 5,000 to 500,000, more preferably from 10,000 to 200,000, even more preferably from 20,000 to 100,000. , 23,000 to 70,000. When the weight-average molecular weight of component (A) is at least the above lower limit, it becomes easier to maintain a uniform thickness of the photosensitive resin layered body and to ensure the resistance of the exposed portion to the developing solution. Moreover, it becomes easy to maintain the developability of a photosensitive resin laminated body because the weight average molecular weight of (A) component is below said upper limit.
In addition, the polydispersity (Mw/Mn), which is the ratio of the weight average molecular weight (Mw) of component (A) to the number average molecular weight (Mn) of component (A), is 1.0 to 6.0. Preferably.
The weight average molecular weight and polydispersity are measured by gel permeation chromatography (GPC) using a polystyrene calibration curve. The weight average molecular weight can be measured, for example, under the following conditions.
(GPC conditions)
Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd., trade name)
Column: total of 3 Gelpack GL-R420
Gelpack GL-R430
Gelpack GL-R440 (manufactured by Hitachi Chemical Co., Ltd., trade name)
Eluent: Tetrahydrofuran Measurement temperature: 40°C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., trade name)
　感光性樹脂組成物における（Ａ）成分の含有量（感光性樹脂組成物の固形分総量を基準とする。以下、特に明示しない限り、各含有成分において同様である。）は、好ましくは１０～９０質量％であり、より好ましくは２０～８０質量％であり、更に好ましくは３０～６０質量％である。（Ａ）成分の含有量は、感光性樹脂層のアルカリ現像性を維持する観点から、上記下限値以上であることが好ましい。他方、露光によって形成されるレジストパターンがレジスト材料としての性能を十分に発揮する観点から、上記上限値以下であることが好ましい。 The content of component (A) in the photosensitive resin composition (based on the total solid content of the photosensitive resin composition. Hereinafter, unless otherwise specified, the same applies to each component.) is preferably 10 to It is 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 60% by mass. From the viewpoint of maintaining the alkali developability of the photosensitive resin layer, the content of component (A) is preferably at least the above lower limit. On the other hand, from the viewpoint that the resist pattern formed by exposure fully exhibits the performance as a resist material, it is preferably not more than the above upper limit.
　ここで、（Ａ）成分は、少なくとも、下記のコモノマー成分：
　（ａ）メタクリル酸又はアクリル酸、
　（ｂ）上記（ａ）酸コモノマー成分として選択された酸とは異なるカルボン酸、及び
　（ｃ）芳香族構造又は脂環式構造を有する化合物、
を重合することにより得られる。従って、（Ａ）成分は、少なくとも、（ａ）酸コモノマー成分、（ｂ）酸コモノマー成分、及び（ｃ）コモノマー成分、のそれぞれに由来する構成単位を有する。 Here, component (A) is at least the following comonomer components:
(a) methacrylic acid or acrylic acid,
(b) a carboxylic acid different from the acid selected as the (a) acid comonomer component, and (c) a compound having an aromatic or alicyclic structure,
obtained by polymerizing Therefore, component (A) has at least structural units derived from each of (a) acid comonomer component, (b) acid comonomer component, and (c) comonomer component.
　（（ａ）酸コモノマー成分）
　（ａ）酸コモノマー成分は、メタクリル酸又はアクリル酸である。一態様において、「メタクリル酸」は、化学式Ｃ４Ｈ６Ｏ２で表される化合物を指し、「アクリル酸」は、化学式Ｃ３Ｈ４Ｏ２で表される化合物を指す。 ((a) acid comonomer component)
(a) the acid comonomer component is methacrylic acid or acrylic acid; In one aspect, "methacrylic acid" refers to the compound represented by the chemical formula C4H6O2 , and "acrylic acid" refers to the compound represented by the chemical formula C3H4O2 .
　（（ｂ）酸コモノマー成分）
　（ｂ）酸コモノマー成分は、上記（ａ）酸コモノマー成分で選択された酸コモノマー成分とは異なるカルボン酸である。（ａ）酸コモノマー成分がメタクリル酸である場合、（ｂ）酸コモノマー成分は、メタクリル酸とは異なるカルボン酸でよい。また、（ａ）酸コモノマー成分がアクリル酸である場合、（ｂ）酸コモノマー成分は、アクリル酸とは異なるカルボン酸でよい。また、（ａ）酸コモノマー成分の種類に関わらず、（ｂ）酸コモノマー成分は、メタクリル酸及びアクリル酸の、いずれとも異なるカルボン酸でよい。（ｂ）酸コモノマー成分は、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であってよい。（ｂ）酸コモノマー成分は、１種単独でもよく、２種以上を併用してもよい。 ((b) acid comonomer component)
The (b) acid comonomer component is a carboxylic acid different from the acid comonomer component selected for (a) the acid comonomer component above. When the (a) acid comonomer component is methacrylic acid, the (b) acid comonomer component may be a carboxylic acid different from methacrylic acid. Also, when the (a) acid comonomer component is acrylic acid, the (b) acid comonomer component may be a carboxylic acid different from acrylic acid. Also, regardless of the type of the (a) acid comonomer component, the (b) acid comonomer component may be a carboxylic acid different from both methacrylic acid and acrylic acid. (b) The acid comonomer component may be a compound having an ethylenically unsaturated bond and may be a compound having a (meth)acryloyl group. (b) The acid comonomer component may be used alone or in combination of two or more.
　（ｂ）酸コモノマー成分は、例えば、（ａ）酸コモノマー成分がメタクリル酸である場合、アクリル酸であり得て、（ａ）酸コモノマー成分がアクリル酸である場合、メタクリル酸であり得る。
　また、（ｂ）酸コモノマー成分は、例えば、メタクリル酸及びアクリル酸の、いずれとも異なるカルボン酸であり得る。メタクリル酸及びアクリル酸のいずれとも異なるカルボン酸としては、例えば、ケイ皮酸、クロトン酸、コハク酸半エステル、マレイン酸半エステル、フマル酸半エステル、４－ビニル安息香酸、コハク酸、マレイン酸、フマル酸、イタコン酸等が挙げられる。 The (b) acid comonomer component can be, for example, acrylic acid when the (a) acid comonomer component is methacrylic acid, or methacrylic acid when the (a) acid comonomer component is acrylic acid.
Also, the (b) acid comonomer component can be a carboxylic acid different from both methacrylic acid and acrylic acid, for example. Examples of carboxylic acids different from methacrylic acid and acrylic acid include cinnamic acid, crotonic acid, succinic acid half ester, maleic acid half ester, fumaric acid half ester, 4-vinylbenzoic acid, succinic acid, maleic acid, fumaric acid, itaconic acid, and the like.
　ここで、（Ａ）成分における、
　（ａ）酸コモノマー成分に由来する構成単位の質量割合（ａ１）と、
　（ｂ）酸コモノマー成分に由来する構成単位の質量割合（ｂ１）と、
の比率（質量割合（ａ１）／質量割合（ｂ１））が、１／１０～１０（例えば、１０．０）である。 Here, in the component (A),
(a) mass ratio (a1) of structural units derived from the acid comonomer component;
(b) the mass ratio (b1) of structural units derived from the acid comonomer component;
(mass ratio (a1)/mass ratio (b1)) is 1/10 to 10 (eg, 10.0).
　（ａ）酸コモノマー成分及び（ｂ）酸コモノマー成分として選択可能なカルボン酸は、その種類により、感光性樹脂組成物、及び感光性樹脂層の特性に与える影響が異なる。従って、アルカリ可溶性高分子のコモノマー成分のうち、少なくとも酸コモノマー成分について、その種類及び比率を制御することで、感光性樹脂層の各種特性の向上を図ることができる。 The carboxylic acids that can be selected as the (a) acid comonomer component and (b) the acid comonomer component have different effects on the properties of the photosensitive resin composition and the photosensitive resin layer depending on the type. Therefore, by controlling the type and ratio of at least the acid comonomer component among the comonomer components of the alkali-soluble polymer, various properties of the photosensitive resin layer can be improved.
　上記と同様の観点から、比率（質量割合（ａ１）／質量割合（ｂ１））は、１／８～８（例えば８．０）であることが好ましく、１／７～７．０であることがより好ましく、１／５～５．０であることが更に好ましく、１／４．２～４．２であることがより更に好ましい。 From the same viewpoint as above, the ratio (mass ratio (a1)/mass ratio (b1)) is preferably 1/8 to 8 (eg, 8.0), and 1/7 to 7.0. is more preferable, 1/5 to 5.0 is more preferable, and 1/4.2 to 4.2 is even more preferable.
　（ａ）酸コモノマー成分は、メタクリル酸であることが好ましい。これによれば、メタクリル酸による貢献を得て、各種特性に優れた感光性樹脂層を実現し易くなる。 (a) The acid comonomer component is preferably methacrylic acid. According to this, the contribution of methacrylic acid is obtained, and it becomes easy to realize a photosensitive resin layer excellent in various properties.
　ここで、（ａ）酸コモノマー成分はメタクリル酸、及び（ｂ）酸コモノマー成分はアクリル酸であることがより好ましい。メタクリル酸及びアクリル酸のうち、疎水性が比較的高いメタクリル酸による貢献を得ることで、レジストパターンの解像性の向上を図り易くなり、また、ガラス転移温度が比較的低いアクリル酸による貢献を得ることで、現像性向上を図り易くなる。従って、両者の酸による貢献を好適に得ることができ、その結果、各種特性（感光性樹脂層の現像性、及びレジストパターンの解像性等）の向上を図ることができる。 Here, it is more preferable that the (a) acid comonomer component is methacrylic acid and the (b) acid comonomer component is acrylic acid. Among methacrylic acid and acrylic acid, the contribution of methacrylic acid, which is relatively hydrophobic, makes it easier to improve the resolution of the resist pattern, and the contribution of acrylic acid, which has a relatively low glass transition temperature. It becomes easy to aim at the developability improvement by obtaining. Therefore, the contribution of both acids can be preferably obtained, and as a result, various characteristics (developability of the photosensitive resin layer, resolution of the resist pattern, etc.) can be improved.
　例えば、（ａ）成分として使用可能なメタクリル酸に比べて、（ｂ）成分として使用可能なアクリル酸は、そのガラス転移温度（Ｔｇ）が小さい。従って、例えば、メタクリル酸及びアクリル酸の場合に着目したとき、少なくとも酸コモノマー成分について、その種類及び含有比率を制御することで、（Ａ）成分全体としての疎水性を確保しつつ、かつ、解像性向上に有利なようにＴｇを調整することができる。 For example, acrylic acid that can be used as component (b) has a lower glass transition temperature (Tg) than methacrylic acid that can be used as component (a). Therefore, for example, when focusing on the case of methacrylic acid and acrylic acid, by controlling the type and content ratio of at least the acid comonomer component, the hydrophobicity of the component (A) as a whole can be secured and the solution can be obtained. Tg can be adjusted to favor image quality improvement.
　また、（ａ）酸コモノマー成分は、メタクリル酸又はアクリル酸であり、（ｂ）酸コモノマー成分は、メタクリル酸及びアクリル酸の、いずれとも異なるカルボン酸を含んでよい。これによれば、メタクリル酸及びアクリル酸の、いずれとも異なるカルボン酸による貢献を得て、各種特性に優れた感光性樹脂層を実現し易くなる。 In addition, the (a) acid comonomer component is methacrylic acid or acrylic acid, and the (b) acid comonomer component may contain a carboxylic acid different from both methacrylic acid and acrylic acid. According to this, the contributions of carboxylic acids different from methacrylic acid and acrylic acid can be obtained, and it becomes easy to realize a photosensitive resin layer excellent in various properties.
　（Ａ）成分における、（ａ）酸コモノマー成分に由来する構成単位の質量割合（ａ１）と、（ｂ）酸コモノマー成分に由来する構成単位の質量割合（ｂ１）と、の合計は、１～６５質量％であることが好ましい。これによれば、他のコモノマー成分が含まれる余地を確保することができ、各種用途に応じた組成設計の幅を広げ易くなる。なお、（Ａ）成分における、コモノマー成分の構成単位の割合は、おおよそ、そのコモノマー成分の仕込み量に相当する。上記合計は、上記と同様の観点から、５～５０質量％であることがより好ましく、１５～３５質量％であることが更に好ましく、２０～３０質量％であることが特に好ましい。 In the component (A), the sum of (a) the mass ratio (a1) of structural units derived from the acid comonomer component and (b) the mass ratio (b1) of the structural units derived from the acid comonomer component is 1 to It is preferably 65% by mass. According to this, it is possible to ensure room for other comonomer components to be included, and it becomes easy to widen the range of composition design according to various uses. In addition, the ratio of the constituent units of the comonomer component in the component (A) roughly corresponds to the amount of the comonomer component charged. From the same viewpoint as above, the total is more preferably 5 to 50% by mass, even more preferably 15 to 35% by mass, and particularly preferably 20 to 30% by mass.
　（（ｃ）コモノマー成分の併用）
　（ｃ）コモノマー成分は、（Ａ）成分を得るためのコモノマー成分の一つであり、芳香族構造又は脂環式構造を有する化合物である。（ｃ）コモノマー成分がかかる構成を有することで、レジストパターンの密着性の向上を図ることができる。（ｃ）コモノマー成分は、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であってよい。（ｃ）コモノマー成分は、１種単独でもよく、２種以上を併用してもよい。 (Combination of (c) comonomer component)
(c) A comonomer component is one of the comonomer components for obtaining the (A) component, and is a compound having an aromatic structure or an alicyclic structure. (c) By having such a configuration of the comonomer component, it is possible to improve the adhesion of the resist pattern. (c) The comonomer component may be a compound having an ethylenically unsaturated bond or a compound having a (meth)acryloyl group. (c) The comonomer component may be used alone or in combination of two or more.
