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CN118192168A - Photosensitive resin composition - Google Patents
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CN118192168A - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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Publication number
CN118192168A
CN118192168A CN202410326078.6A CN202410326078A CN118192168A CN 118192168 A CN118192168 A CN 118192168A CN 202410326078 A CN202410326078 A CN 202410326078A CN 118192168 A CN118192168 A CN 118192168A
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CN
China
Prior art keywords
group
component
resin composition
photosensitive resin
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202410326078.6A
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Chinese (zh)
Inventor
星野有辉
汤川升志郎
大村浩之
畑中真
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Nissan Chemical Corp
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Nissan Chemical Corp
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Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Publication of CN118192168A publication Critical patent/CN118192168A/en
Pending legal-status Critical Current

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional [2D] radiating surfaces
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional [2D] radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional [2D] radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/122—Pixel-defining structures or layers, e.g. banks
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/124—Insulating layers formed between TFT elements and OLED elements

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials For Photolithography (AREA)
  • Electroluminescent Light Sources (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

The invention provides a photosensitive resin composition which can form an image of a cured film used in a liquid crystal display element, an organic EL display element, etc., which maintains a good image after curing, and which has high hydrophobicity and high oleophobicity even without plasma treatment, UV ozone treatment, etc., and which has little residue and high lyophilic and high oleophilic properties on a substrate. The solution is a heat-curable photosensitive resin composition containing the following component (A), component (B), solvent (C) and component (D). Component (A): a trialkoxysilyl group as a lyophobic group (A2) of the polymer (A1) having the following groups (A1) and (A2), and a component (B): an alkali-soluble resin, (C) a solvent, (D) a component: and (3) a sensitizer.

Description

Photosensitive resin composition
The present application is a divisional application of patent application having a filing date of 2018, 4, 20, 201880025855.6 and a name of "photosensitive resin composition".
Technical Field
The present invention relates to a photosensitive resin composition and a cured film obtained from the photosensitive resin composition.
More specifically, the present invention relates to a photosensitive resin composition capable of forming an image having high hydrophobicity and oleophobicity on the surface of a cured film, a cured film thereof, and various materials using the cured film. The photosensitive resin composition is particularly suitable for use as an interlayer insulating film, a light shielding material and a partition wall material in a liquid crystal display or an EL display according to an ink jet system.
Background
In recent years, a full-color display substrate manufacturing technique using ink jet in a manufacturing process of a display element such as a Thin Film Transistor (TFT) type liquid crystal display element or an organic Electroluminescence (EL) element has been actively studied. For example, as for the color filter production in a liquid crystal display device, there have been proposed a color filter in which a region (hereinafter referred to as bank) defining pixels to be patterned is formed in advance in a photosensitive resin layer blocking light, and ink droplets are dropped in the region surrounded by the bank, and a method for producing the same (patent document 1). In addition, a method of manufacturing an organic EL display element by previously manufacturing a bank and similarly dropping an ink to be a light-emitting layer has been proposed (patent document 2).
However, in the case of dropping ink droplets in the region surrounded by the banks by the ink jet method, in order to prevent the ink droplets from overflowing beyond the banks to adjacent pixels, it is necessary to impart ink-philicity (hydrophilicity) to the substrate and to impart hydrophobicity to the bank surface.
In order to achieve the above object, it has been proposed that a substrate be rendered hydrophilic and a bank be rendered hydrophobic by a continuous plasma (ozone) treatment such as an oxygen plasma treatment or a fluorine plasma treatment (patent document 3), but the process is complicated. In addition, it has been proposed to blend a fluorine-based surfactant or a fluorine-based polymer into a photosensitive organic film (patent document 4), but it is not practical because of the reduced hydrophobicity of the surface in UV ozone treatment at the time of hydrophilic treatment of a substrate, since there are many factors such as compatibility, addition amount, and the like, which are considered to be considered, including photosensitivity as well as coatability.
On the other hand, conventionally, japanese patent application laid-open No. 2015-172742 (patent document 5) has been used as a lyophobic dam and as a negative lyophobic dam. Further, as a positive lyophobic dike, japanese patent application laid-open No. 2012-220860 (patent document 6) is known.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2000-187111
Patent document 2: japanese patent laid-open No. 11-54270
Patent document 3: japanese patent laid-open No. 2000-353594
Patent document 4: japanese patent laid-open No. 10-197715
Patent document 5: japanese patent laid-open No. 2015-172742
Patent document 6: japanese patent application laid-open No. 2012-220860
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above-described circumstances, and an object of the present invention is to form an image of a cured film having high hydrophobicity and high oleophobicity, having little residue, and having high lyophilic properties and high oleophilic properties on a substrate, even when the cured film is used for a liquid crystal display element, an organic EL display element, or the like, without performing plasma treatment, UV ozone treatment, or the like. In particular, an object of the present invention is to form an image of a cured film capable of preventing an ink droplet from overflowing beyond a bank to an adjacent pixel in the production of a substrate using an inkjet.
Means for solving the problems
The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that hydrophobicity and lyophobicity can be efficiently imparted to a film surface by forming a cured film from a composition containing a polymer having at least one group selected from the group consisting of a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group, and a polysiloxane group, and a trialkoxysilyl group, and have completed the present invention.
Namely, the present invention relates to the following.
1. A heat-curable photosensitive resin composition comprising the following component (A), component (B), solvent (C) and component (D).
(A) The components are as follows: polymers having the following groups (A1) and (A2)
(A1) Lyophobic group
(A2) A trialkoxysilyl group, which is a group,
(B) The components are as follows: an alkali-soluble resin, a solvent,
(C) The solvent is used for the preparation of the aqueous solution,
(D) The components are as follows: and (3) a sensitizer.
2. The photosensitive resin composition according to the above 1, wherein the component (A) is a polymer further comprising the following component (A3).
(A3) : at least 1 group selected from the group consisting of hydroxyl, carboxyl, amide, and amino.
3. The photosensitive resin composition according to the above 1 or 2, which satisfies at least 1 of the following (Z1) to (Z4).
(Z1): also contains a crosslinking agent as component (E);
(Z2): (B) The alkali-soluble resin of the component (a) further has a self-crosslinking group or a group reactive with at least 1 group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group;
(Z3): (D) The component (C) is a photoradical generator, and the photosensitive resin composition further contains a compound having 2 or more olefinic double bonds as component (F);
(Z4): (D) The component (C) is a photoacid generator, and the photosensitive resin composition further contains, as the component (G), a compound having 2 or more functional groups that form covalent bonds with an acid generated by the component (D).
