CN105765458B - Negative photosensitive resin composition - Google Patents

Negative photosensitive resin composition Download PDF

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Publication number
CN105765458B
CN105765458B CN201480065093.4A CN201480065093A CN105765458B CN 105765458 B CN105765458 B CN 105765458B CN 201480065093 A CN201480065093 A CN 201480065093A CN 105765458 B CN105765458 B CN 105765458B
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component
photosensitive resin
resin composition
group
mass
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CN105765458A (en
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内山芽育
菅野裕太
石田智久
畑中真
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/18—Diffraction gratings
    • G02B5/1847—Manufacturing methods
    • G02B5/1857—Manufacturing methods using exposure or etching means, e.g. holography, photolithography, exposure to electron or ion beams
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133345—Insulating layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/02—Materials and properties organic material
    • G02F2202/022—Materials and properties organic material polymeric
    • G02F2202/023—Materials and properties organic material polymeric curable

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

The invention provides a negative photosensitive resin composition, which has an increased curing speed, can fully cure the surface of a coating film by exposure from the back of a substrate even if the film thickness is more than 15 mu m, and can form a fine transparent structure. The photosensitive resin composition contains a component (A), a component (B), a component (C-1), a component (C-2) and a component (D). (A) The components: an alkali-soluble copolymer, (B) component: a compound having at least 1 polymerizable group of 2 or more selected from an acrylate group, a methacrylate group, a vinyl group and an allyl group, component (C-1): a photoinitiator having an oxime ester group and having an absorption coefficient at 365nm in methanol or acetonitrile of 5,000ml/g cm or more, a component (C-2): a photoinitiator having an absorption coefficient at 365nm in methanol or acetonitrile of 100ml/g cm or less, and a component (D): a solvent.

Description

Negative photosensitive resin composition
Technical Field
The present invention relates to a negative photosensitive resin composition and a cured film obtained from the negative photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition suitable for use in display materials, a cured film thereof, and various materials using the cured film.
Background
It is known that: an epoxy cationic polymerization-based UV curable resin composition containing an epoxy compound and a photoacid generator, which has been proposed as a negative photosensitive resin composition, has high transparency and can be formed into a thick film (for example, patent document 1).
Further, as a negative-type material capable of alkaline development, a radical polymerization type negative-type material containing a polymer having an acryloyl group, a polyfunctional acrylic monomer, and a photo radical initiator is known (for example, patent document 2).
On the other hand, it is known that a positive type material has high resolution, but is difficult to form a thick film and has low transparency (for example, patent document 3).
Documents of the prior art
Patent document
Patent document 1: international publication No. 2008/007764 pamphlet
Patent document 2: japanese laid-open patent publication No. 2004-302389
Patent document 3: japanese laid-open patent publication No. 8-339082
Disclosure of Invention
Problems to be solved by the invention
The photosensitive resin composition disclosed in patent document 1 is liable to cause wrinkles (tack) in the coating film after coating and before exposure, and is poor in workability. In addition, development with an aqueous alkaline solution is not possible, and therefore development with an organic solvent is necessary. It is considered that the alkali development can be achieved by introducing a carboxyl group into the polymer, but when a monomer having an epoxy group and a monomer having a carboxyl group are copolymerized, the reaction of the epoxy group and the carboxyl group is likely to occur in the polymerization, and the synthesis control of the polymer is difficult. Further, even if the polymer can be synthesized by controlling the reaction, the storage stability is low.
The negative-type material described in patent document 2, which is capable of alkali development, has low curability for a thick film of 15 μm or more, and cannot be sufficiently cured to the surface of a coating film in a process such as exposure from the back surface of a substrate, and it is difficult to form a rectangular pattern. In addition, when a photo radical initiator having a high absorption coefficient is added in an excessive amount, it can be cured to the surface even in the case of exposure from the back surface of the substrate, but in this case, the transmittance of the cured film is lowered, and it is difficult to use the cured film as an optical element.
From these points of view, a material having high transparency, capable of alkali development, high workability even when the film is made thick, and excellent curability is desired.
The present invention has been made in view of the above circumstances, and provides a negative photosensitive resin composition which has a film thickness of 15 μm or more, can be cured from the back surface of a substrate with a small exposure amount, has high transparency after curing, and can form a fine transparent structure.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a photosensitive resin composition having excellent curability even with a low exposure dose, capable of pattern formation, and excellent transparency can be obtained by using 2 types of photoinitiators having different absorption coefficients as a photoinitiator in combination, and have completed the present invention.
That is, the invention relates to 1 st aspect, which relates to a photosensitive resin composition containing the following component (A), component (B), component (C-1), component (C-2) and component (D).
(A) The components: an alkali-soluble copolymer of a carboxylic acid and a carboxylic acid,
(B) the components: a compound having at least 1 polymerizable group of 2 or more selected from an acrylate group, a methacrylate group, a vinyl group and an allyl group,
(C-1) component: a photoinitiator having an oxime ester group and having an absorption coefficient of 5,000ml/g cm or more in methanol or acetonitrile at 365nm,
(C-2) component: a photoinitiator having an absorption coefficient of 100ml/g cm or less in methanol or acetonitrile at 365nm,
(D) the components: a solvent.
A 2 nd aspect relates to the photosensitive resin composition according to the 1 st aspect, which further contains a thiol compound as the component (E).
In a 3 rd aspect, the photosensitive resin composition according to the 1 st or 2 nd aspect, the component (a) is an alkali-soluble copolymer having a number average molecular weight of 2,000 to 50,000 in terms of polystyrene.
As a4 th aspect, the photosensitive resin composition according to any one of the 1 st to 3 rd aspects, wherein the alkali-soluble copolymer of the component (a) is a copolymer produced by copolymerization of a monomer mixture containing at least 1 selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride and maleimide.
The photosensitive resin composition according to any one of aspects 1 to 4, wherein the content of the component (C-1) is 0.3 to 5 parts by mass based on 100 parts by mass of the component (A).
The photosensitive resin composition according to claim 6 relates to any one of claims 1 to 5, wherein the content of the component (C-2) is 0.5 to 10 parts by mass based on 100 parts by mass of the component (A).