　芳香族構造を有する化合物としては、例えば、スチレン、スチレン誘導体、ベンジル（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、等が挙げられる。スチレン誘導体としては、例えば、４－メチルスチレン、４－ヒドロキシスチレン、４－メトキシスチレン、４－クロロスチレン、４－（クロロメチル）スチレン等が挙げられる。 Examples of compounds having an aromatic structure include styrene, styrene derivatives, benzyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, and the like. Examples of styrene derivatives include 4-methylstyrene, 4-hydroxystyrene, 4-methoxystyrene, 4-chlorostyrene, 4-(chloromethyl)styrene and the like.
　脂環式構造を有する化合物としては、例えば、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基等の環状炭化水素基を１つ有する基又はそれらの誘導体からなる基を有する（メタ）アクリル酸エステル、ジシクロペンタニル基、ジシクロペンテニル基、アダマンチル基、イソボルニル基等の環状炭化水素を２以上有する基又はそれらの誘導体からなる基を有する（メタ）アクリル酸エステル等が挙げられる。 Examples of compounds having an alicyclic structure include groups having one cyclic hydrocarbon group such as cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group, or (meth)acrylic acid esters having groups composed of derivatives thereof. , a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group, an isobornyl group, a group having two or more cyclic hydrocarbons, or a (meth)acrylic acid ester having a group consisting of derivatives thereof.
　（ｃ）コモノマー成分は、スチレン及び／又はベンジル（メタ）アクリレートを含むことが好ましく、なかでも、スチレンを含むことが好ましい。これによれば、現像時間が長期化する場合においても、レジストパターンの密着性の向上を図り易くなる。 (c) The comonomer component preferably contains styrene and/or benzyl (meth)acrylate, and more preferably contains styrene. This makes it easier to improve the adhesion of the resist pattern even when the development time is prolonged.
　（Ａ）成分における（ｃ）コモノマー成分の含有割合は、１０～９５質量％であることが好ましく、２０～９０質量％であることがより好ましく、４０～９０質量％であることが更に好ましく、４５～８０質量％であることが更により好ましく、６５～８０質量％であることが特に好ましい。かかる範囲によれば、良好なアルカリ可溶性を維持し易く、かつ、レジストパターンの密着性の向上を図り易い。 The content of (c) comonomer component in component (A) is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, even more preferably 40 to 90% by mass, 45 to 80 mass % is even more preferred, and 65 to 80 mass % is particularly preferred. According to this range, it is easy to maintain good alkali solubility, and it is easy to improve the adhesion of the resist pattern.
　（ｃ）コモノマー成分がスチレンを含み、スチレンの含有割合が４５質量％以上、好ましくは５０質量％以上、より好ましくは５５質量％、更に好ましくは６０質量％以上、特に好ましくは６５質量％以上であることが、レジストパターンの密着性の向上を図り易い観点で好ましい。（ｃ）コモノマー成分がスチレンを含む場合、そのスチレンの含有割合は９５質量％以下でよい。 (c) the comonomer component contains styrene, and the styrene content is 45% by mass or more, preferably 50% by mass or more, more preferably 55% by mass, even more preferably 60% by mass or more, and particularly preferably 65% by mass or more; It is preferable that there is one from the viewpoint of facilitating the improvement of the adhesion of the resist pattern. (c) When the comonomer component contains styrene, the content of styrene may be 95% by mass or less.
　感光性樹脂層の現像性と、得られるレジストパターンの解像性を両立させ、また、基板への密着性を向上させる観点で、（Ａ）成分は、（ａ）メタクリル酸、（ｂ）アクリル酸、及び（ｃ）スチレンをコモノマー成分として含有することが好ましく、（ａ）メタクリル酸に由来する構成単位の質量割合（ａ１）と、（ｂ）アクリル酸に由来する構成単位の質量割合（ｂ１）と、（ｃ）スチレンに由来する構成単位の質量割合（ｃ１）を用いて、　下記式（１）～（３）：
　　１０≦（ａ１）＋（ｂ１）≦５０　・・・　（１）
　　０．５≦（ａ１）／（ｂ１）≦８．０　・・・　（２）
　　３０≦（ｃ１）≦８０　・・・　（３）
　をすべて満たすことが好ましく、
　下記式（４）～（６）：
　　１５≦（ａ１）＋（ｂ１）≦３５　・・・　（４）
　　１．０≦（ａ１）／（ｂ１）≦６．０　・・・　（５）
　　４５≦（ｃ１）≦７５　・・・　（６）
　をすべて満たすことがより好ましく、
　下記式（７）～（９）：
　　２０≦（ａ１）＋（ｂ１）≦３０　・・・　（７）
　　２．０≦（ａ１）／（ｂ１）≦４．２　・・・　（８）
　　５０≦（ｃ１）≦７０　・・・　（９）
　をすべて満たすことが更に好ましい。 From the viewpoint of achieving both the developability of the photosensitive resin layer and the resolution of the resulting resist pattern and improving the adhesion to the substrate, the component (A) is composed of (a) methacrylic acid and (b) acrylic acid. It is preferable to contain an acid and (c) styrene as comonomer components, and (a) the mass ratio (a1) of structural units derived from methacrylic acid, and (b) the mass ratio (b1 ) and (c) the mass ratio (c1) of structural units derived from styrene, the following formulas (1) to (3):
10≦(a1)+(b1)≦50 (1)
0.5≦(a1)/(b1)≦8.0 (2)
30≦(c1)≦80 (3)
preferably satisfy all
Formulas (4) to (6) below:
15≦(a1)+(b1)≦35 (4)
1.0≦(a1)/(b1)≦6.0 (5)
45≦(c1)≦75 (6)
It is more preferable to satisfy all
Formulas (7) to (9) below:
20≦(a1)+(b1)≦30 (7)
2.0≦(a1)/(b1)≦4.2 (8)
50≦(c1)≦70 (9)
is more preferably satisfied.
　（（ｄ）コモノマー成分の任意的な併用）
　（Ａ）成分は、コモノマー成分として、ヒドロキシアルキル（メタ）アクリル酸エステル（「（ｄ）コモノマー成分」とも称する。）に由来する構成単位を更に有することができる。かかる化合物は、水酸（ＯＨ）基を有しており、そのため、例えばメタクリル酸又はアクリル酸と比べて親水性が高い。よって、（Ａ）成分は、（ｄ）コモノマー成分の任意的な併用により、感光性樹脂層の現像性を制御し易くなる。（ｄ）コモノマー成分は１種単独でもよく、２種以上を併用してもよい。 (Optional combination of (d) comonomer components)
The component (A) can further have a structural unit derived from a hydroxyalkyl (meth)acrylic acid ester (also referred to as “(d) comonomer component”) as a comonomer component. Such compounds have hydroxyl (OH) groups and are therefore highly hydrophilic compared to, for example, methacrylic acid or acrylic acid. Therefore, the component (A) can easily control the developability of the photosensitive resin layer by optional combination with the comonomer component (d). (d) The comonomer component may be used singly or in combination of two or more.
　ヒドロキシアルキル（メタ）アクリル酸エステルとしては、例えば、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、ヒドロキシペンチル（メタ）アクリレート等が挙げられる。 Examples of hydroxyalkyl (meth)acrylate esters include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and hydroxypentyl (meth)acrylate.
　（ｄ）コモノマー成分は、ヒドロキシエチルメタクリレートを含むことが好ましい。これによれば、入手が容易であり、それでいて、現像性を制御し易い。
　（Ａ）成分における（ｄ）コモノマー成分の含有割合は、１．０～５０質量％であることが好ましく、１．５～４０質量％であることがより好ましく、２．０～２０質量％であることが更に好ましい。 (d) The comonomer component preferably comprises hydroxyethyl methacrylate. According to this, it is easy to obtain and easy to control the developability.
The content of (d) comonomer component in component (A) is preferably 1.0 to 50% by mass, more preferably 1.5 to 40% by mass, and 2.0 to 20% by mass. It is even more preferable to have
　（他のコモノマー成分の更なる任意的な併用）
　（Ａ）成分は、上記（ａ）酸コモノマー成分及び（ｂ）酸コモノマー成分、並びに（ｃ）コモノマー成分及び（ｄ）コモノマー成分として選択可能なコモノマーの、いずれとも異なるコモノマー成分（「他のコモノマー成分」とも称する。）を、更に併用することができる。 (Further optional combined use of other comonomer components)
The component (A) is a comonomer component ("another comonomer (also referred to as "component") can be further used in combination.
　他のコモノマー成分としては、例えば、（メタ）アクリル酸アルキルエステル、共役ジエン化合物、極性モノマー（ヒドロキシアルキル（メタ）アクリレートを除く。）、架橋性モノマー、酸無水物（例えば、マレイン酸無水物）等が挙げられる。 Other comonomer components include, for example, (meth)acrylic acid alkyl esters, conjugated diene compounds, polar monomers (excluding hydroxyalkyl (meth)acrylates), crosslinkable monomers, acid anhydrides (e.g., maleic anhydride). etc.
　（メタ）アクリル酸アルキルエステルは、鎖状アルキルエステル及び環状アルキルエステルの双方を包含する概念であり、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、ｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ｎ－テトラデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等が挙げられる。 (Meth)acrylic acid alkyl ester is a concept that includes both chain alkyl esters and cyclic alkyl esters, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl ( meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth) Acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, n-tetradecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate and the like.
　共役ジエン化合物としては、例えば、１，３－ブタジエン、イソプレン、２，３－ジメチル－１，３－ブタジエン、２－フェニル－１，３－ブタジエン、１，３－ペンタジエン、２－メチル－１，３－ペンタジエン、１，３－ヘキサジエン、４，５－ジエチル－１，３－オクタジエン、３－ブチル－１，３－オクタジエン等が挙げられる。 Examples of conjugated diene compounds include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1, 3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene and the like.
　極性モノマーとしては、例えば、メタクリル酸２－アミノエチル等のアミノ基含有モノマー；(メタ)アクリルアミド、Ｎ－メチロール（メタ)アクリルアミド等のアミド基含有モノマー；アクリロニトリル、メタクリロニトリル、α－クロロアクリロニトリル、α－シアノエチルアクリレート等のシアノ基含有モノマー；グリシジル（メタ）アクリレート、（メタ）アクリル酸３，４－エポキシシクロヘキシル等のエポキシ基含有モノマー；等が挙げられる。 Polar monomers include, for example, amino group-containing monomers such as 2-aminoethyl methacrylate; amide group-containing monomers such as (meth)acrylamide and N-methylol(meth)acrylamide; acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, cyano group-containing monomers such as α-cyanoethyl acrylate; epoxy group-containing monomers such as glycidyl (meth)acrylate and 3,4-epoxycyclohexyl (meth)acrylate; and the like.
　架橋性モノマーとしては、例えば、トリメチロールプロパントリアクリレート、ジビニルベンゼン等が挙げられる。 Examples of crosslinkable monomers include trimethylolpropane triacrylate and divinylbenzene.
　（（Ａ）成分に関する各種態様）
　（Ａ）成分は、複数のアルカリ可溶性高分子を含むことができる。例えば、（Ａ）成分は、（Ａ１）メタクリル酸及びスチレンを含むアルカリ可溶性高分子と、（Ａ２）アクリル酸及びスチレンを含むアルカリ可溶性高分子との組み合わせでもよく、（Ａ２）アクリル酸及びスチレンを含むアルカリ可溶性高分子と、（Ａ３）メタクリル酸及びヒドロキシエチルメタクリレートを含むアルカリ可溶性高分子との組み合わせであってよい。 (Various aspects related to component (A))
(A) A component can contain several alkali-soluble polymers. For example, the component (A) may be a combination of (A1) an alkali-soluble polymer containing methacrylic acid and styrene and (A2) an alkali-soluble polymer containing acrylic acid and styrene. and (A3) an alkali-soluble polymer containing methacrylic acid and hydroxyethyl methacrylate.
