WO2023136333A1 - 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 - Google Patents

感光性樹脂組成物、感光性樹脂積層体、及びレジストパターンの形成方法 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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Prior art keywords
photosensitive resin
component
resin composition
mass
composition according
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PCT/JP2023/000842
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English (en)
French (fr)
Japanese (ja)
Inventor
大介 宇野
隆覚 櫻井
秀昭 西本
裕樹 松尾
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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/ko
Publication of WO2023136333A1 publication Critical patent/WO2023136333A1/ja

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—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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PCT/JP2023/000842 2022-01-14 2023-01-13 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 WO2023136333A1 (ja)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002023365A (ja) * 2000-07-13 2002-01-23 Asahi Kasei Corp 感光性樹脂積層体
WO2007080698A1 (ja) * 2006-01-13 2007-07-19 Fujifilm Corporation 感光性樹脂組成物及び感光性転写フィルム並びにパターン形成方法
CN108287452A (zh) * 2018-01-24 2018-07-17 浙江福斯特新材料研究院有限公司 一种具有快速显影和优异掩盖异形孔性能的感光树脂组合物

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JPH08339081A (ja) 1995-06-09 1996-12-24 Tokyo Ohka Kogyo Co Ltd 感光性樹脂組成物及びその製造方法
WO2019244724A1 (ja) 2018-06-22 2019-12-26 旭化成株式会社 感光性樹脂組成物およびレジストパターンの形成方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002023365A (ja) * 2000-07-13 2002-01-23 Asahi Kasei Corp 感光性樹脂積層体
WO2007080698A1 (ja) * 2006-01-13 2007-07-19 Fujifilm Corporation 感光性樹脂組成物及び感光性転写フィルム並びにパターン形成方法
CN108287452A (zh) * 2018-01-24 2018-07-17 浙江福斯特新材料研究院有限公司 一种具有快速显影和优异掩盖异形孔性能的感光树脂组合物

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