The photosensitive resin composition according to any one of aspects 1 to 6, wherein the content of the component (B) is 10 to 150 parts by mass based on 100 parts by mass of the component (a) as aspect 7.
The photosensitive resin composition according to any one of aspects 1 to 7, wherein the component (C-1) is a photoinitiator having a carbazole structure.
The photosensitive resin composition according to claim 9 relates to any one of claims 1 to 8, wherein the component (C-2) is a photoinitiator having a hydroxyl group.
The 10 th aspect relates to the photosensitive resin composition according to any one of the 1 st to 9 th aspects, further comprising a surfactant as the component (F).
The 11 th aspect relates to a cured film obtained by using the photosensitive resin composition according to any one of the 1 st to 10 th aspects.
The 12 th aspect relates to a cured film obtained by exposing a coating film on a light-transmitting substrate to light from a surface of the substrate opposite to the coating film surface, the coating film being formed from the photosensitive resin composition according to any one of the 1 st to 10 th aspects.
From the 13 th viewpoint, the present invention relates to an interlayer insulating film for a liquid crystal display, which comprises the cured film according to the 11 th or 12 th viewpoint.
The 14 th aspect of the present invention relates to an optical filter comprising the cured film according to the 11 th or 12 th aspect.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, by using a mixture of an oxime ester photoinitiator having an absorption coefficient of 5,000 ml/g-cm or more in methanol or acetonitrile at 365nm and a photoinitiator having an absorption coefficient of 100 ml/g-cm or less in methanol or acetonitrile at 365nm as a photoinitiator of a radical curing type negative resist composition, the curing rate by exposure can be increased, and even if the film thickness is 15 μm or more, the surface of the coating film can be sufficiently cured by exposure from the back surface of the substrate, and a fine transparent structure can be formed.
Detailed Description
The photosensitive resin composition of the present invention is a photosensitive resin composition containing the following component (A), component (B), component (C-1), component (C-2) and component (D).
(A) The components: an alkali-soluble copolymer of a carboxylic acid and a carboxylic acid,
(B) the components: a compound having at least 1 polymerizable group of 2 or more selected from an acrylate group, a methacrylate group, a vinyl group and an allyl group,
(C-1) component: a photoinitiator having an oxime ester group and having an absorption coefficient of 5,000ml/g cm or more in methanol or acetonitrile at 365nm,
(C-2) component: a photoinitiator having an absorption coefficient of 100ml/g cm or less in methanol or acetonitrile at 365nm,
(D) the components: a solvent.
< component (A) >
(A) The component (a) is an alkali-soluble polymer and is a copolymer produced by copolymerization of a monomer mixture containing a monomer having an alkali-soluble group and another monomer (hereinafter, also simply referred to as a copolymer of the component (a)).
(A) The copolymer of component (a) may be any copolymer having such a structure, and the types of the backbone and side chain of the main chain of the polymer constituting the copolymer are not particularly limited.
However, if the number average molecular weight of the copolymer of the component (a) exceeds 50,000 and is too large, the developability of unexposed portions is lowered, while if the number average molecular weight is less than 2,000 and is too small, the curing of exposed portions is insufficient, and thus the components may elute during development. Therefore, the copolymer as the component (A) is preferably selected to have a number average molecular weight in the range of 2,000 to 50,000. In the present specification, the number average molecular weight and the weight average molecular weight described later are both measured in terms of polyester by Gel Permeation Chromatography (GPC).
Examples of the monomer having an alkali-soluble group include monomers having a carboxyl group, a phenolic hydroxyl group, an acid anhydride group, and a maleimide group.
Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, and 4-vinylbenzoic acid.
Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, and N- (hydroxyphenyl) maleimide.
Examples of the monomer having an acid anhydride group include maleic anhydride and itaconic anhydride.
Examples of the monomer having a maleimide group include maleimide, the above-mentioned N- (carboxyphenyl) maleimide, and N- (hydroxyphenyl) maleimide.
Among these monomers having an alkali-soluble group, preferred is a copolymer obtained by copolymerizing a monomer mixture containing at least 1 selected from acrylic acid, methacrylic acid, maleic anhydride, and maleimide.
Further, in the present invention, in obtaining the above-mentioned copolymer, another monomer copolymerizable with the above-mentioned monomer having an alkali-soluble group is used in combination.
Specific examples of such other monomers include acrylate compounds, methacrylate compounds, N-substituted maleimide compounds, acrylonitrile compounds, acrylamide compounds, methacrylamide compounds, styrene compounds, vinyl compounds, and the like.
Specific examples of the other monomers are given below, but the monomers are not limited thereto.
Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, phenyl acrylate, phenoxyethyl acrylate, 2,2, 2-trifluoroethyl acrylate, t-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecanyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and mixtures thereof, 4-hydroxybutyl acrylate, 2, 3-dihydroxypropyl acrylate, diethylene glycol monoacrylate, caprolactone 2- (acryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, acryloylethyl isocyanate and 8-ethyl-8-tricyclodecanyl acrylate, glycidyl acrylate, and the like.
Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate, 2,2, 2-trifluoroethyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ -butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, and mixtures thereof, 8-methyl-8-tricyclodecyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2, 3-dihydroxypropyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, methacryloylethyl isocyanate and 8-ethyl-8-tricyclodecyl methacrylate, glycidyl methacrylate and the like.
Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.
Examples of the N-substituted maleimide compound include N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
Examples of the acrylonitrile compound include acrylonitrile and the like.
The method for obtaining the copolymer of the component (a) used in the present invention is not particularly limited, and for example, the copolymer is obtained by performing a polymerization reaction in a solvent in which a monomer mixture containing the monomer having the alkali-soluble group and the other monomer and a polymerization initiator and the like are coexistent as necessary at a temperature of 50 to 110 ℃. In this case, the solvent to be used is not particularly limited as long as it dissolves the monomer having an alkali-soluble group and the copolymer of the other monomer and the component (a). Specific examples thereof include those described in the solvent for component (D) described later.
The alkali-soluble copolymer thus obtained is usually in the state of a solution dissolved in a solvent.