　そして、上記質量割合（ａ１）、上記質量割合（ｂ１）、上記質量割合（ｃ１）のそれぞれの質量平均は、例えば、（Ａ）成分がＮ種のアルカリ可溶性高分子を含む場合、そのアルカリ可溶性高分子の総和に対して、
　第１のアルカリ可溶性高分子（高分子１）の割合をＸ１、
　第２のアルカリ可溶性高分子（高分子２）の割合をＸ２、
　第Ｎのアルカリ可溶性高分子（高分子Ｎ）の割合をＸＮ、
　としたとき、下記式：
　（ａ１）＝（Ｘ１×ａ１－１）＋（Ｘ２×ａ１－２）＋・・＋（ＸＮ×ａ１－Ｎ）
　（ｂ１）＝（Ｘ１×ｂ１－１）＋（Ｘ２×ｂ１－２）＋・・＋（ＸＮ×ｂ１－Ｎ）
　（ｃ１）＝（Ｘ１×ｃ１－１）＋（Ｘ２×ｃ１－２）＋・・＋（ＸＮ×ｃ１－Ｎ）
　　　　ａ１－１：高分子１における（ａ）成分の質量割合
　　　　ａ１－２：高分子２における（ａ）成分の質量割合
　　　　ａ１－Ｎ：高分子Ｎにおける（ａ）成分の質量割合
　　　　ｂ１－１：高分子１における（ｂ）成分の質量割合
　　　　ｂ１－２：高分子２における（ｂ）成分の質量割合
　　　　ｂ１－Ｎ：高分子Ｎにおける（ｂ）成分の質量割合
　　　　ｃ１－１：高分子１における（ｃ）成分の質量割合
　　　　ｃ１－２：高分子２における（ｃ）成分の質量割合
　　　　ｃ１－Ｎ：高分子Ｎにおける（ｃ）成分の質量割合で表される。 Then, the mass average of each of the mass ratio (a1), the mass ratio (b1), and the mass ratio (c1) is, for example, when the component (A) contains an N-type alkali-soluble polymer, the alkali-soluble For the sum of macromolecules,
The ratio of the first alkali-soluble polymer (polymer 1) is X1,
The ratio of the second alkali-soluble polymer (polymer 2) is X2,
XN the ratio of the Nth alkali-soluble polymer (polymer N),
and the following formula:
(a1)=(X1×a1-1)+(X2×a1-2)+..+(XN×a1-N)
(b1)=(X1×b1-1)+(X2×b1-2)+..+(XN×b1-N)
(c1)=(X1×c1-1)+(X2×c1-2)+..+(XN×c1-N)
a1-1: mass ratio of component (a) in polymer 1 a1-2: mass ratio of component (a) in polymer 2 a1-N: mass ratio of component (a) in polymer N b1-1: high mass ratio of component (b) in molecule 1 b1-2: mass ratio of component (b) in polymer 2 b1-N: mass ratio of component (b) in polymer N c1-1: (c ) component mass ratio c1-2: mass ratio of component (c) in polymer 2 c1-N: mass ratio of component (c) in polymer N.
　この場合、アルカリ可溶性高分子の全体として、比率（（ａ１）／（ｂ１））が上記比率の範囲であればよく、単独のアルカリ可溶性高分子としては上記比率の範囲でない場合もあり得る。
　本実施形態においては、質量割合（ａ１）の質量平均と、質量割合（ｂ１）の質量平均と、の関係（質量割合（ａ１）の質量平均／質量割合（ｂ１）の質量平均）が、１／１０～１０であることが、本実施形態の効果を奏し易い観点から好ましい。　 In this case, the ratio ((a1)/(b1)) of the alkali-soluble polymer as a whole may be within the above ratio range, and the ratio of the alkali-soluble polymer alone may not be within the above ratio range.
In the present embodiment, the relationship between the mass average of the mass ratio (a1) and the mass average of the mass ratio (b1) (mass average of the mass ratio (a1) / mass average of the mass ratio (b1)) is 1 /10 to 10 is preferable from the viewpoint that the effect of the present embodiment can be easily exhibited.
　他方、（Ａ）成分に含まれるアルカリ可溶性高分子の少なくとも一つは、（ａ）～（ｂ）酸コモノマー成分と、（ｃ）コモノマー成分と、に由来する構成単位を有し、かつ、上記比率を満たすことができる。すなわち、（Ａ）成分がある単独のアルカリ可溶性高分子により構成される場合には該アルカリ可溶性高分子が、また、（Ａ）成分が複数のアルカリ可溶性高分子により構成される場合にはその複数のうちの少なくとも一つのアルカリ可溶性高分子が、単独で、本発明の（Ａ）成分として求められる必須要件を満たすことができる。 On the other hand, at least one of the alkali-soluble polymers contained in component (A) has structural units derived from (a) to (b) acid comonomer components and (c) comonomer components, and ratio can be met. That is, when the component (A) is composed of a single alkali-soluble polymer, the alkali-soluble polymer, and when the component (A) is composed of a plurality of alkali-soluble polymers, a plurality of them At least one of the alkali-soluble polymers alone can satisfy the essential requirements required as the component (A) of the present invention.
　感光性樹脂組成物は、一態様において、（Ａ）成分に含まれるアルカリ可溶性高分子のうち、（ａ）成分～（ｃ）成分に由来する構成単位を有し、かつ、比率を満たすアルカリ可溶性高分子の割合は１０質量％以上であることが好ましい。
　また、（Ａ）成分に含まれるアルカリ可溶性高分子の少なくとも一つが、本発明の（Ａ）成分として求められる必須要件を満たす場合、（Ａ）成分に含まれるアルカリ可溶性高分子のうち、その要件を満たすアルカリ可溶性高分子の割合は、１０質量％以上であることが好ましい。かかるアルカリ可溶性高分子の割合は、３０質量％以上でもよく、４０質量％以上でもよく、５０質量％以上でもよい。かかるアルカリ可溶性高分子の割合は、１００質量％以下でもよく、６０質量％以下でもよい。 In one embodiment, the photosensitive resin composition has constitutional units derived from components (a) to (c) among the alkali-soluble polymers contained in component (A), and the alkali-soluble It is preferable that the proportion of the polymer is 10% by mass or more.
Further, when at least one of the alkali-soluble polymers contained in component (A) satisfies the essential requirements for component (A) of the present invention, among the alkali-soluble polymers contained in component (A), the requirements The ratio of the alkali-soluble polymer that satisfies is preferably 10% by mass or more. The proportion of such alkali-soluble polymer may be 30% by mass or more, 40% by mass or more, or 50% by mass or more. The proportion of such alkali-soluble polymer may be 100% by mass or less, or 60% by mass or less.
　〔（Ｂ）成分：エチレン性不飽和結合を有する化合物〕
　（Ｂ）成分は、その構造中に、エチレン性不飽和結合を有する化合物である。（Ｂ）成分は、ビスフェノールＡ構造、及び／又は水添ビスフェノールＡ構造を有する化合物を含むことが好ましい。これによれば、本発明の効果を奏し易くなる。（Ｂ）成分の総量のうち、ビスフェノールＡ構造、及び／又は水添ビスフェノールＡ構造を有する化合物が、３０質量％以上、５０質量％以上、８０質量％以上、９０質量％以上含まれてよい。（Ｂ）成分のうち、ビスフェノールＡ構造、及び／又は水添ビスフェノールＡ構造を有する化合物の含量が、他の（Ｂ）成分の各化合物の含量の中で、最も多くてよい。なお、（Ｂ）成分としては、エチレン性不飽和結合を１個有する化合物、エチレン性不飽和結合を２個有する化合物、エチレン性不飽和結合を３個有する化合物、エチレン性不飽和結合を４個有する化合物、及びエチレン性不飽和結合を５個以上有する化合物、が挙げられる。異なる種類のこれらの化合物が併用されてもよい。
　一態様において、（Ｂ）成分が、エチレン性不飽和結合を２個以上有する化合物を、３０質量％以上、５０質量％以上、８０質量％以上、９０質量％以上含むことが好ましい。これによれば、本実施形態による効果を奏し易くなる。 [Component (B): a compound having an ethylenically unsaturated bond]
Component (B) is a compound having an ethylenically unsaturated bond in its structure. (B) Component preferably contains a compound having a bisphenol A structure and/or a hydrogenated bisphenol A structure. According to this, the effects of the present invention can be easily achieved. Compounds having a bisphenol A structure and/or a hydrogenated bisphenol A structure may be contained in an amount of 30% by mass or more, 50% by mass or more, 80% by mass or more, and 90% by mass or more of the total amount of component (B). Among components (B), the content of compounds having a bisphenol A structure and/or a hydrogenated bisphenol A structure may be the highest among the contents of each compound of the other components (B). The component (B) includes a compound having one ethylenically unsaturated bond, a compound having two ethylenically unsaturated bonds, a compound having three ethylenically unsaturated bonds, and four ethylenically unsaturated bonds. and compounds having 5 or more ethylenically unsaturated bonds. Different types of these compounds may be used in combination.
In one aspect, the component (B) preferably contains 30% by mass or more, 50% by mass or more, 80% by mass or more, 90% by mass or more of a compound having two or more ethylenically unsaturated bonds. According to this, it becomes easy to show the effect by this embodiment.
　（Ｂ）成分として、例えば、エチレン性不飽和結合を２個有する化合物と、エチレン性不飽和結合を３個以上有する化合物とは、併用されてよく、また、エチレン性不飽和結合を３個以上有する、互いに異なる化合物は、併用されてよい。エチレン性不飽和結合を３個以上有する化合物としては、例えば、４個のエチレン性不飽和結合、５個のエチレン性不飽和結合、又は６個のエチレン性不飽和結合、を有する化合物が挙げられる。なかでも、（Ｂ）成分は、一分子中に、エチレン性不飽和結合を３つ以上有する化合物を含むことが好ましく、また、一分子中に、エチレン性不飽和結合を４つ以上有する化合物を含むことも好ましい。 As component (B), for example, a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds may be used in combination. Compounds different from each other may be used in combination. Examples of compounds having 3 or more ethylenically unsaturated bonds include compounds having 4 ethylenically unsaturated bonds, 5 ethylenically unsaturated bonds, or 6 ethylenically unsaturated bonds. . Among them, component (B) preferably contains a compound having 3 or more ethylenically unsaturated bonds in one molecule, and a compound having 4 or more ethylenically unsaturated bonds in one molecule. It is also preferred to include
　例えば、（Ｂ）成分としては、ビスフェノールＡの両端にそれぞれ平均１モル～１５モルずつのアルキレンオキサイドを付加したポリアルキレングリコールのジ（メタ）アクリレート；トリメチロールプロパンに平均３モル～２５モルのアルキレンオキサイドを付加したポリアルキレントリオールのトリ（メタ）アクリレート；グリセリン；トリメチロールプロパン；ペンタエリスリトール；ジグリセリン；ジトリメチロールプロパン；イソシアヌレート環等にポリアルキレンオキシド基を付加したり、ε－カプロラクトン変性したりすることにより得られたアルコールを（メタ）アクリレートに変換することで得られる化合物、又はそれらをアルキレンオキシド基又はε－カプロラクトンで変性せずに、直接（メタ）アクリル酸を反応させた化合物；ペンタエリスリトールに平均４モル～３５モルのアルキレンオキサイドを付加したポリオールのテトラ（メタ）アクリレート；ジペンタエリスリトールに平均４～３０モルのアルキレンオキサイドを付加したポリオールのヘキサ（メタ）アクリレート；等を挙げることができる。これらは１種を単独で又は２種類以上を組み合わせて用いることができる。
　具体的に、（Ｂ）成分に含まれてよい化合物の種類としては、
　ビスフェノールＡの両端にそれぞれ平均５モルずつのＥＯ（エチレンオキサイド）を付加したポリエチレングリコールのジメタクリレート、
　ジペンタエリスリトールに平均１３モルのＥＯ（エチレンオキサイド）を付加したヘキサメタクリレート、
　ビスフェノールＡの両端にそれぞれ平均１モルずつのＥＯ（エチレンオキサイド）を付加したポリエチレングリコールのジメタクリレート、
　ＥＯ（エチレンオキサイド）変性水添ビスフェノールＡジメタクリレート、
　ポリテトラメチレングリコールジメタクリレート、
　ペンタエリスリトールに平均１５モルのＥＯ（エチレンオキサイド）を付加したテトラメタクリレート、
　ポリ（プロピレングリコール）ジメタクリレート、
　ＥＯ（エチレンオキサイド）変性ビスフェノールＡジメタクリレート、及び
　グリセリンに平均９モルのＥＯ（エチレンオキサイド）を付加したトリメタクリレート、等が挙げられる。 For example, as component (B), di(meth)acrylate of polyalkylene glycol obtained by adding an average of 1 to 15 moles of alkylene oxide to each end of bisphenol A; tri(meth)acrylate of polyalkylenetriol with oxide added; glycerin; trimethylolpropane; pentaerythritol; diglycerin; ditrimethylolpropane; Compounds obtained by converting the alcohol obtained by converting to (meth) acrylate, or compounds obtained by directly reacting (meth) acrylic acid without modifying them with an alkylene oxide group or ε-caprolactone; penta Tetra (meth) acrylate of polyol obtained by adding an average of 4 to 35 moles of alkylene oxide to erythritol; Hexa (meth) acrylate of polyol obtained by adding an average of 4 to 30 moles of alkylene oxide to dipentaerythritol; can. These can be used individually by 1 type or in combination of 2 or more types.
Specifically, the types of compounds that may be contained in component (B) include:
dimethacrylate of polyethylene glycol obtained by adding an average of 5 moles of EO (ethylene oxide) to each end of bisphenol A;
Hexamethacrylate obtained by adding an average of 13 mol of EO (ethylene oxide) to dipentaerythritol,
dimethacrylate of polyethylene glycol obtained by adding an average of 1 mol of EO (ethylene oxide) to each end of bisphenol A;
EO (ethylene oxide) modified hydrogenated bisphenol A dimethacrylate,
polytetramethylene glycol dimethacrylate,
Tetramethacrylate obtained by adding an average of 15 mol of EO (ethylene oxide) to pentaerythritol,
poly(propylene glycol) dimethacrylate,
EO (ethylene oxide)-modified bisphenol A dimethacrylate, and trimethacrylate obtained by adding an average of 9 mol of EO (ethylene oxide) to glycerin, and the like.