4. The photosensitive resin composition according to any one of the above 1 to 3, wherein the component (D) is a quinone diazonium compound.
5. The photosensitive resin composition according to the above 3, wherein the component (D) is a quinone diazonium compound, and the photosensitive resin composition satisfies the above (Z1) or (Z2).
6. The photosensitive resin composition according to any one of the above 1 to 5, wherein the lyophobic group of the component (A) is at least one group selected from the group consisting of a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group and a polysiloxane group.
7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the polymer of component (A) is an acrylic polymer.
8. The photosensitive resin composition according to the above 7, wherein the number average molecular weight of the acrylic polymer of the component (A) is 2,000 ～ 100,000 in terms of polystyrene.
9. The photosensitive resin composition according to any one of the above 1 to 8, wherein the alkali-soluble resin of component (B) has a number average molecular weight of 2,000 to 50,000 in terms of polystyrene.
10. The photosensitive resin composition according to any one of the above 1 to 9, wherein the component (A) is contained in an amount of 0.1 to 20 parts by mass based on 100 parts by mass of the component (B).
11. The photosensitive resin composition according to any one of the above 3 to 10, wherein the component (E) is 1 to 50 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B).
12. A cured film comprising a heat-cured product of the photosensitive resin composition according to any one of the above 1 to 11.
13. A display element having the cured film described in 12 above.
14. A display element having the cured film described in 12 above as a partition wall for image formation.
ADVANTAGEOUS EFFECTS OF INVENTION
The photosensitive resin composition of the present invention can effectively impart hydrophobicity and lyophobicity to the film surface, and can form a cured film without impairing the wettability of the pattern opening during development.
Detailed Description
The photosensitive resin composition of the present invention is a photosensitive resin composition containing the following component (A), component (B), solvent (C) and component (D).
(A) The components are as follows: polymers having the following groups (A1), (A2)
(A1) Lyophobic group
(A2) A trialkoxysilyl group, which is a group,
(B) The components are as follows: an alkali-soluble resin, a solvent,
(C) The solvent is used for the preparation of the aqueous solution,
(D) The components are as follows: and (3) a sensitizer.
The photosensitive resin composition of the present invention preferably contains a polymer having the following component (A3).
(A3) : at least 1 group selected from the group consisting of hydroxyl, carboxyl, amide, and amino.
The photosensitive resin composition of the present invention preferably further satisfies at least 1 of the following (Z1) to (Z4).
(Z1): also contains a crosslinking agent as component (E);
(Z2): (B) The alkali-soluble resin of the component (a) further has a self-crosslinking group or a group reactive with at least 1 group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group;
(Z3): (D) The component (C) is a photoradical generator, and the photosensitive resin composition further contains a compound having 2 or more ethylenically polymerizable groups as component (F);
(Z4): (D) The component (C) is a photoacid generator, and the photosensitive resin composition further contains, as the component (G), a compound having 2 or more functional groups that form covalent bonds with an acid generated by the component (D).
The photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition containing a quinone diazonium compound as the component (D).
The details of the components are described below.
Component (A)
(A) The component (A) is a polymer having the following groups (A1) and (A2), and more preferably a polymer having the following group (A3).
(A1) Lyophobic group
(A2) Trialkoxysilyl groups
(A3) At least 1 group selected from the group consisting of hydroxyl, carboxyl, amide and amino
In the present invention, examples of the polymer include polyimide, polyamic acid, polyamide, polyurea, polyurethane, phenol resin, epoxy resin, polysiloxane, polyester, and acrylic polymer, and examples of the preferable polymer include acrylic polymer.
Here, the acrylic polymer is a polymer obtained by using a monomer having a polymerizable unsaturated group, that is, a polymerizable group having a c=c double bond in the structure, such as acrylate, methacrylate, styrene, and maleimide.
The polyamide acid, polyimide, polyamide and polyurea are polyamide acid obtained by reacting diamine with acid dianhydride, polyimide obtained by imidizing the polyamide acid, polyamide obtained by reacting diamine with dicarboxylic acid anhydride or polyurea obtained by reacting diamine with diisocyanate, and examples thereof include polymers obtained from a monomer mixture comprising at least one monomer having a fluoroalkyl group or a fluoroalkoxy group, at least one monomer having at least 1 group selected from hydroxyl groups, carboxyl groups, amide groups and amino groups, and a monomer having a trialkoxysilyl group.
The polyurethane may be obtained by reacting a diol having a fluoroalkyl group or a fluoroalkoxy group and a diol having an amino group with a diisocyanate.
Examples of the phenolic resin include a phenolic novolac resin obtained by polymerizing a phenol having a fluoroalkyl group or a fluoroalkoxy group with formaldehyde.
Examples of the epoxy resin include an epoxy resin obtained by reacting bisphenol a and/or bisphenol F having a fluoroalkyl group or a fluoroalkoxy group with diglycidyl ether of bisphenol a and/or bisphenol F.
As the polysiloxane, a polymer obtained by polymerizing a silane monomer mixture containing a trialkoxysilane having a fluoroalkyl group or a dialkoxysilane having a fluoroalkyl group and a trialkoxysilane having an amino group or a dialkoxysilane having an amino group can be exemplified.
Examples of the polyester include polyesters obtained by reacting dicarboxylic acid or tetracarboxylic dianhydride with a diol having a fluoroalkyl group or a fluoroalkoxy group.
Introduction of lyophobic group (A1)
The lyophobic group includes, for example, at least one group selected from a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group, and a polysiloxane group.
The fluoroalkyl group is preferably a fluoroalkyl group having 3 to 10 carbon atoms, preferably 4 to 10 carbon atoms.
Examples of such fluoroalkyl groups include 2, 2-trifluoroethyl group, 2, 3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group, 3-perfluorobutyl-2-hydroxypropyl group, 2- (perfluorohexyl) ethyl group, 3-perfluorohexyl-2-hydroxypropyl group, 2- (perfluorooctyl) ethyl group, 3-perfluorooctyl-2-hydroxypropyl group, 2- (perfluorodecyl) ethyl group, 2- (perfluoro-3-methylbutyl) ethyl group, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl group, 2- (perfluoro-5-methylhexyl) ethyl group, 2- (perfluoro-5-methylhexyl) -2-hydroxypropyl group, 2- (perfluoro-7-methyloctyl) ethyl group, and 2- (perfluoro-7-methyloctyl) -2-hydroxypropyl group.