The copolymer solution of the component (a) obtained as described above is put into diethyl ether, water or the like under stirring to reprecipitate, and the resultant precipitate is filtered and washed, and then dried at normal temperature or under reduced pressure, whereby the copolymer powder can be prepared. By such an operation, the polymerization initiator and the unreacted monomer coexisting with the copolymer can be removed, and as a result, a purified powder of the copolymer can be obtained. When the purification cannot be sufficiently performed in one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
In the present invention, the polymerization solution of the alkali-soluble copolymer (a) may be used as it is, or the powder may be redissolved in a solvent of, for example, component (D) described later to prepare a solution.
The copolymerization ratio of the monomers is preferably 5 to 50 parts by mass of the alkali-soluble monomer/other monomer/50 to 95 parts by mass. If the copolymerization ratio of the alkali-soluble monomer is too low, the unexposed portion does not dissolve in the developer, and thus tends to cause a residual film or residue. In addition, when the copolymerization ratio of the alkali-soluble monomer is too large, the exposed portion may have insufficient curability and a pattern may not be formed.
< ingredient (B) >
(B) The component (A) is a compound having 2 or more polymerizable groups. The compound having 2 or more polymerizable groups as used herein means a compound having 2 or more polymerizable groups in one molecule and these polymerizable groups are at the molecular terminals. The polymerizable group is an acrylate group, a methacrylate group, a vinyl group or an allyl group, and the component (B) is a compound having at least one group of 2 or more.
The compound having 2 or more polymerizable groups as the component (B) is preferably a compound having a weight average molecular weight of 1,000 or less, from the viewpoint that the compatibility with each component in the solution of the negative photosensitive resin composition of the present invention is good and the developability is not affected.
Specific examples of such compounds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethylacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,3, 5-triacryloylhexahydro-S-triazine, 1,3, 5-trimethacryloylhexahydro-S-triazine, tris (hydroxyethylacryloyl) isocyanurate, tris (hydroxyethylmethacryloyl) isocyanurate, triacrylformal, trimethylacryloyl formal, 1, 6-hexanediol acrylate, 1, 6-hexanediol methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 2-hydroxypropanediol diacrylate, 2-hydroxypropanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, isopropylene glycol diacrylate, isopropylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, N '-bis (acryloyl) cysteine, N' -bis (methacryloyl) cysteine, N, 6-hexanediol methacrylate, 2-hydroxypropanediol dimethacrylate, and mixtures thereof, Thiodiglycol diacrylate, thiodiglycol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate, bisphenol S dimethacrylate, bisphenoxyethanolfluorene diacrylate, bisphenoxyethanolfluorene dimethacrylate, diallyl ether bisphenol A, orthodiallyl bisphenol A, diallyl maleate, triallyl trimellitate, and the like.
The above-mentioned polyfunctional acrylate compound can be easily obtained as a commercially available product, and as a specific example thereof, examples thereof include KAYARAD (registered trademark) T-1420, KAYARAD DPHA, KAYARAD DPHA-2C, KAYARAD-310, KAYARAD D-330, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD DN-0075, KAYARAD DN-2475, KAYARAD R-526, KAYARAD NPGDA, KAYARAD PEG400DA, KAYARAD MANDA, KAYARAD R-167, KAYARAD HX-220, KAYARAD HX620, KAYARAD R-684, KARADYA R-712, KAYARAD R-604, KAYARAD R-684, KAYARAD GPO-303, KAYARAD TMPTA, KAYARAD THE-330, KAYARAD TPA-320, KAYARAD TPA-330, KAYARAD PET-30 and KAYARAD RP-1040 (manufactured by KAYARAD COR CORPORATION, CORPORATION, CORPORATION AND CORPORATION, CORPORATION CO-551); アロニックス (registered trademark) M-210, アロニックス M-208, アロニックス M-211B, アロニックス M-215, アロニックス M-220, アロニックス M-225, アロニックス M-270, アロニックス M-240, アロニックス M-6100, アロニックス M-6250, アロニックス M-6500, アロニックス M-6200, アロニックス M-309, アロニックス M-310, アロニックス M-321, アロニックス M-350, アロニックス M-360, アロニックス M-313, アロニックス M-315, アロニックス M-306, アロニックス M-303, アロニックス M-306, and the like, アロニックス M-452, アロニックス M-408, アロニックス M-403, アロニックス M-400, アロニックス M-402, アロニックス M-405, アロニックス M-406, アロニックス M-450, アロニックス M-460, アロニックス M-510, アロニックス M-520, アロニックス M-1100, アロニックス M-1200, アロニックス M-6100, アロニックス M-6200, アロニックス M-6250, アロニックス M-6500, アロニックス M-7100, アロニックス M8030, アロニックス M8060, アロニックス M8100, アロニックス M8530, アロニックス M-8560, 464M 8100, アロニックス M9050 (manufactured by Toyo Seiya Kagaku Co., Ltd.); ビスコート 295, ビスコート 300, ビスコート 360, ビスコート GPT, ビスコート 3PA, ビスコート 400, ビスコート 260, ビスコート 312, ビスコート 335HP, ビスコート 700 (manufactured by Osaka organic chemical industries, Ltd.); a-200, A-400, A-600, A-1000, A-B1206PE, ABE-300, A-BPE-10, A-BPE-20, A-BPE-30, A-BPE-4, A-BPEF, A-BPP-3, A-DCP, A-DOD-N, A-HD-N, A-NOD-N, APG-100, APG-200, APG-400, APG-700, A-PTMG-65, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP, TMATM-35E, A-TMT, A-9550, A-DPH, TMPT, 9PG, 701A, 1206PE, NPG, NOD-N, HD-N, DOD-N, DCP, BPE-1300N, BPE-900, BPE-200, BPE-100, BPE-80N, 