　感光性樹脂組成物における（Ｂ）成分の含有量は、好ましくは５～７０質量％、より好ましくは２０～６０質量％、更に好ましくは３０～５０質量％である。（Ｂ）成分の含有量は、感光性樹脂層の硬化不良、及び現像時間の遅延を抑える観点から、上記の下限値以上であることが好ましい。また、硬化した感光性樹脂層の除去性を向上させる観点から、上記の上限値以下であることが好ましい。 The content of component (B) in the photosensitive resin composition is preferably 5-70% by mass, more preferably 20-60% by mass, still more preferably 30-50% by mass. The content of component (B) is preferably at least the above lower limit from the viewpoint of suppressing poor curing of the photosensitive resin layer and delay in development time. Moreover, it is preferable that it is below said upper limit from a viewpoint of improving the removability of the cured photosensitive resin layer.
　〔（Ｃ）成分：光重合開始剤〕
　（Ｃ）成分は、活性光線によりラジカルを発生し、これにより、（Ｂ）成分の重合を開始させることができる化合物である。 [(C) component: photopolymerization initiator]
Component (C) is a compound capable of generating radicals upon exposure to actinic rays, thereby initiating polymerization of component (B).
　（Ｃ）成分としては、例えば、ヘキサアリールビイミダゾール化合物、Ｎ－アリール－α－アミノ酸化合物、キノン化合物、芳香族ケトン化合物、アントラセン誘導体、アセトフェノン化合物、アシルフォスフィンオキサイド化合物、ベンゾイン化合物、ベンゾインエーテル化合物、ジアルキルケタール化合物、チオキサントン化合物、ジアルキルアミノ安息香酸エステル化合物、オキシムエステル化合物、アクリジン化合物、ピラゾリン誘導体、Ｎ－アリールアミノ酸のエステル化合物、及びハロゲン化合物等が挙げられる。 Examples of component (C) include hexaarylbiimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, anthracene derivatives, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, and benzoin ether compounds. , dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-arylamino acid ester compounds, and halogen compounds.
　ヘキサアリールビイミダゾール化合物としては、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）、２，２’，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、ロフィン二量体等が挙げられる。 Examples of hexaarylbiimidazole compounds include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole (alias: 2,2′-bis(2-chlorophenyl)-4,4′,5,5′- tetraphenyl-1,2'-biimidazole), 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2, 4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl) -bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl )-biimidazole, 2,2′-bis-(2,3-difluoromethylphenyl)-4,4′,5,5′-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2′-bis -(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4, 4′,5,5′-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2′-bis-(2,6-difluorophenyl)-4,4′,5,5′-tetrakis-(3 -methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2 ,2′-bis-(2,3,5-trifluorophenyl)-4,4′,5,5′-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2′-bis-(2, 3,6-trifluorophenyl)-4,4′,5,5′-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2′-bis-(2,4,5-trifluorophenyl)- 4,4′,5,5′-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2′-bis-(2,4,6-trifluorophenyl)-4,4′,5,5′ -tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxy phenyl)-biimidazole, 2,2′-bis-(2,3,4,6-tetrafluorophenyl)-4,4′,5,5′-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, lophine dimer, etc. are mentioned.
　ロフィン二量体、すなわち、２，４，５－トリアリールイミダゾールの二量体としては、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。なかでも、高感度、解像性及び密着性の観点から、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が好ましい。 lophine dimers, that is, dimers of 2,4,5-triarylimidazole, for example, 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. Among them, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferable from the viewpoint of high sensitivity, resolution and adhesion.
　Ｎ－アリール－α－アミノ酸化合物としては、例えば、Ｎ－フェニルグリシン、Ｎ－メチル－Ｎ－フェニルグリシン、Ｎ－エチル－Ｎ－フェニルグリシン等が挙げられる。なかでも、Ｎ－フェニルグリシンは、増感効果が高いため好ましい。 Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. Among them, N-phenylglycine is preferable because of its high sensitizing effect.
　キノン化合物としては、例えば、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、２－クロロアントラキノン、２－メチルアントラキノン、１，４－ナフトキノン、９，１０－フェナントラキノン、２－メチル－１，４－ナフトキノン、２，３－ジメチルアントラキノン、３－クロロ－２－メチルアントラキノン等が挙げられる。 Examples of quinone compounds include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloro anthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone, etc. be done.
　芳香族ケトン化合物としては、例えば、ベンゾフェノン、ミヒラーズケトン［４，４’－ビス（ジメチルアミノ）ベンゾフェノン］、４－メトキシ－４’－ジメチルアミノベンゾフェノン等が挙げられる。芳香族ケトン化合物としては、増感効果及び密着性の観点から、４，４’－ビス（ジエチルアミノ）ベンゾフェノンも挙げられる。 Examples of aromatic ketone compounds include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4-methoxy-4'-dimethylaminobenzophenone, and the like. The aromatic ketone compound also includes 4,4'-bis(diethylamino)benzophenone from the viewpoint of sensitizing effect and adhesion.
　本明細書では、用語「アントラセン誘導体」は、アントラセン及びそれから誘導される化合物の両方を含むものである。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等が挙げられる。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。 As used herein, the term "anthracene derivative" includes both anthracene and compounds derived therefrom. Examples of anthracene derivatives include anthracene, 9,10-dialkoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethyl anthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone and the like. From the viewpoint of sensitizing effect and adhesion, 9,10-dibutoxyanthracene and 9,10-diphenylanthracene are preferred, and 9,10-diphenylanthracene is particularly preferred.
　アセトフェノン化合物としては、例えば、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、１－（４－ドデシルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、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、１－ヒドロキシシクロヘキシルフェニルケトン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタノン－１、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノ－プロパノン－１等が挙げられる。アセトフェノン化合物の市販品としては、例えば、イルガキュアシリーズ（チバ・スペシャリティ・ケミカルズ社製：イルガキュア－９０７、イルガキュア－３６９、及びイルガキュア－３７９等）が挙げられる。 Examples of 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, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1 and the like. Examples of commercially available acetophenone compounds include Irgacure series (Ciba Specialty Chemicals: Irgacure-907, Irgacure-369, Irgacure-379, etc.).
　アシルフォスフィンオキサイド化合物としては、例えば、２，４，６－トリメチルベンジルジフェニルフォスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フォスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチル－ペンチルフォスフィンオキサイド等が挙げられる。アシルフォスフィンオキサイド化合物の市販品としては、例えば、ルシリンＴＰＯ（ＢＡＳＦ社製）、及びイルガキュア－８１９（チバ・スペシャリティ・ケミカルズ社製）が挙げられる。 Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, bis(2,6-dimethoxybenzoyl)-2 , 4,4-trimethyl-pentylphosphine oxide and the like. Commercially available acylphosphine oxide compounds include, for example, Lucirin TPO (manufactured by BASF) and Irgacure-819 (manufactured by Ciba Specialty Chemicals).
　ベンゾイン化合物及びベンゾインエーテル化合物としては、例えば、ベンゾイン、ベンゾインエチルエーテル、ベンゾインフェニルエーテル、メチルベンゾイン、エチルベンゾイン等が挙げられる。
　ジアルキルケタール化合物としては、例えば、ベンジルジメチルケタール、ベンジルジエチルケタール等が挙げられる。
　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等が挙げられる。
　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）ベンゾエート等が挙げられる。 Examples of benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, ethylbenzoin and the like.
Examples of dialkyl ketal compounds include benzyl dimethyl ketal and benzyl diethyl ketal.
Thioxanthone compounds include, for example, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.
Examples of dialkylaminobenzoic acid ester compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.
　オキシムエステル化合物としては、例えば、１－フェニル－１，２－プロパンジオン－２－Ｏ－ベンゾイルオキシム、１－フェニル－１，２－プロパンジオン－２－（Ｏ－エトキシカルボニル）オキシム等が挙げられる。オキシムエステル化合物の市販品としては、例えば、ＣＧＩ－３２５、イルガキュア－ＯＸＥ０１、及びイルガキュア－ＯＸＥ０２（いずれもチバ・スペシャリティ・ケミカルズ社製）が挙げられる。 Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, and the like. . Commercially available oxime ester compounds include, for example, CGI-325, Irgacure-OXE01, and Irgacure-OXE02 (all manufactured by Ciba Specialty Chemicals).
　アクリジン化合物としては、感度、解像性、入手性等の点で、１，７－ビス（９，９’－アクリジニル）ヘプタン又は９－フェニルアクリジンが好ましい。 The acridine compound is preferably 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine in terms of sensitivity, resolution, availability, etc.
　ピラゾリン誘導体としては、密着性及びレジストパターンの矩形性の観点から、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－ビフェニル）－５－（４－ｔｅｒｔ－ブチル－フェニル）－ピラゾリン及び１－フェニル－３－（４－ビフェニル）－５－（４－ｔｅｒｔ－オクチル－フェニル）－ピラゾリンが好ましい。 As pyrazoline derivatives, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl -3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline and 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline are preferred .
　Ｎ－アリールアミノ酸のエステル化合物としては、例えば、Ｎ－フェニルグリシンのメチルエステル、Ｎ－フェニルグリシンのエチルエステル、Ｎ－フェニルグリシンのｎ－プロピルエステル、Ｎ－フェニルグリシンのイソプロピルエステル、Ｎ－フェニルグリシンの１－ブチルエステル、Ｎ－フェニルグリシンの２－ブチルエステル、Ｎ－フェニルグリシンのｔｅｒｔブチルエステル、Ｎ－フェニルグリシンのペンチルエステル、Ｎ－フェニルグリシンのヘキシルエステル、Ｎ－フェニルグリシンのペンチルエステル、Ｎ－フェニルグリシンのオクチルエステル等が挙げられる。 Ester compounds of N-arylamino acids include, for example, methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, and 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, N -octyl ester of phenylglycine, and the like.
　ハロゲン化合物としては、例えば、臭化アミル、臭化イソアミル、臭化イソブチレン、臭化エチレン、臭化ジフェニルメチル、臭化ベンジル、臭化メチレン、トリブロモメチルフェニルスルフォン、四臭化炭素、トリス（２，３－ジブロモプロピル）ホスフェート、トリクロロアセトアミド、ヨウ化アミル、ヨウ化イソブチル、１，１，１－トリクロロ－２，２－ビス（ｐ－クロロフェニル）エタン、クロル化トリアジン化合物、ジアリルヨードニウム化合物等が挙げられる。なかでも、トリブロモメチルフェニルスルフォンが好ましい。 Halogen compounds include, for example, 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, diallyliodonium compounds, and the like. be done. Among them, tribromomethylphenylsulfone is preferred.
　感光性樹脂組成物における（Ｃ）成分の含有量は、０．０１～２０質量％が好ましく、０．５～１０質量％がより好ましい。（Ｃ）成分の含有量を上記範囲内に調整することにより、十分な感度を得られ易くなるため、感光性樹脂層の底部にまで十分に光を透過させ易くなり、ひいては、高解像を実現し易くなる。 The content of component (C) in the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.5 to 10% by mass. By adjusting the content of the component (C) within the above range, it becomes easy to obtain sufficient sensitivity, so that light can be sufficiently transmitted to the bottom of the photosensitive resin layer, and high resolution can be achieved. easier to implement.
　高感度、解像性及び密着性の観点から、（Ｃ）成分として、ロフィン二量体を含むことが好ましい。この場合、感光性樹脂組成物中のロフィン二量体の含有量は、０．１～１５質量％が好ましく、０．５～１０質量％がより好ましい。 From the viewpoint of high sensitivity, resolution and adhesion, it is preferable that the component (C) contains a lophine dimer. In this case, the content of the lophine dimer in the photosensitive resin composition is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass.
　（Ｃ）成分としては、アントラセン誘導体と、ヘキサアリールビイミダゾール化合物と、を併用することが好ましい。この場合、感光性樹脂組成物中の（Ｃ）成分（例えば、アントラセン誘導体）の含有量は、０．５質量％以下であることが好ましく、０．０１質量％～０．４質量％であることがより好ましく、また感光性樹脂組成物中のヘキサアリールビイミダゾール化合物の含有量は、０．１～１０質量％であることが好ましく、０．５～５質量％であることがより好ましい。 As the component (C), it is preferable to use an anthracene derivative and a hexaarylbiimidazole compound in combination. In this case, the content of component (C) (eg, anthracene derivative) in the photosensitive resin composition is preferably 0.5% by mass or less, and is 0.01% by mass to 0.4% by mass. The content of the hexaarylbiimidazole compound in the photosensitive resin composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.
　〔（Ｄ）成分：ロイコ染料〕
　（Ｄ）成分は、未露光部の発色性と、優れた剥離特性を付与するために、本実施形態の感光性樹脂組成物に配合することができる。
　（Ｄ）成分としては、例えば、ロイコクリスタルバイオレット（トリス［４－（ジメチルアミノ）フェニル］メタン）、３，３－ビス（ｐ－ジメチルアミノフェニル）－６－ジメチルアミノフタリド等が挙げられる。なかでも、ロイコクリスタルバイオレットが好ましい。 [(D) component: leuco dye]
The component (D) can be blended in the photosensitive resin composition of the present embodiment in order to impart color developability to unexposed areas and excellent peeling properties.
Component (D) includes, for example, leuco crystal violet (tris[4-(dimethylamino)phenyl]methane), 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, and the like. Among them, leuco crystal violet is preferred.