In introducing a fluoroalkyl group having 3 to 10 carbon atoms into the polymer as the component (A) of the present invention, a monomer having a fluoroalkyl group having 3 to 10 carbon atoms may be copolymerized.
As a specific example of the monomer having a fluoroalkyl group having 3 to 10 carbon atoms in the case where the component (A) is an acrylic polymer, examples thereof include 2, 2-trifluoroethyl acrylate, 2-trifluoroethyl methacrylate, 2, 3-pentafluoropropyl acrylate, 2, 3-pentafluoropropyl methacrylate, 2- (perfluorobutyl) ethyl acrylate, 2- (perfluorobutyl) ethyl methacrylate 3-perfluorobutyl-2-hydroxypropyl acrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2- (perfluorohexyl) ethyl acrylate, 2- (perfluorohexyl) ethyl methacrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate 3-perfluorohexyl-2-hydroxypropyl methacrylate, 2- (perfluorooctyl) ethyl acrylate, 2- (perfluorooctyl) ethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2- (perfluorodecyl) ethyl acrylate, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluoro-3-methylbutyl) ethyl acrylate, 2- (perfluoro-3-methylbutyl) ethyl methacrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl methacrylate, 2- (perfluoro-5-methylhexyl) ethyl acrylate, 2- (perfluoro-5-methylhexyl) ethyl methacrylate, 2- (perfluoro-5-methylhexyl) -2-hydroxypropyl acrylate, 2- (perfluoro-5-methylhexyl) -2-hydroxypropyl methacrylate, 2- (perfluoro-7-methyloctyl) ethyl acrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate, 2- (perfluoro-7-methyloctyl) -2-hydroxypropyl acrylate, and 2- (perfluoro-7-methyloctyl) -2-hydroxypropyl methacrylate, and the like.
The polyfluoroether group may be a Rf group (a) having a polyfluoroether structure represented by the following formula 1.
- (X-O) n -Y type 1
In formula 1, X is a 2-valent saturated hydrocarbon group having 1 to 10 carbon atoms or a fluorinated 2-valent saturated hydrocarbon group having 1 to 10 carbon atoms, and each unit enclosed by n represents the same group or different groups, Y represents a hydrogen atom (limited to the case where a fluorine atom is not bonded to a carbon atom adjacent to an oxygen atom adjacent to Y), a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms or a fluorinated 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 2 to 50. Wherein the total number of fluorine atoms in formula 1 is 2 or more.
As X, Y in the formula 1, preferred examples are those wherein X is a fluorinated alkylene group having 1 to 10 carbon atoms and 1 hydrogen atoms removed or a perfluorinated alkylene group having 1 to 10 carbon atoms, each unit enclosed by n represents the same group or a different group, and Y represents a fluorinated alkyl group having 1 to 20 carbon atoms and 1 hydrogen atoms removed or a perfluorinated alkyl group having 1 to 20 carbon atoms.
As the X, Y in the formula 1, more preferable examples are those wherein X is a perfluorinated alkylene group having 1 to 10 carbon atoms, each unit enclosed by n represents the same group or different groups, and Y represents a perfluorinated alkyl group having 1 to 20 carbon atoms.
In formula 1, n represents an integer of 2 to 50. n is preferably 2 to 30, more preferably 2 to 15. If n is 2 or more, the lyophobicity is good. If n is 50 or less, the compatibility of the monomer becomes good when the polymer as the component (A) is synthesized by copolymerizing the monomer having the Rf group (a) with the monomer having the hydroxyl group, carboxyl group, amide group, amino group, or trialkoxysilyl group, or other monomer.
The total number of carbon atoms in the Rf group (a) composed of the polyfluoroether structure represented by formula 1 is preferably 2 to 50, more preferably 2 to 30. In this range, the polymer as the component (A) exhibits excellent liquid repellency. In addition, when the polymer as the component (a) is synthesized by copolymerizing a monomer having the Rf group (a) with a monomer having a hydroxyl group, a carboxyl group, an amide group, an amino group, or a trialkoxysilyl group, or other monomers, the compatibility of the monomers becomes good.
Specific examples of X include -CF2-、-CF2CF2-、-CF2CF2CF2-、-CF2CF(CF3)-、-CF2CF2CF2CF2-、-CF2CF2CF(CF3)-、 and CF 2CF(CF3)CF2 -.
Specific examples of Y include -CF3、-CF2CF3、-CF2CHF2、-(CF2)2CF3、-(CF2)3CF3、-(CF2)4CF3、-(CF2)5CF3、-(CF2)6CF3、-(CF2)7CF3、-(CF2)8CF3、-(CF2)9CF3、 and (CF 2)11CF3、-(CF2)15CF3).
Preferable examples of the Rf group (a) composed of the polyfluoroether structure represented by formula 1 include the Rf group (a) represented by formula 2.
-C p-1F2(p-1)-O-(CpF2p-O)n-1-CqF2q+1 type 2
In formula 2, p represents an integer of 2 or 3, each unit enclosed by n is the same group, q represents an integer of 1 to 20, and n represents an integer of 2 to 50.
Specifically, the Rf group (a) represented by formula 2 is preferably selected from the viewpoint of ease of synthesis:
CF 2O(CF2CF2O)n-1CF3 (n is 2 to 9),
CF (CF 3)O(CF2CF(CF3)O)n-1C6F13 (n is 2 to 6),
CF (CF 3)O(CF2CF(CF3)O)n-1C3F7 (n is 2 to 6).
The Rf groups (a) in the polymer as component (A) may be the same or different.
The silyl ether group is a group in which a hydroxyl group of an alcohol is protected with a trialkylsilyl group, and is preferably a group represented by the following formula.
-X4-Si(O-SiX1X2X3)3
(Wherein X 1、X2、X3 each independently represents an alkyl group having 1 to 3 carbon atoms, and X 4 represents an alkylene group having 1 to 6 carbon atoms.)
In introducing silyl ether groups into the polymer as component (A) of the present invention, the silyl ether group-containing monomer may be copolymerized.
Examples of the silyl ether group-containing monomer in the case where the component (A) is an acrylic polymer include methacryloxypropyl tris (trimethylsiloxy) silane, acryloxypropyl tris (trimethylsiloxy) silane, and the like.
The polysiloxane group includes a group (a) having a polysiloxane structure represented by formula 3. Hereinafter, the group (a) having the polysiloxane structure represented by formula 3 is referred to as pSi group (a).
- (SiR 1R2-O)n-SiR1R2R3 type 3
(Wherein R 1、R2 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, R 3 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and n represents an integer of 1 to 200).