23G, 14G, 9G, 4G, 3G, 2G, 1G (manufactured by Mitsukamura chemical industries, Ltd.); ライトエステル EG, ライトエステル 2EG, ライトエステル 3EG, ライトエステル 4EG, ライトエステル 9EG, ライトエステル 14EG, ライトエステル 1.4BG, ライトエステル NP, ライトエステル 1.6.6 HX, ライトエステル 1.9.9 ND, ライトエステル G-101P, ライトエステル G-201P, ライトエステル DCP-M, ライトエステル BP-2EMK, ライトエステル BP-4EM, ライトエステル BP-6EM, ライトエステル TMP, ライトアクリレート 3EG-A, ライトアクリレート 4EG-A, ライトアクリレート 9EG-A, ライトアクリレート 14EG-A, ライトアクリレート PTMG-250, PTMG-1, and, ライトアクリレート NP-A, ライトアクリレート MPD-A, ライトアクリレート 1.6.6 HX-A, ライトアクリレート 1.9.9 ND-A, ライトアクリレート MOD-A, ライトアクリレート DCP-A, ライトアクリレート BP-4PA, ライトアクリレート BA-134, ライトアクリレート BP-10EA, ライトアクリレート HPP-A, ライトアクリレート G-201P, ライトアクリレート TMP-A, ライトアクリレート TMP-3EO-A, ライトアクリレート TMP-6EO-3A, ライトアクリレート PE-3A, ライトアクリレート PE-4A, B, C, E, B, C, ライトアクリレート DPE-6A, エポキシエステル 40EM, エポキシエステル 70PA, エポキシエステル 200PA, エポキシエステル 80MFA, エポキシエステル 3002M, エポキシエステル 3002A, エポキシエステル 3000MK, エポキシエステル 3000A, エポキシエステル EX-0205, AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167 (manufactured by Kyoeisha chemical Co., Ltd.); EBECRYL (registered trademark) TPGDA, EBECRYL 145, EBECRYL 150, EBECRYL PEG400DA, EBECRYL 11, EBECRYL HPNDA, EBECRYL PEIA, EBECRYL PERA, EBECRYL TMPTA, EBECRYL TMPEOTA, EBECRYL OTA480, EBECRYL DPHA, EBECRYL 180, EBECRYL 40, EBECRYL 140, EBECRYL 204, EBECRYL 205, EBECRYL 210, EBECRYL 215, EBECRYL 220, EBECRYL 6202, EBECRYL 230, EBECRRRRYL 244, EBECRYL 245, EBECRYL 264, EBECRYL 265, EBECRRYL 270, EBECRYL 280/15IB 284, EBECRYL 285, EBECRYL 294/25, EBECRYL 9, EBECRYL 78, EBECRYL 84RYL 8435, EBECRYL 84RYL 8435, EBECRYL GCRYL 8435, EBECRYL GCRYL 8435, EBECRYL GCRYL 8435, EBECRYL GCRYL GCR, EBECRYL 810, EBECRYL 811, EBECRYL 812, EBECRYL 1830, EBECRYL 846, EBECRYL 851, EBECRYL 852, EBECRYL 853, EBECRYL 1870, EBECRYL 884, EBECRYL 885, EBECRYL 600, EBECRYL 605, EBECRYL 645, EBECRYL 648, EBECRYL 860, EBECRYL 1606, EBECRYL 3500, EBECRYL 3608, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, EBECRYL 3708, EBECRYL 6040 (manufactured by ダイセル & オルネクス strain); SR212, SR213, SR230, SR238F, SR259, SR268, SR272, SR306H, SR344, SR349, SR508, CD560, CD561, CD564, SR601, SR602, SR610, SR833S, SR9003, CD9043, SR9045, SR9209, SR205, SR206, SR209, SR210, SR214, SR231, SR239, SR248, SR252, SR297, SR348, SR480, CD540, CD541, CD542, SR603, SR644, SR9036, SR351S, SR368, SR415, SR444, SR454, SR492, SR499, CD501, SR502, SR9020, CD9021, SR9035, SR350, SR295, SR355, SR399, SR494, SR9041 (manufactured by Sartomer corporation), and the like.
These compounds having 2 or more polymerizable groups may be used in 1 kind or in combination of 2 or more kinds.
The content of the component (B) in the negative photosensitive resin composition of the present invention is preferably 10 to 150 parts by mass, more preferably 20 to 120 parts by mass, and particularly preferably 30 to 110 parts by mass, based on 100 parts by mass of the component (a). When the proportion of the component (B) is too small, the exposed portion may be insufficiently cured, and thus the pattern may not be formed, or even if the pattern can be formed, the film may be a film with low reliability. When the ratio is too large, the coating film after the prebaking may be wrinkled or the unexposed portion may be poorly dissolved during the development.
< ingredient (C) >
(C) The component (A) is a photoinitiator, and in the present invention, photoinitiators having 2 different absorption coefficients (g) of the following (C-1) and (C-2) are used.
(C-1) component
The component (C-1) is a photoinitiator which has an oxime ester group and has an absorption coefficient of 5,000ml/g cm or more in methanol or acetonitrile at 365 nm. Specifically, the compound has an oxime ester group and a light absorption site, and has an absorption coefficient of 5,000ml/g cm or more in methanol or acetonitrile at 365 nm.
Examples of the oxime ester group include groups represented by the following formula (1).
Figure BDA0001002067570000121
(in the formula, R1Represents phenyl, straight-chain, branched or cyclic alkyl or benzyl with 1-10 carbon atoms, R2Represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or a phenyl group, and the dotted line represents a bond. )
Examples of the straight, branched or cyclic alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a cyclopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a neopentyl group, a cyclopentyl group, a n-hexyl group, a cyclohexyl group, a n-octyl group, a n-decyl group, a 1-adamantyl group and the like.
The light absorbing moiety is preferably a moiety obtained by substituting a group selected from phenyl, thiophenylphenyl, N-alkylcarbazolyl, naphthyl, coumarinyl, alkoxyphenyl, phenylalkoxyphenyl, and phenoxyalkoxyphenyl with a group having a benzoyl structure such as benzoyl or naphthylcarbonyl. Further, the structure may be substituted with phenyl, phenylthio, diphenylamino, or the like.
The component (C-1) is preferably a compound in which an oxime ester group represented by the above formula (1) is bonded to a group selected from the group consisting of a phenyl group, a phenylthiophenyl group, an N-alkylcarbazolyl group, a naphthyl group, a coumarinyl group, an alkoxyphenyl group, a phenylalkoxyphenyl group and a phenoxyalkoxyphenyl group at the light absorbing portion via a single bond or a carbonyl group.