　感光性樹脂組成物における（Ｄ）成分の含有量は、該感光性樹脂組成物の固形分の合計質量に対して、０．０１～２質量％であることが好ましく、０．１～１．５質量％であることがより好ましい。（Ｄ）成分の含有量をこの範囲内に調節することで、良好な発色性と感度とを実現することができる。 The content of component (D) in the photosensitive resin composition is preferably 0.01 to 2% by mass, more preferably 0.1 to 1.0% by mass, based on the total mass of the solid content of the photosensitive resin composition. More preferably, it is 5% by mass. By adjusting the content of component (D) within this range, good color developability and sensitivity can be achieved.
　〔他の成分〕
　感光性樹脂組成物は、所望により、ベース染料（（Ｄ）成分以外の染料）、酸化防止剤、安定化剤、増感剤、可塑剤、等を含むことができる。他の成分は、上記（Ａ）～（Ｄ）以外の成分である。 [Other ingredients]
The photosensitive resin composition may optionally contain base dyes (dyes other than component (D)), antioxidants, stabilizers, sensitizers, plasticizers, and the like. Other components are components other than the above (A) to (D).
　ベース染料としては、例えば、ベーシックグリーン１［ＣＡＳ番号（以下、同じ）：６３３－０３－４］（例えば、Ａｉｚｅｎ　Ｄｉａｍｏｎｄ　Ｇｒｅｅｎ　ＧＨ、商品名、保土谷化学工業製）、フクシン［６３２－９９－５］、メチルバイオレット［６０３－４７－４］、メチルグリーン［８２－９４－０］、ビクトリアブルーＢ［２５８０－５６－５］、ベーシックブルー７［２３９０－６０－５］（例えば、Ａｉｚｅｎ　Ｖｉｃｔｏｒｉａ　Ｐｕｒｅ　Ｂｌｕｅ　ＢＯＨ、商品名、保土谷化学工業製）、ローダミンＢ［８１－８８－９］、ローダミン６Ｇ［９８９－３８－８］、ベーシックイエロー２［２４６５－２７－２］等が挙げられる。なかでも、着色性、色相安定性、及び露光コントラストを向上させる観点から、ベーシックグリーン１が好ましい。これらは、１種を単独で又は２種以上を組み合わせて使用可能である。 Examples of base dyes include Basic Green 1 [CAS number (hereinafter the same): 633-03-4] (for example, Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Industry), 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] (for example, Aizen Victoria Pure Blue BOH, trade name, manufactured by Hodogaya Chemical Industry), Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], Basic Yellow 2 [2465-27-2], and the like. Among them, Basic Green 1 is preferable from the viewpoint of improving colorability, hue stability, and exposure contrast. These can be used individually by 1 type or in combination of 2 or more types.
　感光性樹脂組成物におけるベース染料の含有量は、好ましくは０．００１～３質量％であり、より好ましくは０．０１～２質量％であり、更に好ましくは０．０４～１質量％である。ベース染料の含有量は、良好な着色性を得る観点から、上記の下限値以上であることが好ましく、他方、感光性樹脂層の感度を維持する観点から、上記の上限値以下であることが好ましい。 The content of the base dye in the photosensitive resin composition is preferably 0.001 to 3% by mass, more preferably 0.01 to 2% by mass, and still more preferably 0.04 to 1% by mass. . The content of the base dye is preferably at least the above lower limit from the viewpoint of obtaining good coloring properties, and on the other hand, from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, it is preferably at most the above upper limit. preferable.
　酸化防止剤としては、例えば、トリフェニルホスファイト（例えば、ＡＤＥＫＡ社製、商品名：ＴＰＰ）、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト（例えば、ＡＤＥＫＡ社製、商品名２１１２）、トリス（モノノニルフェニル）ホスファイト（例えばＡＤＥＫＡ社製、商品名：１１７８）、ビス（モノノニルフェニル）－ジノニルフェニルホスファイト（例えば、ＡＤＥＫＡ社製、商品名：３２９Ｋ）等が挙げられる。これらは、１種を単独で又は２種以上を組み合わせて使用可能である。 Antioxidants include, for example, triphenyl phosphite (for example, manufactured by ADEKA, trade name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (for example, manufactured by ADEKA, trade name 2112 ), tris(monononylphenyl) phosphite (eg, ADEKA, trade name: 1178), bis(monononylphenyl)-dinonylphenyl phosphite (eg, ADEKA, trade name: 329K), and the like. . These can be used individually by 1 type or in combination of 2 or more types.
　感光性樹脂組成物における酸化防止剤の含有量は、好ましくは０．０１～０．８質量％であり、より好ましくは０．０１～０．３質量％である。酸化防止剤の含有量は、レジストパターンの色相安定性を良好に発現させ、かつ、感光性樹脂層の感度を向上させる観点から、上記の下限値以上であることが好ましい。他方、レジストパターンの発色性を抑えながら色相安定性を良好に発現させ、かつ、密着性を向上させる観点から、上記の上限値以下であることが好ましい。 The content of the antioxidant in the photosensitive resin composition is preferably 0.01-0.8% by mass, more preferably 0.01-0.3% by mass. The content of the antioxidant is preferably at least the above lower limit, from the viewpoint of exhibiting good hue stability of the resist pattern and improving the sensitivity of the photosensitive resin layer. On the other hand, from the viewpoint of exhibiting good hue stability while suppressing the color development of the resist pattern and improving adhesion, it is preferably not more than the above upper limit.
　安定化剤は、感光性樹脂組成物の熱安定性及び／又は保存安定性を向上させる観点で用いることができる。安定化剤としては、例えば、ラジカル重合禁止剤と、グリシジル基を有するアルキレンオキシド化合物と、の少なくとも一方が挙げられる。これらは、１種を単独で又は２種以上を組み合わせて使用可能である。 The stabilizer can be used from the viewpoint of improving the thermal stability and/or storage stability of the photosensitive resin composition. Examples of the stabilizer include at least one of a radical polymerization inhibitor and an alkylene oxide compound having a glycidyl group. These can be used individually by 1 type or in combination of 2 or more types.
　ラジカル重合禁止剤としては、例えば、ｐ－メトキシフェノール、ハイドロキノン、ピロガロール、ナフチルアミン、ｔｅｒｔ－ブチルカテコール、塩化第一銅、２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、２，２’－メチレンビス（４－メチル－６－ｔｅｒｔ－ブチルフェノール）、２，２’－メチレンビス（４－エチル－６－ｔｅｒｔ－ブチルフェノール）、トリエチレングリコール－ビス［３－（３－ｔ－ブチル－５－メチル－４－ヒドロキシフェニル）プロピオネート］、ニトロソフェニルヒドロキシアミンアルミニウム塩（例えば、ニトロソフェニルヒドロキシルアミンが３モル付加したアルミニウム塩など）、ジフェニルニトロソアミン等が挙げられる。なかでも、トリエチレングリコール－ビス［３－（３－ｔ－ブチル－５－メチル－４－ヒドロキシフェニル）プロピオネート］、又はニトロソフェニルヒドロキシルアミンが３モル付加したアルミニウム塩が好ましい。これらは、１種を単独で又は２種以上を組み合わせて使用可能である。 Examples of radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, 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 to which 3 mol of nitrosophenylhydroxylamine is added), diphenylnitrosamine, and the like. Among them, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate] or an aluminum salt to which 3 mol of nitrosophenylhydroxylamine is added is preferable. These can be used individually by 1 type or in combination of 2 or more types.
　グリシジル基を有するアルキレンオキシド化合物としては、例えば、ネオペンチルグリコールジグリシジルエーテル（例えば、共栄社化学（株）製エポライト１５００ＮＰ）、ノナエチレングリコールジグリシジルエーテル（例えば、共栄社化学（株）製エポライト４００Ｅ）、ビスフェノールＡ－プロピレンオキシド　２モル付加物ジグリシジルエーテル（例えば、共栄社化学（株）製エポライト３００２）、１，６－ヘキサンジオールジグリシジルエーテル（例えば、共栄社化学（株）製エポライト１６００）等が挙げられる。これらは、１種を単独で又は２種以上を組み合わせて使用可能である。 Examples of the alkylene oxide compound having a glycidyl group include neopentyl glycol diglycidyl ether (e.g. Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (e.g. Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), Bisphenol A-propylene oxide 2 mol adduct diglycidyl ether (eg Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), 1,6-hexanediol diglycidyl ether (eg Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.), etc. . These can be used individually by 1 type or in combination of 2 or more types.
　感光性樹脂組成物における、ラジカル重合禁止剤と、グリシジル基を有するアルキレンオキシド化合物と、の合計含有量は、好ましくは０．００１～３質量％であり、より好ましくは０．０５～１質量％である。合計含有量は、感光性樹脂組成物に良好な保存安定性を付与する観点から、上記の下限値以上であることが好ましく、他方、感光性樹脂層の感度を維持する観点から、上記の上限値以下であることが好ましい。 The total content of the radical polymerization inhibitor and the alkylene oxide compound having a glycidyl group in the photosensitive resin composition is preferably 0.001 to 3% by mass, more preferably 0.05 to 1% by mass. is. The total content is preferably at least the above lower limit from the viewpoint of imparting good storage stability to the photosensitive resin composition, and on the other hand, from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, the above upper limit is preferably less than or equal to
　［感光性樹脂組成物調合液］
　感光性樹脂組成物に溶媒を添加することで、感光性樹脂組成物調合液を作製できる。好適な溶媒としては、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。感光性樹脂組成物調合液の粘度が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好ましい。 [Photosensitive resin composition preparation]
By adding a solvent to the photosensitive resin composition, a photosensitive resin composition preparation liquid can be prepared. Suitable solvents include, for example, ketones such as acetone and methyl ethyl ketone (MEK); alcohols such as methanol, ethanol, and isopropyl alcohol. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition prepared liquid is 500 to 4000 mPa·sec at 25°C.
　［感光性樹脂積層体、ドライフィルムレジスト及び転写フィルム］
　感光性樹脂組成物又は感光性樹脂組成物調合液を用いて、感光性樹脂層、ひいては感光性樹脂積層体を得ることができる。感光性樹脂積層体は、例えば、支持体（支持フィルム）と、支持体に積層された感光性樹脂層と、を有する。感光性樹脂積層体は、必要により、支持体とは反対側の面に保護フィルムを有することができる。感光性樹脂積層体は、本発明の効果を顕著に奏し易くなる観点から、ドライフィルムレジスト又は転写フィルムであることが好ましく、ドライフィルムレジストであることがより好ましい。 [Photosensitive resin laminate, dry film resist and transfer film]
A photosensitive resin layer and, in turn, a photosensitive resin laminate can be obtained using a photosensitive resin composition or a photosensitive resin composition preparation. A photosensitive resin laminate has, for example, a support (support film) and a photosensitive resin layer laminated on the support. If necessary, the photosensitive resin laminate may have a protective film on the side opposite to the support. The photosensitive resin laminate is preferably a dry film resist or a transfer film, more preferably a dry film resist, from the viewpoint that the effect of the present invention can be remarkably exhibited.
　支持体は、露光光源から放射される光を透過する透明なものであることが望ましい。このような支持体としては、好ましくはプラスチックフィルムであり、具体的には例えば、ポリエチレンテレフタレートフィルム、ポリビニルアルコールフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリ塩化ビニリデンフィルム、塩化ビニリデン共重合フィルム、ポリメタクリル酸メチル共重合体フィルム、ポリスチレンフィルム、ポリアクリロニトリルフィルム、スチレン共重合体フィルム、ポリアミドフィルム、セルロース誘導体フィルム等が挙げられる。これらのフィルムは、必要に応じて延伸されたものを使用してよい。 The support is desirably transparent through which the light emitted from the exposure light source is transmitted. Such a support is preferably a plastic film, and specific examples include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, and vinylidene chloride copolymer film. film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film and the like. These films may be stretched if necessary.
　支持体のヘイズは５以下であることが好ましい。支持体の厚みは、薄い方が画像形成性及び経済性の面で有利であるが、強度を維持する機能も考慮すると、１０～３０μｍであることが好ましい。 The haze of the support is preferably 5 or less. The thickness of the support is preferably 10 to 30 μm in consideration of the function of maintaining the strength, although a thinner support is advantageous in terms of image formation and economic efficiency.
　上記で説明された感光性樹脂層は、感光性樹脂組成物を含むか、又は感光性樹脂組成物から成ることができる。感光性樹脂積層体における感光性樹脂層の膜厚は、好ましくは、３～１００μｍであり、より好ましくは１０～５０μｍ、更に好ましくは１５～５０μｍである。感光性樹脂層の厚みが３μｍに近づくほど、解像性は向上し、１００μｍに近づくほど、膜強度が向上するので、用途に応じて適宜選択することができる。 The photosensitive resin layer described above can contain or consist of a photosensitive resin composition. The film thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 3 to 100 μm, more preferably 10 to 50 μm, still more preferably 15 to 50 μm. As the thickness of the photosensitive resin layer approaches 3 μm, the resolution improves, and as the thickness approaches 100 μm, the film strength improves.
　感光性樹脂積層体に用いられる保護フィルムの重要な特性は、適当な密着力を有することである。つまり、保護フィルムの感光性樹脂層に対する密着力が、支持体の感光性樹脂層に対する密着力よりも充分小さく、保護フィルムが感光性樹脂積層体から容易に剥離できることが好ましい。保護フィルムとしては、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリエチレンテレフタラートフィルム、ポリエステルフィルムなどを用いることができる。保護フィルムの膜厚は、１０～１００μｍが好ましく、１０～５０μｍがより好ましい。 An important property of the protective film used for the photosensitive resin laminate is to have appropriate adhesion. In other words, it is preferable that the adhesive strength of the protective film to the photosensitive resin layer is sufficiently lower than the adhesive strength of the support to the photosensitive resin layer so that the protective film can be easily peeled off from the photosensitive resin laminate. Examples of protective films that can be used include polyethylene films, polypropylene films, polyethylene terephthalate films, and polyester films. The thickness of the protective film is preferably 10-100 μm, more preferably 10-50 μm.