R 1、R2 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and furthermore each siloxy unit may be the same or different. In view of the excellent liquid repellency exhibited by the polymer as component (a), R 1、R2 is preferably a hydrogen atom, a methyl group or a phenyl group, and more preferably R 1、R2 of all siloxy units is a methyl group. In addition, R 3 may contain a nitrogen atom, an oxygen atom, or the like.
Examples of the method of introducing the pSi group (a) into the polymer as the component (a) include a method of copolymerizing a monomer having the pSi group (a), various modification methods of reacting a compound having the pSi group (a) with a polymer having a reaction site, a method of using a polymerization initiator having the pSi group (a), and the like.
Examples of the monomer having pSi group (a) include CH 2＝CHCOO(pSi)、CH2＝C(CH3) COO (pSi). Wherein pSi represents pSi group (a). The monomer having pSi group (a) may be used alone or in combination of 2 or more.
Examples of various modification methods for reacting a compound having pSi group (a) with a polymer having a reaction site include the following methods.
A method of copolymerizing a monomer having an epoxy group in advance and then reacting a compound having a carboxyl group at a single terminal and a pSi group (a) at a single terminal. A method in which a monomer having an epoxy group is copolymerized in advance and then a compound having an amino group at a single terminal and a pSi group (a) at a single terminal is reacted. A method in which a monomer having an epoxy group is copolymerized in advance, and then a compound having a mercapto group at a single terminal and a pSi group (a) at a single terminal is reacted. A method in which a monomer having an amino group is copolymerized in advance and then a compound having a carboxyl group at a single terminal and a pSi group (a) at a single terminal is reacted.
A method in which a monomer having an amino group is copolymerized in advance and then a compound having an epoxy group at a single terminal and a pSi group (a) at a single terminal is reacted. A method of copolymerizing a monomer having a carboxyl group in advance and then reacting a compound having an epoxy group at a single terminal and a pSi group (a) at a single terminal. A method in which a monomer having a carboxyl group is copolymerized in advance and then a compound having an amino group at a single terminal and a pSi group (a) at a single terminal is reacted. A method in which a monomer having a carboxyl group is copolymerized in advance and then a compound having a chlorosilyl group at a single terminal and a pSi group (a) at a single terminal is reacted. A method in which a monomer having a hydroxyl group is copolymerized in advance and then a compound having a chlorosilyl group at a single terminal and a PSi group (a) at a single terminal is reacted.
As the polymerization initiator having the pSi group (a), a group having a 2-valent polysiloxane structure may be contained in the main chain of the initiator molecule, and a group having a 1-valent polysiloxane structure may be contained in the terminal portion or side chain of the initiator molecule. Examples of the initiator having a group having a 2-valent polysiloxane structure in the main chain of the initiator molecule include compounds having groups having a 2-valent polysiloxane structure and azo groups alternately. As commercial products, VPS-1001 and VPS-0501 (manufactured by Wako pure chemical industries, ltd.).
Introduction of (A2) trialkoxysilyl group
In the case of introducing (A2) a trialkoxysilyl group into the polymer as the component (a) of the present invention, the monomer having (A2) a trialkoxysilyl group may be copolymerized.
Examples of the monomer having a trialkoxysilyl group in the case where the component (A) is an acrylic polymer include 3-trimethoxysilylpropyl acrylate, 3-triethoxysilylpropyl acrylate, 3-trimethoxysilylpropyl methacrylate, 3-triethoxysilylpropyl methacrylate and the like.
The method for producing a polymer of the component (A) when the component (A) is an acrylic polymer is as follows: the liquid repellent agent is obtained by polymerizing a monomer having a liquid repellent group, for example, at least one of a monomer having a fluoroalkyl group having 3 to 10 carbon atoms, a monomer having a polyfluoroether group, a monomer having a silyl ether group and a monomer having a polysiloxane group, a monomer having at least 1 group selected from a hydroxyl group, a carboxyl group, an amide group and an amino group, a monomer having a trialkoxysilyl group, and, if necessary, a monomer other than the above (hereinafter also referred to as other monomer A) in a solvent in the presence of a polymerization initiator at a temperature of 50 to 110 ℃. In this case, the solvent to be used is not particularly limited as long as it is a solvent that dissolves the monomer constituting the alkali-soluble polymer and the polymer having a specific functional group. Specific examples thereof include the solvents described in the following (C) solvents.
As a specific example of the other monomer a, examples thereof include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthalene methacrylate, anthracene methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, gamma-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthalene acrylate, anthracene methyl acrylate, phenyl acrylate, glycidyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminomethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, gamma-butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, styrene, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, and the like.
The polymer having a specific functional group obtained by such an operation is usually in the state of a solution dissolved in a solvent.
The solution of the specific copolymer obtained in the above-described manner is added to diethyl ether, water, or the like with stirring to reprecipitate, and the resulting precipitate is filtered and washed, and then dried at normal temperature or under reduced pressure, thereby producing a powder of the specific copolymer. By such an operation, the polymerization initiator and unreacted monomer which coexist with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. In the case where the purification cannot be performed sufficiently by one operation, the obtained powder is dissolved in a solvent again, and the above-described operation may be repeated.
In the present invention, the powder of the specific copolymer may be used as it is, or may be re-dissolved in, for example, a solvent (C) described later to prepare a solution.
(A3) introduction of at least 1 group selected from the group consisting of hydroxyl group, carboxyl group, amide group and amino group
In introducing (A3) at least 1 group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group into the polymer as the component (A) of the present invention, a monomer having (A3) at least 1 group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group may be copolymerized.
Examples of the monomer having a carboxyl group in the case where the component (a) is an acrylic polymer include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, and N- (carboxyphenyl) acrylamide.
Examples of the monomer having a hydroxyl group in the case where the component (A) is an acrylic polymer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2, 3-dihydroxypropyl acrylate, 2, 3-dihydroxypropyl methacrylate, glycerol monomethacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) acrylate, poly (propylene glycol) ethyl ether acrylate, poly (ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxy norbornene-2-carboxy-6-lactone, and 5-methacryloyloxy-6-hydroxy norbornene-2-carboxy-6-lactone, p-hydroxystyrene, α -methyl-p-hydroxystyrene, N-hydroxyphenylmaleimide, N-hydroxyphenylacrylamide, p-hydroxyphenylacrylamide, and the like. Among them, monomers selected from the group consisting of 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferable.