Specific examples of the component (C-1) include, for example, 1- (4-phenylthiophenyl) -1, 2-octanedione-2- (O-benzoyloxime), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), (E) -4- (4(4- (diphenylamino) benzoyl) benzyloxy) benzaldehyde-O-acetyloxime, (E) -4- (4, 8-dimethoxy-1-naphthoyl) benzaldehyde-O-acetyloxime, 1- (9-propyl-9H-carbazol-3-yl) butane-1, 3-dione-1- (O-acetyloxime), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] butane-1, 3-dione-1- (O-acetyloxime), and the like.
The photoinitiator of the component (C-1) can be easily obtained as a commercially available product (photopolymerization initiator), and specific examples thereof include IRGACURE (registered trademark) OXE01, IRGACURE (registered trademark) OXE02 (available from BASF corporation), アデカオプトマー N-1919, アデカアークルズ NCI-831, and アデカアークルズ NCI-930 (available from ADEKA, Ltd.).
These photoinitiators as the component (C-1) may be used alone or in combination of two or more.
The content of the component (C-1) in the negative photosensitive resin composition of the present invention is preferably 0.3 to 5 parts by mass, and more preferably 0.5 to 4 parts by mass, based on 100 parts by mass of the component (a). When the proportion of the component (C-1) is too small as compared with 0.3 parts by mass, curability may decrease until the surface of a coating film obtained by applying the resin composition to a substrate when the coating film is exposed from the back surface of the substrate as described later, and when the proportion is too large as compared with 5 parts by mass, transmittance of the cured film may decrease, or curability may decrease at the surface when the coating film is exposed from the back surface of the substrate.
< component (C-2) >
The component (C-2) is a photoinitiator having an absorption coefficient of 100ml/g cm or less in methanol or acetonitrile at 365 nm. As the component (C-2), for example, a photoinitiator having a hydroxyl group is preferable.
Specific examples of the component (C-2) include 1-hydroxy-cyclohexyl-phenyl-ketone, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, methyl benzoylformate, 2- [ 2-hydroxy-ethoxy ] ethyl 2-oxy-2-phenylacetate, and the like.
The photoinitiator of the component (C-2) can be easily obtained as a commercially available product (photopolymerization initiator), and specific examples thereof include IRGACURE (registered trademark) 2959, IRGACURE (registered trademark) 754, IRGACURE (registered trademark) 184, DAROCURE MBF, DAROCURE 1173 (mentioned above, manufactured by BASF corporation), and the like.
These photoinitiators as the component (C-2) may be used alone or in combination of two or more.
The content of the component (C-2) in the negative photosensitive resin composition of the present invention is preferably 0.5 to 10 parts by mass, and more preferably 1 to 7 parts by mass, based on 100 parts by mass of the component (a). When the proportion of the component (C-2) is too small as compared with 0.5 parts by mass, curability of the surface may be lowered, and when the proportion is too large as compared with 10 parts by mass, transmittance of the cured film may be lowered or residue may be generated in an unexposed portion.
< (D) component: solvent (A)
The solvent for the component (D) used in the present invention is a solvent which dissolves the components (A), (B) and (C) and also dissolves the components (E) and (F) which are added as required, and the type, structure and the like of the solvent are not particularly limited if the solvent has such a dissolving ability.
Examples of the solvent of component (D) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-heptanone, γ -butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl acetate, methyl acetate, ethyl, Ethyl 3-ethoxypropionate, methyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, and the like.
These solvents may be used singly or in combination of two or more.
Among the solvents of the component (D), propylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and the like are preferable from the viewpoint of good film coatability and high safety. These solvents are generally used as solvents for photoresist materials.
< ingredient (E) >
(E) The component (B) is a thiol compound. The negative photosensitive resin composition of the present invention may further contain a thiol compound for the purpose of increasing the curing rate thereof, as long as the effects of the present invention are not impaired.
The thiol compound of the component (E) is not particularly limited, and examples thereof include 1-hexanethiol, 1-heptanethiol, 1-octanethiol, 1-nonanethiol, 1-decanethiol, 1-undecanethiol, 1-dodecanethiol, 1-octadecanethiol, 2-mercaptobenzothiazole, 6-methyl-2-mercaptobenzothiazole, 5-chloro-2-mercaptobenzothiazole, 2-naphthalenethiol, 2, 5-dimercapto-1, 3, 4-thiadiazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole
Figure BDA0001002067570000151
Oxazole, beta-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), tris- [ (3-mercaptopropionyloxy) -ethyl ] propane]Isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane, 1,3, 5-tris [2- (3-mercaptobutyryloxy) ethyl ] isocyanurate]-1,3, 5-triazine-2, 4, 6-trione and the like.
These thiol compounds as the component (E) may be used singly or in combination of two or more kinds.
Among these thiol compounds as the component (E), pentaerythritol tetrakis (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane, 1,3, 5-tris [2- (3-mercaptobutyryloxy) ethyl ] -1,3, 5-triazine-2, 4, 6-trione, and the like are preferable from the viewpoint that the negative photosensitive resin solution has high storage stability and sufficient curability can be obtained.
When the thiol compound is used, the content thereof is 0.01 to 10 parts by mass, preferably 0.03 to 5 parts by mass, based on 100 parts by mass of the component (a). Even if the amount of the thiol compound of component (E) is set to be excessively large, pattern resolution may be reduced. If the amount is too small, the effect of improving curability may not be exhibited.
< ingredient (F) >
(F) The component is surfactant. The negative photosensitive resin composition of the present invention may further contain a surfactant for the purpose of improving the coatability thereof, as long as the effects of the present invention are not impaired.
The surfactant of component (F) is not particularly limited, and examples thereof include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. As such a surfactant, commercially available products such as Sumitomo スリーエム, DIC, and AGC セイミケミカル can be used. These commercially available products are readily available and therefore convenient. Specific examples thereof include ポリフォックス F-136A, 151, 156A, 154N, 159, 636, 6320, 656, 6520 (manufactured by Omnova), メガファック (registered trademark) R30, R08, R40, R41, R43, F251, F477, F552, F553, F554, F555, F556, F557, F558, F559, F560, F561, F562, F563, F565, F567, F570 (manufactured by DIC corporation), FC4430, FC4432 (manufactured by Sumitomo スリーエム corporation), アサヒガード (registered trademark) AG710, サーフロン (registered trademark) S-386, S-611, S-651 (manufactured by AGC セイミケミカル corporation), フタージェント (registered trademark) X-218, DFX-18, 220P, 251, 212M, 215M ネオス and the like ((manufactured by registered trademark); silicone surfactants such as BYK-300, 302, 306, 307, 310, 313, 315, 320, 322, 323, 325, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455 (manufactured by ビックケミージャパン Co., Ltd.), SH3746, SH3749, SH3771, SH8400, SH8410, SH8700, SF8428 (manufactured by east レ, ダウコーニング, シリコーン Co., Ltd.), KF-351, KF-352, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-618, KF-6011, and KF-6015 (manufactured by shin-Etsu chemical Co., Ltd.).