　感光性樹脂層から保護フィルムを好適に剥がせるよう、離型層を、保護フィルムの表面に付与することができる。離型層は、例えば、シリコーン化合物と、非シリコーン化合物と、に分類される。 A release layer can be applied to the surface of the protective film so that the protective film can be suitably peeled off from the photosensitive resin layer. Release layers are classified into, for example, silicone compounds and non-silicone compounds.
　シリコーン化合物としては、例えば、両末端シラノールポリジメチルシロキサンと、ポリメチル水素シロキサン又はポリメチルメトキシシロキサンと、を反応させた縮合反応型シリコーン樹脂；ジメチルシロキサン・メチルビニルシロキサン共重合体又はジメチルシロキサン・メチルヘキセニルシロキサン共重合体と、ポリメチル水素シロキサンと、を反応させた付加反応型シリコーン樹脂；アクリルシリコーン及びエポキシ基含有シリコーン等を、紫外線又は電子線で硬化させた紫外線硬化型又は電子線硬化型シリコーン樹脂；エポキシ変性シリコーン樹脂（シリコーンエポキシ）、ポリエステル変性シリコーン樹脂（シリコーンポリエステル）、アクリル変性シリコーン樹脂（シリコーンアクリル）、フェノール変性シリコーン樹脂（シリコーンフェノール）、アルキッド変性シリコーン樹脂（シリコーンアルキッド）、メラミン変性シリコーン樹脂（シリコーンメラミン）等の変性シリコーン樹脂；が挙げられる。 As the silicone compound, for example, a condensation reaction type silicone resin obtained by reacting both end-silanol polydimethylsiloxane with polymethylhydrogensiloxane or polymethylmethoxysiloxane; dimethylsiloxane/methylvinylsiloxane copolymer or dimethylsiloxane/methylhexenyl addition reaction type silicone resin obtained by reacting a siloxane copolymer with polymethylhydrogensiloxane; UV-curable or electron beam-curable silicone resin obtained by curing acrylic silicone, epoxy group-containing silicone, etc. with ultraviolet rays or electron beams; Epoxy-modified silicone resin (silicone epoxy), polyester-modified silicone resin (silicone polyester), acrylic-modified silicone resin (silicone acryl), phenol-modified silicone resin (silicone phenol), alkyd-modified silicone resin (silicone alkyd), melamine-modified silicone resin ( modified silicone resins such as silicone melamine;
　非シリコーン化合物としては、例えば、アルキド（又はアルキッドともいう）樹脂、長鎖アルキル系樹脂、アクリル系樹脂、及びポリオレフィン系樹脂等が挙げられる。 Examples of non-silicone compounds include alkyd (or alkyd) resins, long-chain alkyl resins, acrylic resins, and polyolefin resins.
　離型層の膜厚は、好ましくは０．００１～２μｍ、より好ましくは０．００５～１μｍ、更に好ましくは０．０１～０．５μｍである。膜厚が上記上限値以下であれば、塗膜外観が良好になり易く、また、塗膜を十分に硬化させ易くなる。他方、膜厚が上記下限値以上の場合、十分な離型性を確保し易くなる。 The film thickness of the release layer is preferably 0.001 to 2 μm, more preferably 0.005 to 1 μm, still more preferably 0.01 to 0.5 μm. When the film thickness is equal to or less than the above upper limit, the appearance of the coating film tends to be good, and the coating film can be sufficiently cured. On the other hand, when the film thickness is equal to or greater than the above lower limit, it becomes easier to ensure sufficient releasability.
　［感光性樹脂積層体の作製方法］
　感光性樹脂積層体は、支持体に、感光性樹脂層と、必要により保護フィルムと、を順次積層することで作製することができる。作製方法としては、例えば、感光性樹脂層に用いる感光性樹脂組成物を、これらを溶解する溶剤と混ぜ合わせ、感光性樹脂組成物調合液（塗工液）を作製する。次いで、支持体に、塗工液をバーコーター又はロールコーターを用いて塗布し、乾燥させて、支持体に感光性樹脂層を積層する。そして、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ことにより、感光性樹脂積層体を作製することができる。 [Method for producing photosensitive resin laminate]
A photosensitive resin laminate can be produced by sequentially laminating a photosensitive resin layer and, if necessary, a protective film on a support. As a production method, for example, a photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent for dissolving them to produce a photosensitive resin composition preparation liquid (coating liquid). Next, the coating solution is applied to the support using a bar coater or roll coater and dried to laminate a photosensitive resin layer on the support. Then, if necessary, a photosensitive resin laminate can be produced by laminating a protective film on the photosensitive resin layer.
［レジストパターンの形成方法］
　本実施形態に係る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は、以下の工程：
　感光性樹脂積層体を基板に積層する工程；
　積層した感光性樹脂積層体の感光性樹脂層を露光する工程；及び
　露光した感光性樹脂層を現像する現像工程；
を、好ましくはこの順に、含む。 [Method of forming a resist pattern]
The method for forming a resist pattern using the photosensitive resin laminate according to this embodiment includes the following steps:
Laminating a photosensitive resin laminate on a substrate;
A step of exposing the photosensitive resin layer of the laminated photosensitive resin laminate; and a developing step of developing the exposed photosensitive resin layer;
, preferably in that order.
　〔積層工程〕
　積層工程では、具体的には、感光性樹脂積層体が保護フィルムを有する場合にはその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）等が挙げられる。ラミネート時の加熱温度は一般に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か、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。 [Lamination process]
Specifically, in the lamination step, when the photosensitive resin laminate has a protective film, after peeling the protective film from the photosensitive resin laminate, the photosensitive resin layer is heat-pressed onto the substrate surface with a laminator, Laminate once or multiple times. Examples of substrate materials include copper, stainless steel (SUS), glass, and indium tin oxide (ITO). The heating temperature during lamination is generally 40 to 160°C. The thermocompression bonding can be performed by using a laminator equipped with rolls or by repeatedly passing the laminate of the substrate and the photosensitive resin layer through rolls several times. Thermocompression bonding can be performed under a reduced pressure environment, if desired.
　〔露光工程〕
　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、支持体を剥離した後に行うことができる。フォトマスクを通して露光する場合には、露光量は、光源照度及び露光時間により決定され、光量計を用いて測定してもよい。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。 [Exposure process]
In the exposure step, the photosensitive resin layer is exposed to actinic light using an exposure machine. Exposure can be carried out after peeling off the support, if desired. When exposed through a photomask, the amount of exposure is determined by the illuminance of the light source and the exposure time, and may be measured using a photometer. Direct imaging exposure may be performed in the exposure step. In direct imaging exposure, the substrate is directly exposed by a drawing device without using a photomask. As a light source, a semiconductor laser with a wavelength of 350 to 410 nm or an ultra-high pressure mercury lamp is used. When 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.
　露光工程で使用する光照射方法は、投影露光法、プロキシミティー露光法、コンタクト露光法、ダイレクトイメージング露光法、電子線直描法から選択される少なくとも１種類の方法であることが好ましく、投影露光方法またはダイレクトイメージング露光法により行うことがより好ましい。 The light irradiation method used in the exposure step is preferably at least one method selected from a projection exposure method, a proximity exposure method, a contact exposure method, a direct imaging exposure method, and an electron beam direct drawing method. Alternatively, it is more preferable to carry out by a direct imaging exposure method.
　〔現像工程〕
　現像工程では、支持体を剥離した後、感光性樹脂層の非露光部（非パターン部）を、現像液に溶解させて除去する。現像液は、アルカリ水溶液を含む。ネガ型の感光性樹脂組成物を使用した場合、現像工程では、未露光部を除去することでレジストパターンを得る。ポジ型の感光性樹脂組成物を使用した場合、露光部を除去することでレジストパターンを得る。 [Development process]
In the development step, after peeling the support, the non-exposed area (non-pattern area) of the photosensitive resin layer is dissolved in a developer and removed. The developer contains an alkaline aqueous solution. When a negative photosensitive resin composition is used, a resist pattern is obtained by removing an unexposed portion in the development step. When a positive photosensitive resin composition is used, a resist pattern is obtained by removing the exposed area.
　アルカリ水溶液としては、Ｎａ2ＣＯ3、Ｋ2ＣＯ3等の、無機アルカリ水溶液を用いることが好ましい。アルカリ水溶液は、感光性樹脂層の特性に合わせて選択でき、好ましくは、０．２～２質量％の濃度のＮａ2ＣＯ3水溶液である。アルカリ水溶液には、界面活性剤と、消泡剤と、現像を促進させるための少量の有機溶剤と、等を混入させることができる。現像工程における現像液の温度は、１８～４０℃の範囲で一定温度に保つことが好ましい。 As the alkaline aqueous solution, it is preferable to use an inorganic alkaline aqueous solution such as Na 2 CO 3 or K 2 CO 3 . The alkaline aqueous solution can be selected according to the properties of the photosensitive resin layer, and is preferably an aqueous Na 2 CO 3 solution with a concentration of 0.2 to 2% by mass. A surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like can be mixed in the alkaline aqueous solution. The temperature of the developer in the developing process is preferably kept constant within the range of 18 to 40.degree.
　必要により、現像工程後、得られたレジストパターンを１００～３００℃で加熱する、加熱工程を行うことができる。加熱工程を実施することで、レジストパターンの耐薬品性、及び解像性を向上させ易くなる。ここでの加熱は、熱風、赤外線、遠赤外線等の方式を用いて行うことができる。 If necessary, after the development step, a heating step of heating the obtained resist pattern at 100 to 300° C. can be performed. By performing the heating step, it becomes easier to improve the chemical resistance and resolution of the resist pattern. The heating here can be performed using a method such as hot air, infrared rays, or far infrared rays.
　〔エッチング工程〕
　上記のレジストパターンの形成方法によってレジストパターンを形成し、次いで、必要によりめっき処理を行った後、基板に対してエッチングを行うことによって、レジストパターンに対応する配線パターンを基板に形成することができる。 [Etching process]
A wiring pattern corresponding to the resist pattern can be formed on the substrate by forming a resist pattern by the method of forming a resist pattern described above, then performing plating if necessary, and then etching the substrate. .
　エッチング工程は、例えば、レジストパターンの上からエッチング液を吹き付ける手法を採用することができる。エッチング方法としては、酸性エッチング、アルカリエッチング等が挙げられる。エッチング液としては、例えば、塩酸水溶液、塩化第二鉄水溶液、又はそれらの混合物等が挙げられる。 For the etching process, for example, a method of spraying an etchant from above the resist pattern can be adopted. The etching method includes acid etching, alkali etching, and the like. Examples of the etchant include aqueous hydrochloric acid, aqueous ferric chloride, and mixtures thereof.
　めっき処理は、既知のめっき法に従って、現像により露出した部分を、金属めっき（例えば硫酸銅めっき液による金属めっき）又ははんだめっきすることにより行うことができる。 Plating can be performed by metal plating (for example, metal plating with a copper sulfate plating solution) or solder plating on the exposed portion by development according to a known plating method.
　めっき処理を行う場合はそのめっき処理の後、めっき処理を省略する場合はエッチング工程の後、現像液よりも強いアルカリ性を有する水溶液（剥離液）により、レジストパターンを剥離することができる。剥離液は、例えば、濃度が約２～５質量％、かつ、温度が約４０℃～７０℃の、ＮａＯＨ又はＫＯＨの水溶液、もしくは、有機アミン系化合物の水溶液が好ましい。 The resist pattern can be removed with an aqueous solution (stripping solution) having stronger alkalinity than the developing solution after the plating process when plating is performed, or after the etching process when plating is omitted. The stripping solution is preferably, for example, an aqueous solution of NaOH or KOH or an aqueous solution of an organic amine compound having a concentration of about 2 to 5% by mass and a temperature of about 40°C to 70°C.
　上述した各種パラメータは、特に断りのない限り、後述する実施例における測定方法に準じて測定される。以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。 Unless otherwise specified, the various parameters described above are measured according to the measurement method in Examples described later. EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited by these examples.
　［実施例１～１８及び比較例１～１０］
　＜１．感光性樹脂組成物の調製＞
　後掲する表に示す各成分を混合し、さらに、溶媒であるアセトンを、固形分が６０質量％となるまで添加し、十分に攪拌、混合して感光性樹脂組成物調合液を調製した。表中の値は、固形分量である。 [Examples 1 to 18 and Comparative Examples 1 to 10]
<1. Preparation of photosensitive resin composition>
Each component shown in the table below was mixed, acetone as a solvent was added until the solid content reached 60% by mass, and the mixture was sufficiently stirred and mixed to prepare a photosensitive resin composition preparation. The values in the table are the solid content.