Examples of the amide group-containing monomer in the case where the component (A) is an acrylic polymer include acrylamide, methacrylamide, N-methacrylamide, N-dimethylacrylamide, N-diethylacrylamide, and the like, which may be used alone or in combination of 2 or more. Among them, methacrylamide is preferable.
Examples of the monomer having an amino group in the case where the component (a) is an acrylic polymer include aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, aminopropyl methacrylate, and the like, and these may be used alone or in combination of 2 or more.
In the polymer of the component (A), the amount of the lyophobic group (A1) to be introduced is preferably 5 to 60 mol%, more preferably 5 to 40 mol% based on the total of the repeating units. If the amount is too small as compared with 5 mol%, the liquid repellency effect may not be exhibited. If the amount is too large as compared with 60 mol%, problems such as aggregation may occur.
In the polymer of the component (A), the amount of the trialkoxysilyl group to be incorporated in the component (A2) is preferably 5 to 70 mol%, more preferably 5 to 50 mol%, based on the total of the repeating units. When the amount is too small as compared with 5 mol%, the heat resistance and solvent resistance of the resulting film may be problematic. When the amount is too large as compared with 70 mol%, the developability may be affected.
In the polymer of the component (A), the amount of at least 1 group selected from the group consisting of hydroxyl groups, carboxyl groups, amide groups and amino groups to be introduced into the polymer is preferably 5 to 60 mol%, more preferably 5 to 40 mol%, based on the total amount of the repeating units. If the amount is too small as compared with 5 mol%, the heat resistance and solvent resistance of the resulting film may be problematic. If it is too large compared to 60 mol%, the lyophobic repeating unit becomes too small.
The number average molecular weight of the polymer of the component (A) is preferably 2,000 ～ 100,000. More preferably 3,000 to 50,000, still more preferably 4,000 to 10,000. If the number average molecular weight is too large as compared with 100,000, residues are sometimes generated.
In addition, in the present invention, the polymer of the component (A) may be a mixture of a plurality of specific copolymers.
Component (B)
The component (B) of the present invention is a resin having an alkali-soluble group. Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, an acid anhydride group, an imide group, a sulfonyl group, phosphoric acid, boric acid, an active methylene group and an active methylene group.
The active methylene group means a group having a carbonyl group at an adjacent position and having reactivity to a nucleophile among methylene groups (-CH 2 -). In the present invention, the active methylene group means a group having a structure in which 1 hydrogen atom of the methylene group is substituted with an alkyl group, and having reactivity with a nucleophile.
The active methylene group and the active methine group are more preferably groups represented by the following formula (b 1).
(In the formula (b 1), R represents an alkyl group, an alkoxy group or a phenyl group, and a broken line represents a bond.)
In the above formula (b 1), examples of the alkyl group represented by R include an alkyl group having 1 to 20 carbon atoms, and preferably an alkyl group having 1 to 5 carbon atoms.
Examples of the alkyl group include methyl, ethyl, n-propyl, and isopropyl.
Among them, methyl, ethyl, n-propyl and the like are preferable.
In the above formula (b 1), examples of the alkoxy group represented by R include an alkoxy group having 1 to 20 carbon atoms, and preferably an alkoxy group having 1 to 5 carbon atoms.
Examples of such an alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy and the like.
Among them, methoxy, ethoxy, n-propoxy and the like are preferable.
Examples of the group represented by the above formula (b 1) include the following structures. In the structural formula, a broken line indicates a bond.
The alkali-soluble resin having at least 1 organic group selected from the group consisting of a phenolic hydroxyl group and a carboxyl group in the alkali-soluble group and having a number average molecular weight of 2,000 to 50,000 is preferable.
The alkali-soluble resin of the component (B) may be any alkali-soluble resin having such a structure, and the type of the backbone and side chains of the main chain of the polymer constituting the resin is not particularly limited.
However, the number average molecular weight of the alkali-soluble resin of the component (B) is in the range of 2,000 to 50,000. If the number average molecular weight exceeds 50,000 and is excessively large, development residues tend to be generated, and the sensitivity is greatly reduced, whereas if the number average molecular weight is excessively small, a considerable amount of film reduction in the exposed portion may occur during development, resulting in insufficient curing.
Examples of the alkali-soluble resin as the component (B) include an acrylic resin, a polyhydroxystyrene resin, a polyimide precursor, a polyimide, and the like.
In the present invention, an alkali-soluble resin formed from a copolymer obtained by polymerizing a plurality of monomers (hereinafter, referred to as a specific copolymer) may also be used as the component (B). In this case, the alkali-soluble resin of the component (B) may be a blend of a plurality of specific copolymers.
That is, the specific copolymer is a copolymer formed by using a monomer exhibiting alkali solubility, that is, a monomer having at least one selected from a phenolic hydroxyl group and a carboxyl group, and at least one selected from monomers copolymerizable with these monomers as an essential structural unit, and has a number average molecular weight of 2,000 to 50,000. If the number average molecular weight is too large as compared with 50,000, residues are sometimes generated.
The above-mentioned "monomer having at least one selected from the group consisting of phenolic hydroxyl groups and carboxyl groups" includes monomers having phenolic hydroxyl groups and monomers having carboxyl groups. These monomers are not limited to having one phenolic hydroxyl group or carboxyl group, and may have a plurality.
Hereinafter, specific examples of the above monomers are given, but not limited thereto.
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, and N- (carboxyphenyl) acrylamide.
Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide, and 4-hydroxyphenyl methacrylate.
The ratio of the unsaturated carboxylic acid derivative and/or the monomer having a phenolic hydroxyl group and a polymerizable unsaturated group in the alkali-soluble resin to be produced as the component (B) is preferably 5 to 90 mol%, more preferably 10 to 60 mol%, and most preferably 10 to 30 mol% of all the monomers used for producing the alkali-soluble resin as the component (B). In the case where the unsaturated carboxylic acid derivative is less than 5% by weight, the alkali solubility of the polymer is insufficient.
The alkali-soluble resin as the component (B) of the present invention is preferably an alkali-soluble resin obtained by further copolymerizing a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, in view of more stabilizing the pattern shape after curing.
Examples of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2, 3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2, 3-dihydroxypropyl methacrylate, glycerol monomethacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, and the like.
The ratio of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group in the alkali-soluble resin to be produced as the component (B) is preferably 10 to 60% by mass, more preferably 5 to 50% by mass, and most preferably 20 to 40% by mass. When the monomer having a hydroxyalkyl group and a polymerizable unsaturated group is less than 10% by mass, the effect of stabilizing the pattern shape of the copolymer may not be obtained. When the content is 60% by mass or more, the alkali-soluble group of the component (B) may be insufficient, and the properties such as developability may be lowered.