(F) The surfactants of the components may be used singly or in combination of two or more.
When a surfactant is used, the content thereof is 0.01 to 1 part by mass, preferably 0.02 to 0.8 part by mass, based on 100 parts by mass of the component (a). Even if the amount of the surfactant of component (F) is set to an amount exceeding 1 part by mass, the effect of improving the coatability is not sufficiently exerted, which is uneconomical. When the amount is 0.01 part by mass or less, the effect of improving coatability may not be exhibited.
< other additives >
The negative photosensitive resin composition of the present invention may further contain a sensitizer, a chain transfer agent, a crosslinking agent, a rheology modifier, a pigment, a dye, a storage stabilizer, a defoaming agent, a dissolution accelerator such as a polyhydric phenol or a polycarboxylic acid, and the like as necessary, as long as the effects of the present invention are not impaired.
< negative photosensitive resin composition >
The negative photosensitive resin composition of the present invention is a composition in which an alkali-soluble polymer of component (a), a compound of component (B) having 2 or more polymerizable groups, a photoinitiator of component (C-1) having an oxime ester group and having an absorption coefficient of 5,000 ml/g-cm or more in methanol or acetonitrile at 365nm, and a photoinitiator of component (C-2) having an absorption coefficient of 100 ml/g-cm or less in methanol or acetonitrile at 365nm are dissolved in a solvent of component (D), and may further contain one or more of a thiol compound of component (E), a surfactant of component (F), and other additives, as required.
Among them, preferred examples of the negative photosensitive resin composition of the present invention are as follows.
[1]: a negative photosensitive resin composition comprising, based on 100 parts by mass of the component (A), 10 to 150 parts by mass of the component (B), 0.3 to 5 parts by mass of the component (C-1), and 0.5 to 10 parts by mass of the component (C-2), the components being dissolved in a solvent for the component (D).
[2]: the composition of [1] further contains 0.01 to 10 parts by mass of a negative photosensitive resin composition of component (E) based on 100 parts by mass of component (A).
[3]: the composition of [1] or [2] further contains 0.01 to 1 part by mass of the component (F) based on 100 parts by mass of the component (A).
The proportion of the solid component in the negative photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, and is, for example, 1 to 80% by mass, and further, 5 to 70% by mass, or 10 to 60% by mass. Here, the solid component refers to a component obtained by removing the solvent of the component (D) from the entire components of the negative photosensitive resin composition.
The method for preparing the negative photosensitive resin composition of the present invention is not particularly limited, and examples of the method for preparing the negative photosensitive resin composition include the following methods: for example, a method of dissolving the copolymer of component (A) in the solvent of component (D) and mixing the compound having 2 or more polymerizable groups of component (B), the photoinitiator of component (C-1) and the photoinitiator of component (C-2) at a predetermined ratio in the solution to prepare a uniform solution, or a method of further adding the thiol compound of component (E), the surfactant of component (F) and other additives as needed at an appropriate stage of the preparation method and mixing them.
In the preparation of the negative photosensitive resin composition of the present invention, the polymerization solution of the copolymer of the component (a) obtained by the polymerization reaction in the solvent of the component (D) can be used as it is without purification. In this case, when the component (B), the component (C-1), the component (C-2), and the like are added to the polymerization solution of the component (A) in the same manner as described above to prepare a uniform solution, a solvent of the component (D) may be further added for the purpose of adjusting the concentration. In this case, the solvent of the component (D) used in the process of forming the copolymer of the component (a) may be the same as or different from the solvent of the component (D) used for adjusting the concentration in the preparation of the negative photosensitive resin composition.
The solution of the negative photosensitive resin composition prepared is preferably filtered using a filter having a pore size of about 0.2 μm or the like and then used.
< coating film and cured film >
The negative photosensitive resin composition of the present invention can be applied to a semiconductor substrate (for example, a silicon/silica-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, or the like, a glass substrate, a quartz substrate, an ITO substrate, or the like), a film substrate (for example, a triacetyl cellulose (TAC) film, a cycloolefin polymer (COP) film, a cycloolefin copolymer (COC) film, a polyethylene terephthalate (PET) film, an acrylic film, a resin film such as polyimide, or the like) by spin coating, flow coating, roll coating, slit coating, spin coating after slit coating, inkjet coating, or the like, and then predried with an electric hot plate, an oven, or the like to form a coating film. Then, the coating film is subjected to a heat treatment to form a negative photosensitive resin film.
The conditions for the heat treatment include, for example, a heating temperature and a heating time which are appropriately selected from the range of 70 to 150 ℃ for 0.3 to 60 minutes. The heating temperature and the heating time are preferably 80-120 ℃ and 0.5-10 minutes.
The film thickness of the negative photosensitive resin film formed from the negative photosensitive resin composition is, for example, 0.1 to 50 μm, further, for example, 0.5 to 40 μm, and further, for example, 1 to 30 μm.
The negative photosensitive resin film formed from the negative photosensitive resin composition of the present invention is subjected to ultraviolet rays, ArF, KrF, F using a mask having a predetermined pattern2When light such as laser light is exposed, the exposed portion of the negative photosensitive resin film becomes insoluble in an alkaline developer by the action of radicals generated from the photopolymerization initiators of the component (C-1) and the component (C-2) contained in the film.
In addition, when the negative photosensitive resin film of the present invention is formed on a light-transmitting substrate, not only exposure from the upper part of the surface of the substrate on which the resin film (coating film) is formed, but also exposure from the surface opposite to the surface (coating film surface) on which the resin film (coating film) is formed via a mask or the like, the exposed part becomes a cured product that is sufficiently insoluble in an alkaline developer.