　＜２．感光性樹脂積層体の製造＞
　得られた調合液を、１６μｍ厚のポリエチレンテレフタレート（ＰＥＴ）フィルム（支持体）に、バーコーターを用いて均一に塗布し、９５℃の乾燥機中で３分間乾燥することで、感光性樹脂層（ドライフィルム）を形成した。感光性樹脂層の厚みは、２５μｍであった。その後、感光性樹脂層の、ＰＥＴフィルムを積層していない側に、保護フィルムとして、１９μｍ厚のポリエチレンフィルム（タマポリ（株）製、ＧＦ－１８）を貼り合わせて感光性樹脂積層体を得た。 <2. Manufacture of photosensitive resin laminate>
The resulting prepared solution was uniformly applied to a 16 μm thick polyethylene terephthalate (PET) film (support) using a bar coater and dried in a dryer at 95° C. for 3 minutes to form a photosensitive resin layer. (dry film) was formed. The thickness of the photosensitive resin layer was 25 μm. Thereafter, a 19 μm-thick polyethylene film (GF-18, manufactured by Tamapoly Co., Ltd.) was attached as a protective film to the side of the photosensitive resin layer on which the PET film was not laminated to obtain a photosensitive resin laminate. .
　＜３．基板の整面＞
　銅張積層基板の表面に対して、研磨機を用いた表面処理と、１０質量％Ｈ２ＳＯ４水溶液による洗浄と、を順次行うことで、該表面を整面した、これにより、厚み１８μｍの銅箔が積層された、厚み０．４ｍｍの銅張積層基板（基板）を得た。 <3. Substrate surface preparation>
The surface of the copper-clad laminate substrate was subjected to surface treatment using a polishing machine and washing with a 10% by mass H 2 SO 4 aqueous solution in order to smooth the surface. A copper clad laminate (substrate) having a thickness of 0.4 mm was obtained on which the copper foil was laminated.
　＜４．評価用基板の作製＞
　ラミネート：
　感光性樹脂積層体のポリエチレンフィルム（保護フィルム）を剥がしながら、ホットロールラミネーター（旭化成エレクトロニクス（株）製、ＡＬ－７００）を用い、上記のとおり整面した後に５０℃に予熱した基板に、感光性樹脂積層体をロール温度１０５℃でラミネートした。これにより、評価用基板を得た。エアー圧力は０．３５ＭＰａ、ラミネート速度は１．５ｍ／ｍｉｎとした。 <4. Preparation of substrate for evaluation>
laminate:
While peeling off the polyethylene film (protective film) of the photosensitive resin laminate, using a hot roll laminator (Asahi Kasei Electronics Co., Ltd., AL-700), the substrate was preheated to 50 ° C. after leveling as described above. The flexible resin laminate was laminated at a roll temperature of 105°C. Thus, an evaluation substrate was obtained. The air pressure was 0.35 MPa and the lamination speed was 1.5 m/min.
　露光：
　実施例１～１８、及び、比較例１～１０は、直接描画露光機（オーク製作所製ＦＤｉ－３、主波長４００ｎｍ）により、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、評価用基板を露光した。露光は、前記描画パターンのＬ（ライン）／Ｓ(スペース)＝１０μｍ/１０μｍの箇所を露光、現像したときの硬化レジストパターンの線幅が１０μｍとなる露光量で行った。
　実施例１９、２０は、分割投影露光装置（（株）ウシオ電機製ＵＸ２００３ ＳＭ－ＭＳ０４、ｉ線バンドパスフィルタ使用）により、所定のマスクパターンを用いて、ｉ線単色光で露光した。露光は、前記マスクパターンのＬ（ライン）／Ｓ(スペース)＝１０μｍ/１０μｍの箇所を露光、現像したときの硬化レジストパターンの線幅が１０μｍとなる露光量で行った。 exposure:
Examples 1 to 18 and Comparative Examples 1 to 10 are evaluated using a predetermined drawing pattern for direct imaging (DI) exposure using a direct drawing exposure machine (Oak Manufacturing FDi-3, dominant wavelength 400 nm). The substrate was exposed. The exposure was performed at an exposure amount such that the line width of the hardened resist pattern when exposed and developed was 10 μm at a portion of L (line)/S (space)=10 μm/10 μm in the drawing pattern.
Examples 19 and 20 were exposed to i-line monochromatic light using a predetermined mask pattern by a segmented projection exposure apparatus (UX2003 SM-MS04 manufactured by Ushio Inc., using an i-line bandpass filter). The exposure was performed at an exposure amount such that the line width of the cured resist pattern was 10 μm when exposed and developed at a portion of L (line)/S (space)=10 μm/10 μm of the mask pattern.
　加熱：
　露光後１分経過した評価用基板を、ホットロールラミネーター（旭化成（株）社製、ＡＬ－７００）を用いて加熱した。ロール温度は１０５℃、エアー圧は０．３０ＭＰａ、ラミネート速度は１ｍ／ｍｉｎであった。 heating:
One minute after exposure, the substrate for evaluation was heated using a hot roll laminator (AL-700, manufactured by Asahi Kasei Corp.). The roll temperature was 105° C., the air pressure was 0.30 MPa, and the lamination speed was 1 m/min.
　現像：
　ＰＥＴフィルム（支持フィルム）を剥離した後、アルカリ現像機（（株）フジ機工製、ドライフィルム用現像装置）を用いて、フルコーンタイプのノズルから、スプレー圧０．１５ＭＰａで、３０℃の１質量％Ｎａ２ＣＯ３水溶液を、最小現像時間の２倍の時間に亘ってスプレーした。これにより、感光性樹脂層の未露光部分を溶解除去した（現像）。現像後、現像時間の１．５倍の時間に亘って純水で洗浄し、エアーナイフで水切り処理後、温風乾燥を行うことによって、評価用硬化膜を有する基板を得た。 developing:
After peeling off the PET film (supporting film), using an alkaline developing machine (dry film developing machine manufactured by Fuji Kiko Co., Ltd.), from a full cone type nozzle at a spray pressure of 0.15 MPa, 1 at 30 ° C. A wt % Na 2 CO 3 aqueous solution was sprayed for twice the minimum development time. As a result, the unexposed portions of the photosensitive resin layer were dissolved and removed (development). After development, the substrate was washed with pure water for 1.5 times the development time, drained with an air knife, and dried with warm air to obtain a substrate having a cured film for evaluation.
　＜５．評価方法＞
　最小現像時間：
　上記方法で現像を行い、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た。
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。最小現像時間を下記のような基準によって評価した。
　Ａ：２５秒以下
　Ｂ：２５秒を超え、かつ、３０秒以下
　Ｃ：３０秒を超え、かつ、４０秒以下
　Ｄ：４０秒を超える <5. Evaluation method>
Minimum development time:
Development was carried out by the above method, and the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve was taken as the shortest development time.
A shorter minimum development time (unit: seconds) means better developability. The minimum development time was evaluated according to the following criteria.
A: 25 seconds or less B: Over 25 seconds and 30 seconds or less C: Over 30 seconds and 40 seconds or less D: Over 40 seconds
　解像度評価：
　本評価には、感光性樹脂積層体を、上記＜ラミネート＞に記載の方法でラミネートした後、１５分経過後の評価用基板を用いた。評価用基板に対し、種々のサイズで、ライン／スペース＝１／１のポジパターン又はネガパターンを露光した。その後、上記＜現像＞に記載の方法によって現像した。得られたパターンについて、形成されていた最小のパターン幅を光学顕微鏡により観察し、以下の基準によって解像性を評価した。
　Ａ：最小パターン幅が５μｍ以下
　Ｂ：最小パターン幅が５μｍを超え、かつ、6μｍ以下
　Ｃ：最小パターン幅が６μｍを超え、かつ、７μｍ以下
　Ｄ：最小パターン幅が７μｍを超える Resolution rating:
For this evaluation, the substrate for evaluation was used after 15 minutes had passed since the photosensitive resin laminate was laminated by the method described in <Lamination> above. A positive pattern or a negative pattern of line/space=1/1 was exposed to the substrate for evaluation in various sizes. Thereafter, development was performed by the method described in <Development> above. Regarding the obtained pattern, the formed minimum pattern width was observed with an optical microscope, and the resolution was evaluated according to the following criteria.
A: The minimum pattern width is 5 μm or less B: The minimum pattern width is over 5 μm and 6 μm or less C: The minimum pattern width is over 6 μm and 7 μm or less D: The minimum pattern width is over 7 μm
　密着性評価：
　本評価には、感光性樹脂積層体を、上記＜ラミネート＞に記載の方法でラミネートした後、１５分経過後の評価用基板を用いた。評価用基板に対し、種々のサイズで、独立ラインのパターンを直接描画露光した。その後、上記＜現像＞に記載の方法によって現像した。得られたパターンを光学顕微鏡により、倍率１００倍で観察し、以下の基準によって密着性を評価した。正常に形成とは、レジストに蛇行及び欠けが生じていないことを指す。
　Ａ：正常に形成された最小パターンが８μｍ以下
　Ｂ：正常に形成された最小パターンが８μｍを超え、かつ、９μｍ以下
　Ｃ：正常に形成された最小パターンが９μｍを超え、かつ、１０μｍ以下
　Ｄ：正常に形成された最小パターンが１０μｍを超える Adhesion evaluation:
For this evaluation, the substrate for evaluation was used after 15 minutes had passed since the photosensitive resin laminate was laminated by the method described in <Lamination> above. Independent line patterns of various sizes were directly written and exposed to the substrate for evaluation. Thereafter, development was performed by the method described in <Development> above. The obtained pattern was observed with an optical microscope at a magnification of 100 times, and the adhesion was evaluated according to the following criteria. "Normal formation" means that the resist is neither meandering nor chipped.
A: The normally formed minimum pattern is 8 μm or less B: The normally formed minimum pattern is over 8 μm and 9 μm or less C: The normally formed minimum pattern is over 9 μm and 10 μm or less D: Minimum pattern successfully formed exceeds 10 μm
　プレスフロー評価：
　感光性樹脂積層体を２．５ｃｍ角に切り出し、カバーフィルム（保護フィルム）を剥がした後、ＰＥＴフィルム１０ｃｍ角の中央に挟み、４０℃に加熱した油圧プレスにより、１００ｋｇの力を５分間加えた。その後、感光性樹脂層のはみ出し幅を４方向（計８点）において測定し、その平均値を求めた。本試験は２回行い、その平均値をプレスフロー試験の値とし、以下の基準によってプレスフローを評価した。
　Ａ：１００μｍ以下
　Ｂ：１００μｍを超え、かつ、１５０μｍ以下
　Ｃ：１５０μｍを超え、かつ、２００μｍ以下
　Ｄ：２００μｍを超える Press flow rating:
The photosensitive resin laminate was cut into 2.5 cm squares, the cover film (protective film) was peeled off, and then sandwiched in the center of a 10 cm square PET film. . Thereafter, the protrusion width of the photosensitive resin layer was measured in 4 directions (8 points in total), and the average value was obtained. This test was performed twice, and the average value was used as the value of the press flow test, and the press flow was evaluated according to the following criteria.
A: 100 μm or less B: More than 100 μm and 150 μm or less C: More than 150 μm and 200 μm or less D: More than 200 μm
　支持体の引き剥がし強度（タック性）：
　本評価には、上記＜ラミネート＞に記載の方法で、感光性樹脂積層体を片面にラミネートした評価用基板を用意し、２４時間２３℃、５０％相対湿度下に放置した。その後、１インチ幅の支持体（本実施例ではＰＥＴフィルム）を１００ｍｍ／ｍｉｎの速度で１８０°引き剥がし、そのときの強度を、テンシロンＲＴＭ－５００（東洋精機製）で測定し、以下の基準によって引き剥がし強度を評価した。
　Ａ：引き剥がし強度が、３．０ｇｆ未満
　Ｄ：引き剥がし強度が、３．０ｇｆ以上 Peel strength of support (tackiness):
For this evaluation, a substrate for evaluation was prepared by laminating a photosensitive resin laminate on one side by the method described in <Lamination> above, and left for 24 hours at 23° C. and 50% relative humidity. After that, the 1 inch wide support (PET film in this example) was peeled off 180° at a speed of 100 mm / min, and the strength at that time was measured with Tensilon RTM-500 (manufactured by Toyo Seiki). The peel strength was evaluated by
A: Peel strength is less than 3.0 gf D: Peel strength is 3.0 gf or more
　剥離試験：
　本評価では、３５μｍ圧延銅箔を積層した１．６ｍｍ厚の銅張積層板の表面を、湿式バフロール研磨により整面したものを、評価用基板として用いた。研磨は、スリーエム（株）製、スコッチブライト（登録商標）ＨＤ♯６００を用い、２回行った。 Peel test:
In this evaluation, the surface of a 1.6 mm thick copper-clad laminate laminated with a 35 μm rolled copper foil was smoothed by wet buff roll polishing and used as an evaluation substrate. Polishing was performed twice using Scotch-Brite (registered trademark) HD#600 manufactured by 3M Corporation.