In view of increasing Tg of the copolymer, the alkali-soluble resin as the component (B) of the present invention is preferably an alkali-soluble resin obtained by further copolymerizing an N-substituted maleimide compound.
Examples of the N-substituted maleimide compound include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like. From the viewpoint of transparency, a substance having no aromatic ring is preferable, and from the viewpoints of developability, transparency, and heat resistance, a substance having an alicyclic skeleton is more preferable, and among these, cyclohexylmaleimide is most preferable.
The ratio of the N-substituted maleimide in the alkali-soluble resin of the component (B) is preferably 10 to 60% by mass, more preferably 5 to 50% by mass, and most preferably 20 to 40% by mass. When the amount of the N-substituted maleimide is less than 10% by mass, the Tg of the copolymer may be low and the heat resistance may be poor. When the content is 60% by mass or more, transparency may be lowered.
When the photosensitive resin composition of the present invention satisfies the requirement (Z2), the alkali-soluble resin of the component (B) used in the present invention is preferably a copolymer further having a self-crosslinkable group or a group further having a reaction with at least 1 group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group (hereinafter, also referred to as a crosslinkable group).
Examples of the self-crosslinkable group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetanyl group, a vinyl group, and a blocked isocyanate group.
Examples of the crosslinkable group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, and a blocked isocyanate group.
The content of such self-crosslinkable groups or crosslinkable groups in the alkali-soluble resin of the component (B) is preferably 0.1 to 0.9 per 1 unit of the repeating unit in the resin of the component (B), and more preferably 0.1 to 0.8 per 1 unit from the viewpoints of developability and solvent resistance.
In the case where the alkali-soluble resin of component (B) further contains a repeating unit having at least 1 kind of a self-crosslinkable group selected from the group consisting of an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetanyl group, a vinyl group and a blocked isocyanate group and a crosslinkable group selected from the group consisting of an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group and a blocked isocyanate group, for example, an unsaturated compound having radical polymerization and having at least 1 kind of a self-crosslinkable group selected from the group consisting of an epoxy group, an oxetanyl group, a vinyl group and a blocked isocyanate group and an N-alkoxymethyl group, an N-hydroxymethyl group and an alkoxysilyl group may be copolymerized.
Examples of the unsaturated compound having a radical polymerization property and an N-alkoxymethyl group include N-butoxymethacrylamide, N-isobutoxymethyl acrylamide, N-methoxymethyl methacrylamide, and N-methylol acrylamide.
Examples of the monomer having radical polymerizability and further having an N-hydroxymethyl group include N-methylolacrylamide and N-methylolmethacrylamide.
Examples of the monomer having radical polymerizability and further having an alkoxysilyl group include 3-acryloxytrimethoxysilane, 3-acryloxytriethoxysilane, 3-methacryloxytrimethoxysilane, and 3-methacryloxytriethoxysilane.
Examples of the unsaturated compound having radical polymerization and further having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl α -ethylacrylate, glycidyl α -n-propyl acrylate, glycidyl α -n-butyl acrylate, 3, 4-epoxybutyl methacrylate, 6, 7-epoxyheptyl acrylate, 6, 7-epoxyheptyl methacrylate, 6, 7-epoxyheptyl α -ethylacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3, 4-epoxycyclohexyl methacrylate, and the like. Among them, glycidyl methacrylate, 6, 7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3, 4-epoxycyclohexyl methacrylate and the like are preferably used. They are used alone or in combination.
Examples of the unsaturated compound having radical polymerization and further having an oxetanyl group include (meth) acrylate having an oxetanyl group and the like. Among such monomers, 3- (methacryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl) -3-ethyl-oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyl-oxetane, 3- (acryloyloxymethyl) -2-trifluoromethyl-oxetane, 3- (methacryloyloxymethyl) -2-phenyl-oxetane, 3- (acryloyloxymethyl) -2-phenyl-oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyl-oxetane, 2- (acryloyloxymethyl) -4-trifluoromethyl-oxetane, and 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl) -3-ethyl-oxetane, and the like are preferably used.
Examples of the monomer having a vinyl group and having radical polymerizability include 2- (2-ethyleneoxyethoxy) ethyl acrylate and 2- (2-ethyleneoxyethoxy) ethyl methacrylate.
Examples of the monomer having radical polymerizability and further having a blocked isocyanate group include 2- (0- (1' -methylpropyleneamino) carboxyamino) ethyl methacrylate, 2- (3, 5-dimethylpyrazolyl) carbonylamino) ethyl methacrylate, and the like.
When the photosensitive resin composition of the present invention satisfies (Z1), the total of all the repeating units of the alkali-soluble resin based on the component (B) preferably contains 10 to 70% by mass, particularly preferably 20 to 60% by mass of a structural unit derived from an unsaturated compound having radical-polymerizable properties and having at least 1 group selected from the group consisting of a self-crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetanyl group, a vinyl group and a blocked isocyanate group, and a crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group and a blocked isocyanate group. When the amount of the structural unit is less than 10% by mass, the heat resistance and surface hardness of the resulting cured film tend to be lowered, while when the amount of the structural unit exceeds 70% by mass, the storage stability of the radiation-sensitive resin composition tends to be lowered.
In the present invention, the acrylic polymer as the component (B) may be a copolymer formed by further using a monomer other than the above-mentioned monomer (hereinafter referred to as another monomer) as a structural unit. Specifically, the other monomer is not particularly limited as long as it is a monomer copolymerizable with at least one selected from the above-mentioned monomers having a carboxyl group and monomers having a phenolic hydroxyl group, so long as the properties of the component (B) are not impaired. Specific examples of such monomers include acrylate compounds, methacrylate compounds, maleimide compounds, acrylamide compounds, acrylonitrile, styrene compounds, vinyl compounds, and the like.
Hereinafter, specific examples of the other monomers are given, but the present invention is not limited thereto.
Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene methyl acrylate, phenyl acrylate, glycidyl acrylate, phenoxyethyl acrylate, 2-trifluoroethyl acrylate, t-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, diethylene glycol monoacrylate, caprolactone 2- (acryloyloxy) ethyl ester, and poly (ethylene glycol) ethyl ether acrylate.
Examples of the above-mentioned methacrylate compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthalene methacrylate, anthracene methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2-trifluoroethyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, gamma-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2- (methacryloyl) ethyl ether, and polyethylene glycol (meth) ether.