Then, development is performed using an alkaline developer. Thus, the unexposed portion of the negative photosensitive resin film is removed to form a pattern-like relief.
Examples of the alkaline developing solution that can be used include alkaline aqueous solutions such as aqueous solutions of alkali metal hydroxides such as sodium carbonate, potassium hydroxide, and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Further, a surfactant or the like may be added to these developers.
Among them, an aqueous solution of 0.5 to 3 mass% sodium carbonate, an aqueous solution of 0.01 to 0.5 mass% potassium hydroxide and an aqueous solution of 0.1 to 2.38 mass% tetraethylammonium hydroxide are generally used as a developer for a photoresist, and the alkaline developer can be used in the photosensitive resin composition of the present invention, and can be used for satisfactory development without causing problems such as swelling.
As the developing method, a dipping method, a shaking dipping method, or the like can be used. The developing time at this time is usually 15 to 180 seconds.
After the development, the negative photosensitive resin film is washed with flowing water for 20 to 90 seconds, and then dried by using compressed air or compressed nitrogen gas or by spinning, thereby removing moisture on the substrate to obtain a patterned film.
Next, by performing post-baking for thermal curing or post-exposure for photo-curing, specifically, by heating using a hot plate, an oven, or the like, or performing exposure using an ultraviolet irradiation apparatus with respect to such a pattern-formed film, a film (cured film) having a good relief pattern with improved heat resistance, transparency, planarization, low water absorption, chemical resistance, or the like can be obtained.
As the post-baking, generally, a method of performing the treatment for 1 to 30 minutes on a hot plate at a heating temperature selected from the range of 120 to 250 ℃ and performing the treatment for 1 to 90 minutes in an oven is employed.
Further, by such post-baking, a cured film having a desired and favorable pattern shape can be obtained.
As described above, the negative photosensitive resin composition of the present invention can form a coating film having no wrinkles before exposure, capable of alkali development, sufficiently high sensitivity even at a film thickness of about 15 μm, and having a fine pattern with very little film reduction in an exposed portion during development. Further, the cured film is excellent in transparency, heat resistance and solvent resistance. Therefore, it can be suitably used for various films such as an interlayer insulating film, a protective film, an insulating film, an optical film, and the like in a liquid crystal display, an organic EL display, a touch panel element, and the like.
Examples
The present invention will be described in further detail below with reference to examples, but the present invention is not limited to these examples.
[ shorthand notation used in the examples ]
The abbreviations used in the following examples have the following meanings.
MAA: methacrylic acid
MMA: methacrylic acid methyl ester
AIBN: azobisisobutyronitrile
PRG 1: ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-1- (O-acetyloxime) (365nm absorption: 7,749ml/g cm in CH3CN in)
PRG 2: 1-hydroxy-cyclohexyl-phenyl-ketone (365nm absorption: 88.64ml/g cm in MeOH)
PRG 3: 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one (365nm absorption: 48.93 ml/g-cm in MeOH)
PRG 4: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (365nm absorption: 73.88ml/g cm in MeOH)
PRG 5: benzoic acid methyl ester (365nm absorption coefficient: 38ml/g cm in CH)3CN in)
PRG 6: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (365nm absorption: 7, 858 ml/g-cm in MeOH)
PRG 7: bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide (365nm absorption: 2,309 ml/g-cm in MeOH)
PRG 8: 2-methyl-1- [4- (methylthio) phenyl]2-Morpholinopropane-1-one (365nm absorption: 446.5ml/g cm in CH)3CN in)
DPHA: dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate
CTA: カレンズ -MT (registered trademark) PE1 (product name) (compound name: pentaerythritol tetrakis (3-mercaptobutyrate))
PGME: propylene glycol monomethyl ether
[ measurement of number average molecular weight and weight average molecular weight ]
The number average molecular weight and the weight average molecular weight of the copolymer of the component (a) obtained in the following synthesis example were measured under the condition that an elution solvent, tetrahydrofuran, was flowed into a column at a flow rate of 1 mL/min (column temperature 40 ℃) and eluted using GPC devices (columns KF803L and KF804L, manufactured by shimadzu サイエンス (ltd). The number average molecular weight (hereinafter referred to as Mn) and the weight average molecular weight (hereinafter referred to as Mw) described below are expressed in terms of polystyrene.
< Synthesis example 1 >
MAA (30.0g) and MMA (120.0g) were used as monomer components constituting the copolymer, and AIBN (6.4g) was used as a radical polymerization initiator, and they were subjected to polymerization reaction in a solvent PGME (290g), whereby a copolymer solution (copolymer concentration: 35 mass%) of component (A) of Mn9,700, Mw21,500 (P1) was obtained. The polymerization temperature was adjusted to 60 ℃ to 90 ℃.
< examples 1 to 5 and comparative examples 1 to 7 >
The negative photosensitive resin compositions of examples and comparative examples were prepared by mixing the component (B), the component (C-1), the component (C-2), the solvent for the component (D), and the component (E) in a predetermined ratio in the solution of the component (a) according to the composition shown in table 1 below, and stirring the mixture at room temperature for 3 hours to prepare a uniform solution.
[ Table 1]
TABLE 1
Figure BDA0001002067570000221
The obtained negative photosensitive resin compositions of examples 1 to 5 and comparative examples 1 to 7 were subjected to measurement of film thickness, residual film ratio, transmittance after prebaking and observation of pattern shape, respectively.
[ evaluation of residual film ratio ]
On an alkali-free glass (substrate), a negative photosensitive resin composition was applied using a spin coater, and then prebaked at a temperature of 110 ℃ for 120 seconds on a hot plate to form a coating film (film thickness 20 μm). The light intensity at 365nm was adjusted to 7.1mW/cm by using a PLA-600FA ultraviolet irradiation apparatus manufactured by キヤノン K2The coating film was irradiated with ultraviolet rays of 25mJ/cm from the surface (back surface) of the substrate opposite to the surface on which the coating film was formed2. Then, 90-second jet development was performed with a 2.0 mass% aqueous solution of sodium hydrogencarbonate, followed by 20-second running water washing with ultrapure water, whereby a cured film was obtained.