　感光性樹脂層の厚みが２５μｍである感光性樹脂積層体からポリエチレンフィルムを剥がしながら、整面後の評価用基板に、ホットロールラミネーター（旭化成（株）製、ＡＬ－７００）を用いて、ロール温度１０５℃、エアー圧力０．３５ＭＰａ、及びラミネート速度１．５ｍ／分の条件下でラミネートした。
　ラミネート後１５分経過した評価用基板を用い、該評価用基板に対し、４ｃｍ×６ｃｍの長方形パターンを、上記＜露光＞に記載の方法で露光した後、上記＜現像＞に記載の方法によって現像した。得られた評価用基板を４ｃｍ×６ｃｍに切り出し、５０℃、Ｒ－１０１（三菱ガス化学（株）製）の剥離液に浸し、評価用基板から感光性樹脂層が完全に剥離するまでの時間を測定し、これを剥離時間として、以下の基準によって剥離性を評価した。
　Ａ：剥離時間が、２０ｓ以下
　Ｂ：剥離時間が、２０ｓを超え、かつ、２５ｓ以下
　Ｄ：剥離時間が、２５ｓを超える While peeling off the polyethylene film from the photosensitive resin laminate having a photosensitive resin layer thickness of 25 μm, a hot roll laminator (manufactured by Asahi Kasei Co., Ltd., AL-700) was used to roll the substrate for evaluation after surface preparation. Lamination was performed under conditions of a temperature of 105° C., an air pressure of 0.35 MPa, and a lamination speed of 1.5 m/min.
Using an evaluation substrate 15 minutes after lamination, a rectangular pattern of 4 cm × 6 cm was exposed to the evaluation substrate by the method described in <Exposure> above, and then developed by the method described in <Development> above. bottom. The obtained evaluation substrate was cut into a size of 4 cm × 6 cm, immersed in a stripping solution of R-101 (Mitsubishi Gas Chemical Co., Ltd.) at 50 ° C., and the time until the photosensitive resin layer was completely peeled off from the evaluation substrate. was measured, and using this as the peeling time, the peelability was evaluated according to the following criteria.
A: Peeling time is 20 s or less B: Peeling time is more than 20 s and 25 s or less D: Peeling time is more than 25 s
　表に示される結果から、実施例では、［最小現像時間］、［解像度］、及び［密着性］の全ての項目が「Ｂ」以上であることが確かめられた。 From the results shown in the table, it was confirmed that all items of [Minimum development time], [Resolution], and [Adhesion] were "B" or higher in Examples.

Claims (28)

  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）成分が、少なくとも、下記のコモノマー成分：
    　（ａ）メタクリル酸又はアクリル酸、
    　（ｂ）前記（ａ）成分として選択された酸とは異なるカルボン酸、及び
    　（ｃ）芳香族構造又は脂環式構造を有する化合物、
    に由来する構成単位を有し、
    　前記（Ａ）成分における、
    　前記（ａ）成分に由来する構成単位の質量割合（ａ１）と、
    　前記（ｂ）成分に由来する構成単位の質量割合（ｂ１）と、
    の比率（前記質量割合（ａ１）／前記質量割合（ｂ１））が、１／１０～１０である、感光性樹脂組成物。     Ingredients for:
    (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) contains at least the following comonomer components:
    (a) methacrylic acid or acrylic acid,
    (b) a carboxylic acid different from the acid selected as component (a); and (c) a compound having an aromatic or alicyclic structure,
    has a structural unit derived from
    In the component (A),
    The mass ratio (a1) of structural units derived from the component (a);
    a mass ratio (b1) of structural units derived from the component (b);
    ratio (the mass ratio (a1)/the mass ratio (b1)) is 1/10 to 10, a photosensitive resin composition.
  2. 　前記比率（前記質量割合（ａ１）／前記質量割合（ｂ１））が、１／８～８である、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the ratio (the mass ratio (a1)/the mass ratio (b1)) is 1/8 to 8.
  3. 　前記（Ａ）成分は、コモノマー成分として、（ｄ）ヒドロキシアルキル（メタ）アクリル酸エステルに由来する構成単位、を更に有する、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the (A) component further comprises (d) a structural unit derived from a hydroxyalkyl (meth)acrylic acid ester as a comonomer component.
  4. 　前記（ｄ）成分は、ヒドロキシエチルメタクリレートである、請求項３に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 3, wherein the component (d) is hydroxyethyl methacrylate.
  5. 　前記（ａ）成分は、メタクリル酸である、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the component (a) is methacrylic acid.
  6. 　前記（ｂ）成分は、アクリル酸である、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the component (b) is acrylic acid.
  7. 　前記（Ａ）成分における、
    　前記（ａ）成分に由来する構成単位の質量割合（ａ１）と、
    　前記（ｂ）成分に由来する構成単位の質量割合（ｂ１）と、の合計は、１～６５質量％である、請求項１に記載の感光性樹脂組成物。     In the component (A),
    The mass ratio (a1) of structural units derived from the component (a);
    2. The photosensitive resin composition according to claim 1, wherein the total mass ratio (b1) of the constituent units derived from component (b) is 1 to 65% by mass.
  8. 　前記（ｃ）成分は、スチレン及び／又はベンジル（メタ）アクリレートを含む、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the component (c) contains styrene and/or benzyl (meth)acrylate.
  9. 　前記（Ａ）成分における、前記（ｃ）成分に由来する構成単位の割合は、１０～９５質量％である、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the proportion of structural units derived from component (c) in component (A) is 10 to 95% by mass.
  10. 　前記（ｃ）成分は、スチレンを含む、請求項８に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 8, wherein the component (c) contains styrene.
  11. 　前記（Ａ）成分における、前記スチレンに由来する構成単位の割合が４５～９５質量％である、請求項１０に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 10, wherein the ratio of the structural unit derived from styrene in the component (A) is 45 to 95% by mass.
  12. 　前記感光性樹脂組成物の固形分総量を基準として、
    　前記（Ａ）成分：１０～９０質量％、
    　前記（Ｂ）成分：５～７０質量％、及び
    　前記（Ｃ）成分：０．０１～２０質量％、
    　を含む、請求項１に記載の感光性樹脂組成物。     Based on the total solid content of the photosensitive resin composition,
    Component (A): 10 to 90% by mass,
    The (B) component: 5 to 70% by mass, and the (C) component: 0.01 to 20% by mass,
    The photosensitive resin composition according to claim 1, comprising:
  13. 　前記（Ａ）成分は、複数のアルカリ可溶性高分子を含む、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the component (A) contains a plurality of alkali-soluble polymers.
  14. 　前記質量割合（ａ１）の質量平均と、前記質量割合（ｂ１）の質量平均と、の関係（質量割合（ａ１）の質量平均／質量割合（ｂ１）の質量平均）が、１／１０～１０である、請求項１３に記載の感光性樹脂組成物。 The relationship between the mass average of the mass ratio (a1) and the mass average of the mass ratio (b1) (mass average of mass ratio (a1) / mass average of mass ratio (b1)) is 1/10 to 10 The photosensitive resin composition according to claim 13, which is
  15. 　前記（Ａ）成分に含まれるアルカリ可溶性高分子の少なくとも一つは、
    　前記（ａ）成分～（ｃ）成分に由来する構成単位を有し、かつ、前記比率を満たす、請求項１３に記載の感光性樹脂組成物。     At least one of the alkali-soluble polymers contained in the component (A),
    14. The photosensitive resin composition according to claim 13, which has structural units derived from the components (a) to (c) and satisfies the ratio.
  16. 　前記（Ａ）成分に含まれるアルカリ可溶性高分子のうち、
    　前記（ａ）成分～（ｃ）成分に由来する構成単位を有し、かつ、
    　前記比率を満たすアルカリ可溶性高分子の割合は１０質量％以上である、請求項１５に記載の感光性樹脂組成物。     Among the alkali-soluble polymers contained in the component (A),
    Having structural units derived from the components (a) to (c), and
    16. The photosensitive resin composition according to claim 15, wherein the ratio of the alkali-soluble polymer that satisfies the ratio is 10% by mass or more.
  17. 　前記（Ａ）成分の酸価が、５０～６００ｍｇＫＯＨ／ｇである、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the component (A) has an acid value of 50 to 600 mgKOH/g.
  18. 　前記（Ｂ）成分は、ビスフェノールＡ構造、及び／又は水添ビスフェノールＡ構造を有する化合物を含む、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the component (B) contains a compound having a bisphenol A structure and/or a hydrogenated bisphenol A structure.
  19. 　前記（Ｂ）成分は、一分子中に、前記エチレン性不飽和結合を３つ以上有する化合物を含む、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the component (B) contains a compound having three or more ethylenically unsaturated bonds in one molecule.
  20. 　前記（Ｃ）成分は、ヘキサアリールビイミダゾール（ＨＡＢＩ）化合物を含む、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the component (C) contains a hexaarylbiimidazole (HABI) compound.
  21. 　（Ｄ）成分として、ロイコ染料を更に含む、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, further comprising a leuco dye as the component (D).
  22. 　前記（Ａ）成分における、
    　前記（ａ）成分に由来する構成単位の質量割合（ａ１）と、
    　前記（ｂ）成分に由来する構成単位の質量割合（ｂ１）と、
    　前記（ｃ）成分に由来する構成単位の質量割合（ｃ１）と、が下記式（１）～（３）：
    　　１０≦（ａ１）＋（ｂ１）≦５０　・・・　（１）
    　　０．５≦（ａ１）／（ｂ１）≦８．０　・・・　（２）
    　　３０≦（ｃ１）≦８０　・・・　（３）
    を満たす、請求項１に記載の感光性樹脂組成物。     In the component (A),
    The mass ratio (a1) of structural units derived from the component (a);
    a mass ratio (b1) of structural units derived from the component (b);
    The mass ratio (c1) of the structural unit derived from the component (c) is represented by the following formulas (1) to (3):
    10≦(a1)+(b1)≦50 (1)
    0.5≦(a1)/(b1)≦8.0 (2)
    30≦(c1)≦80 (3)
    The photosensitive resin composition according to claim 1, which satisfies:
  23. 　前記（Ａ）成分は、複数のアルカリ可溶性高分子を含み、
    　前記（Ａ）成分に含まれるアルカリ可溶性高分子の少なくとも一つは、前記（ａ）成分～（ｃ）成分に由来する構成単位を有し、かつ、
    　前記質量割合（ａ１）、（ｂ１）、及び（ｃ１）が、前記式（１）～（３）を満たす、請求項２２に記載の感光性樹脂組成物。     The component (A) contains a plurality of alkali-soluble polymers,
    At least one of the alkali-soluble polymers contained in component (A) has structural units derived from components (a) to (c), and
    The photosensitive resin composition according to claim 22, wherein the mass proportions (a1), (b1), and (c1) satisfy the formulas (1) to (3).
  24. 　前記（Ａ）成分に含まれるアルカリ可溶性高分子のうち、
    　前記（ａ）成分～（ｃ）成分に由来する構成単位を有し、かつ、前記質量割合（ａ１）、（ｂ１）、（ｃ１）が前記式（１）～（３）を満たすアルカリ可溶性高分子の割合は、１０質量％以上である、請求項２３に記載の感光性樹脂組成物。     Among the alkali-soluble polymers contained in the component (A),
    Having structural units derived from the components (a) to (c), and having the mass ratios (a1), (b1), and (c1) satisfying the formulas (1) to (3) 24. The photosensitive resin composition according to claim 23, wherein the proportion of molecules is 10% by mass or more.
  25. 　支持体と、請求項１～２４のいずれか１項に記載の感光性樹脂組成物から得られる感光性樹脂層と、を備える、感光性樹脂積層体。 A photosensitive resin laminate comprising a support and a photosensitive resin layer obtained from the photosensitive resin composition according to any one of claims 1 to 24.
  26. 　前記感光性樹脂層の、前記支持体とは反対側に、保護フィルムを備える、請求項２５に記載の感光性樹脂積層体。 The photosensitive resin laminate according to claim 25, comprising a protective film on the side of the photosensitive resin layer opposite to the support.
  27. 　請求項２５又は２６に記載の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の感光性樹脂層を露光する工程、及び
    　露光した前記感光性樹脂層を現像する工程、
    　を有する、レジストパターン形成方法。     A step of laminating the photosensitive resin laminate according to claim 25 or 26 on a substrate;
    a step of exposing the photosensitive resin layer of the laminated photosensitive resin laminate, and a step of developing the exposed photosensitive resin layer,
    A method of forming a resist pattern, comprising:
  28. 　前記露光を、ダイレクトイメージング露光によって行う、請求項２７に記載のレジストパターン形成方法。 The resist pattern forming method according to claim 27, wherein the exposure is performed by direct imaging exposure.
PCT/JP2023/000842 2022-01-14 2023-01-13 Photosensitive resin composition, photosensitive resin laminate, and resist pattern formation method WO2023136333A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002023365A (en) * 2000-07-13 2002-01-23 Asahi Kasei Corp Photosensitive resin laminate
WO2007080698A1 (en) * 2006-01-13 2007-07-19 Fujifilm Corporation Photosensitive resin composition, photosensitive transfer film, and method for pattern formation
CN108287452A (en) * 2018-01-24 2018-07-17 浙江福斯特新材料研究院有限公司 It is a kind of that there is rapid development and the excellent Photosensitve resin composition for covering special-shaped pore performance

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JPH08339081A (en) 1995-06-09 1996-12-24 Tokyo Ohka Kogyo Co Ltd Photosensitive resin composition and its production
WO2019244724A1 (en) 2018-06-22 2019-12-26 旭化成株式会社 Photosensitive resin composition and resist pattern formation method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002023365A (en) * 2000-07-13 2002-01-23 Asahi Kasei Corp Photosensitive resin laminate
WO2007080698A1 (en) * 2006-01-13 2007-07-19 Fujifilm Corporation Photosensitive resin composition, photosensitive transfer film, and method for pattern formation
CN108287452A (en) * 2018-01-24 2018-07-17 浙江福斯特新材料研究院有限公司 It is a kind of that there is rapid development and the excellent Photosensitve resin composition for covering special-shaped pore performance

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