Examples of the acrylamide compound include N-methylacrylamide, N-dimethylacrylamide, N-methoxymethylacrylamide, N-butoxymethylacrylamide, and N-butoxymethylacrylamide.
Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl carbazole, allyl glycidyl ether, 3-vinyl-7-oxabicyclo [4.1.0] heptane, 1, 2-epoxy-5-hexene, and 1, 7-octadiene monoepoxide.
Examples of the styrene compound include styrene having no hydroxyl group, for example, styrene, α -methylstyrene, chlorostyrene, bromostyrene, and the like.
In the production of the alkali-soluble resin as the component (B), the ratio of the other monomer is preferably 80 mass% or less, more preferably 50 mass% or less, and still more preferably 20 mass% or less. If it exceeds 80 mass%, the essential components are relatively reduced, and thus it becomes difficult to sufficiently obtain the effect of the present invention.
The method for obtaining the alkali-soluble resin as the component (B) used in the present invention is not particularly limited, and is obtained, for example, by polymerizing a monomer having at least one selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and a group which generates a carboxylic acid or a phenolic hydroxyl group by the action of heat or an acid, a monomer having a hydroxyalkyl group, a monomer having a self-crosslinkable group selected from the group consisting of an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetanyl group, a vinyl group, a blocked isocyanate group, and at least one of the groups selected from the group consisting of an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, a blocked isocyanate group, and other copolymerizable monomers as required, and a polymerization initiator as required, in a solvent coexisting at a temperature of 50 to 110 ℃. In this case, the solvent to be used is not particularly limited as long as it is a solvent that dissolves the monomer constituting the alkali-soluble resin and the acrylic polymer having a specific functional group. Specific examples thereof include solvents described in the following (C) solvents.
The acrylic polymer having a specific functional group obtained by such an operation is usually in the form of a solution dissolved in a solvent.
The solution of the specific copolymer obtained in the above-described manner is added to diethyl ether, water, or the like with stirring to reprecipitate, and the resulting precipitate is filtered and washed, and then dried at normal temperature or under reduced pressure, thereby producing a powder of the specific copolymer. By such an operation, the polymerization initiator and unreacted monomer which coexist with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. In the case where the purification cannot be performed sufficiently by one operation, the obtained powder is dissolved in a solvent again, and the above-described operation may be repeated.
In the present invention, the powder of the specific copolymer may be used as it is, or may be dissolved in a solvent (C) described later to prepare a solution.
The alkali-soluble resin as the component (B) may be a polyimide such as a polyimide precursor including a polyamic acid, a polyamic acid ester, a partially imidized polyamic acid, or a polyimide including a carboxylic acid group, and the type of the alkali-soluble resin is not particularly limited.
The polyamic acid as a polyimide precursor can be generally obtained by polycondensing (a) a tetracarboxylic dianhydride compound with (b) a diamine compound.
The tetracarboxylic dianhydride compound (a) is not particularly limited, and specific examples thereof include pyromellitic dianhydride, 3',4,4' -biphenyl tetracarboxylic dianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, 3', 4' -diphenyl ether tetracarboxylic dianhydride, 3', aromatic tetracarboxylic acids such as 4,4' -diphenyl sulfone tetracarboxylic dianhydride, alicyclic tetracarboxylic acid dianhydride such as 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1, 2-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-tetramethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic dianhydride, 1,2,3, 4-cyclohexane tetracarboxylic dianhydride, 3, 4-dicarboxyl-1, 2,3, 4-tetrahydro-1-naphthalene succinic anhydride, and aliphatic tetracarboxylic acid dianhydride such as 1,2,3, 4-butane tetracarboxylic dianhydride.
They may be used alone or in combination of 1 or more than 2 kinds.
The diamine compound (b) is not particularly limited, and examples thereof include 2, 4-diaminobenzoic acid, 2, 5-diaminobenzoic acid, 3, 5-diaminobenzoic acid, 4, 6-diamino-1, 3-phthalic acid, 2, 5-diamino-1, 4-phthalic acid, bis (4-amino-3-carboxyphenyl) ether, bis (4-amino-3, 5-dicarboxyphenyl) ether, bis (4-amino-3-carboxyphenyl) sulfone, bis (4-amino-3, 5-dicarboxyphenyl) sulfone, 4' -diamino-3, 3' -dicarboxybiphenyl, 4' -diamino-3, 3' -dicarboxybiphenyl, 5' -dimethylbiphenyl, 4,4' -diamino-3, 3' -dicarboxy-5, 5' -dimethoxybiphenyl, 1, 4-bis (4-amino-3-carboxyphenoxy) benzene, 1, 3-bis (4-amino-3-carboxyphenoxy) benzene, bis [4- (4-amino-3-carboxyphenoxy) phenyl ] sulfone, bis [4- (4-amino-3-carboxyphenoxy) phenyl ] propane, 2-bis [4- (4-amino-3-carboxyphenoxy) phenyl ] hexafluoropropane, 2, 4-diaminophenol, 3, 5-diaminophenol, 2, 5-diaminophenol, 4, 6-diaminoresorcinol, 2, 5-diaminohydroquinone, Bis (3-amino-4-hydroxyphenyl) ether, bis (4-amino-3, 5-dihydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) methane, bis (4-amino-3, 5-dihydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3, 5-dihydroxyphenyl) sulfone, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2, 2-bis (4-amino-3, 5-dihydroxyphenyl) hexafluoropropane, 4 '-diamino-3, 3' -dihydroxybiphenyl, 4 '-diamino-3, 3' -dihydroxy-5, 5 '-dimethylbiphenyl, 4' -diamino-3, 3 '-dihydroxy-5, 5' -dimethoxybiphenyl, 1, 4-bis (3-amino-4-hydroxyphenoxy) benzene, 1, 3-bis (3-amino-4-hydroxyphenoxy) benzene, 1, 4-bis (4-amino-3-hydroxyphenoxy) benzene, 1, 3-bis (4-amino-3-hydroxyphenoxy) benzene, bis [4- (3-amino-4-hydroxyphenoxy) phenyl ] sulfone, Diamine compounds having a phenolic hydroxyl group such as bis [4- (3-amino-4-hydroxyphenoxy) phenyl ] propane and 2, 2-bis [4- (3-amino-4-hydroxyphenoxy) phenyl ] hexafluoropropane, diamine compounds having a thiophenol group such as 1, 3-diamino-4-mercaptobenzene, 1, 3-diamino-5-mercaptobenzene, 1, 4-diamino-2-mercaptobenzene, bis (4-amino-3-mercaptophenyl) ether and 2, 2-bis (3-amino-4-mercaptophenyl) hexafluoropropane, 1, 3-diaminobenzene-4-sulfonic acid, 1, 3-diaminobenzene-5-sulfonic acid, 1, 4-diaminobenzene-2-sulfonic acid, and the like, Diamine compounds having a sulfonic acid group such as bis (4-aminobenzene-3-sulfonic acid) ether, 4' -diaminobiphenyl-3, 3' -disulfonic acid, and 4,4' -diamino-3, 3' -dimethylbiphenyl-6, 6' -disulfonic acid. Further, p-phenylenediamine, m-phenylenediamine, 4' -methylene-bis (2, 6-ethylaniline), 4' -methylene-bis (2-isopropyl-6-methylaniline), 4' -methylene-bis (2, 6-diisopropylaniline), 2,4, 6-trimethyl-1, 3-phenylenediamine, 2,3,5, 6-tetramethyl-1, 4-phenylenediamine, o-tolidine, m-tolidine, 3',5,5' -tetramethylbenzidine, bis [4- (3-aminophenoxy) phenyl ] sulfone, 2-bis [4- (3-aminophenoxy) phenyl ] propane, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 4,4 '-diamino-3, 3' -dimethyldicyclohexylmethane, 4 '-diaminodiphenyl ether, 3, 4-diaminodiphenyl ether, 4' -diaminodiphenyl methane, 2-bis (4-anilino) hexafluoropropane, 2-bis (3-amino-4-toluoyl) hexafluoropropane 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl ] sulfone, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, Diamine compounds such as 2,2' -bis (trifluoromethyl) benzidine.