A film obtained by firing (post-baking) the cured film prepared for 3 minutes on a hot plate at 140 ℃ was used as the Dektak product manufactured by Vecco3The film thickness was measured. The residual film ratio (%) was calculated as (post-bake film thickness/pre-bake film thickness) × 100.
[ evaluation of transmittance ]
On a quartz substrate, a negative photosensitive resin composition was applied using a spin coater, and then prebaked at a temperature of 110 ℃ for 120 seconds on a hot plate to form a coating film (film thickness 20 μm). The coating film was irradiated with light at 365nm at a light intensity of 7.1mW/cm using a PLA-600FA ultraviolet irradiation apparatus manufactured by キヤノン K2Ultraviolet ray of 100mJ/cm2. The cured film was measured for transmittance at a wavelength of 400nm using an ultraviolet-visible spectrophotometer (SIMADZU UV-2550, manufactured by Shimadzu corporation).
[ evaluation of Pattern formation ]
A negative photosensitive resin composition was applied to an alkali-free glass (substrate) having black lines and spaces of 10 μm in thickness of 200nm by using a spin coater, and then prebaked on a hot plate at a temperature of 110 ℃ for 120 seconds to form a coating film (film thickness of 20 μm). The light intensity at 365nm was adjusted to 7.1mW/cm by using a PLA-600FA ultraviolet irradiation apparatus manufactured by キヤノン K2The coating film is irradiated with 100mJ/cm of ultraviolet light from the surface (back surface) of the substrate opposite to the surface on which the coating film is formed2. Then, 90 seconds of jet development was performed with a 2.0 mass% aqueous solution of sodium carbonate, and then 20 seconds of running water washing was performed with ultrapure water, thereby forming a pattern. The pattern obtained by firing the produced pattern for 3 minutes using a hot plate at 140 ℃ was observed with a scanning microscope (SEM), and the pattern shape was confirmed. The case where the rectangular shape with a period of 20 μm could be produced was indicated by ≈ where the rectangular shape could be produced but the film thickness was insufficient (film thickness of 14 μm or less), and the case where the rectangular shape could not be produced was indicated by ×.
[ results of evaluation ]
The results of the above evaluations are shown in table 2 below.
[ Table 2]
TABLE 2
Figure BDA0001002067570000241
As is clear from the results shown in Table 2, it was confirmed that the negative photosensitive resin compositions of examples 1 to 5 all had a high residual film ratio even at a low exposure level, and that curability was improved by using a photoinitiator (C-2) having a small absorption coefficient at 365nm in combination. The transmittance after further exposure was extremely high, at 90% or more, and high transparency was maintained even when the film was thick (film thickness: 20 μm). Further, a pattern having a rectangular shape can be formed.
On the other hand, in comparative examples 1 to 4 using only the photoinitiator with a large extinction coefficient of 365nm and comparative example 6 using both the photoinitiator and the photoinitiator with a large extinction coefficient, the residual film ratio was low and the pattern (rectangle) could be formed but the film thickness was lost at the same exposure level as in the above examples. In addition, the transmittance after exposure was as low as 90% or less for comparative examples 1 to 3. Further, in comparative example 5 using only a photoinitiator with a small absorption coefficient at 365nm and comparative example 7 using a combination of an initiator with a large absorption coefficient not containing an oxime ester group and a photoinitiator with a small absorption coefficient, the results were obtained that although the transmittance was high, the photoinitiator was dissolved in an alkaline developer after exposure, the curability such as the residual film ratio became 0 and the like was low, and a pattern could not be formed.
Industrial applicability
The negative photosensitive resin composition of the present invention is suitable as a material for forming a cured film such as a protective film, a planarization film, or an insulating film in various displays such as a Thin Film Transistor (TFT) type liquid crystal display device, an organic EL device, and a touch panel device, and is particularly suitable as a material for forming an interlayer insulating film of a TFT type liquid crystal device, a protective film of a color filter, an array planarization film, an interlayer insulating film of a capacitance type touch panel, an insulating film of an organic EL device, a structure sheet as an optical property adjustment layer on a display surface, and the like.

Claims (11)

1. A photosensitive resin composition comprising a component (A), a component (B), a component (C-1), a component (C-2) and a component (D), wherein the content of the component (C-1) is 0.3 to 5 parts by mass per 100 parts by mass of the component (A), the content of the component (C-2) is 0.5 to 10 parts by mass per 100 parts by mass of the component (A),
(A) the components: an alkali-soluble copolymer of a carboxylic acid and a carboxylic acid,
(B) the components: a compound having at least 1 polymerizable group of 2 or more selected from an acrylate group, a methacrylate group, a vinyl group and an allyl group,
(C-1) component: a photoinitiator having an oxime ester group and having an absorption coefficient of 5,000ml/g cm or more in methanol or acetonitrile at 365nm,
(C-2) component: a photoinitiator having an absorption coefficient of 100ml/g cm or less in methanol or acetonitrile at 365nm,
(D) the components: a solvent, a water-soluble organic solvent,
the photosensitive resin composition further contains a thiol compound as the component (E).
2. The photosensitive resin composition according to claim 1, wherein the component (A) is an alkali-soluble copolymer having a number average molecular weight of 2,000 to 50,000 in terms of polystyrene.
3. The photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble copolymer of the component (a) is a copolymer produced by copolymerization of a monomer mixture containing at least 1 selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride and maleimide.
4. The photosensitive resin composition according to claim 1 or 2, wherein the content of the component (B) is 10 to 150 parts by mass based on 100 parts by mass of the component (A).
5. The photosensitive resin composition according to claim 1 or 2, wherein the component (C-1) is a photoinitiator having a carbazole structure.
6. The photosensitive resin composition according to claim 1 or 2, wherein the component (C-2) is a photoinitiator having a hydroxyl group.
7. The photosensitive resin composition according to claim 1 or 2, which further contains a surfactant as the (F) component.
8. A cured film obtained by using the photosensitive resin composition according to any one of claims 1 to 7.
9. A cured film obtained by exposing a coating film on a light-transmitting substrate to light from the surface of the substrate opposite to the coating film surface, the coating film being formed from the photosensitive resin composition according to any one of claims 1 to 7.
10. An interlayer insulating film for a liquid crystal display comprising the cured film according to claim 8 or 9.
11. An optical filter comprising the cured film of claim 8 or 9.
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