They may be used alone or in combination of 1 or more than 2 kinds.
In the case where the polyamic acid used in the present invention is produced from (a) a tetracarboxylic dianhydride compound and (b) a diamine compound, the compounding ratio of the two compounds, that is, the total mole number of (b) diamine compound/(the total mole number of (a) tetracarboxylic dianhydride compound) is desirably 0.7 to 1.2. As in the case of the usual polycondensation reaction, the more the molar ratio is close to 1, the higher the polymerization degree of the polyamide acid to be produced, and the higher the molecular weight.
In addition, when the diamine compound is excessively used for polymerization, the carboxylic anhydride may be reacted with the terminal amino group of the remaining polyamic acid to protect the terminal amino group.
Examples of such carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalene dicarboxylic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2, 3-dicarboxylic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, and the like.
In the production of the polyamic acid, the reaction temperature of the reaction of the diamine compound and the tetracarboxylic dianhydride compound may be selected to be any temperature of-20℃to 150℃and preferably-5℃to 100 ℃. In order to obtain a polyamic acid having a high molecular weight, the reaction temperature is 5 to 40℃and the reaction time is appropriately selected from the range of 1 to 48 hours. In order to obtain a polyamide acid having a low molecular weight and high storage stability, the partially imidized polyamide acid is more preferably selected from the group consisting of a reaction temperature of 40 to 90℃and a reaction time of 10 hours or more.
The reaction temperature in the case where the terminal amino group is protected with an acid anhydride may be any temperature selected from-20℃to 150℃and preferably-5℃to 100 ℃.
The reaction of the diamine compound and the tetracarboxylic dianhydride compound may be performed in a solvent. Examples of the solvent that can be used in this case include N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, m-cresol, γ -butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate, cyclohexanone, methyl ethyl ketone, 2-isobutyl ketone, and the like. They may be used alone or in combination. Further, even if the solvent does not dissolve the polyamic acid, the solvent may be used by mixing the solvent in such a range that the polyamic acid produced by the polymerization reaction does not precipitate.
The polyamic acid-containing solution thus obtained can be directly used for preparation of a photosensitive resin composition. In addition, the polyamic acid may be recovered by precipitation and separation in a poor solvent such as water, methanol, or ethanol.
Further, as the component (B), any polyimide may be used. The polyimide used in the present invention is a polyimide obtained by subjecting a polyimide precursor such as the polyamic acid to chemical imidization or thermal imidization at least 50%.
In order to obtain alkali solubility of the polyimide used in the photosensitive resin composition of the present invention, it is preferable to have a group selected from a carboxyl group and a phenolic hydroxyl group.
The method for introducing the carboxyl group or phenolic hydroxyl group into the polyimide is as follows: a method of using a monomer having a carboxyl group or a phenolic hydroxyl group, a method of blocking the amine end with an acid anhydride having a carboxyl group or a phenolic hydroxyl group, a method of imidizing a polyimide precursor such as polyamic acid to a degree of imidization of 99% or less, and the like.
Such polyimide can be obtained by synthesizing a polyimide precursor such as the polyamic acid, and then subjecting the resultant polyimide precursor to chemical imidization or thermal imidization.
As a method of chemical imidization, a method of adding an excessive amount of acetic anhydride and pyridine to a polyimide precursor solution and reacting at room temperature to 100 ℃ is generally used. In addition, as a method of thermal imidization, generally, a method of dehydrating a polyimide precursor solution at a temperature of 180 to 250 ℃ and simultaneously superheating the solution is used.
Further, as the alkali-soluble resin of the component (B), a phenol novolac resin can be further used.
Further, as the alkali-soluble resin of the component (B), polyester polycarboxylic acid may be used. The polyester polycarboxylic acid can be obtained from an acid dianhydride and a diol by the method described in WO 2009/051186.
As the acid dianhydride, the above-mentioned (a) tetracarboxylic dianhydride can be mentioned.
Examples of the diol include aromatic diols such as bisphenol A, bisphenol F, 4' -dihydroxybiphenyl, benzene-1, 3-dimethanol, and benzene-1, 4-dimethanol, alicyclic diols such as hydrogenated bisphenol A, hydrogenated bisphenol F, 1, 4-cyclohexanediol, 1, 3-cyclohexanedimethanol, and 1, 4-cyclohexanedimethanol, and aliphatic diols such as ethylene glycol, propylene glycol, 1, 4-butanediol, and 1, 6-hexanediol.
In addition, in the present invention, the alkali-soluble resin of the component (B) may be a mixture of various alkali-soluble resins.
(A) The ratio of the component (A) to the component (B) is 0.1 to 20 parts by mass per 100 parts by mass of the component (B).
Solvent (C)
The solvent (C) used in the present invention is not particularly limited in type and structure as long as it dissolves the component (a), the component (B), and if necessary, the component (D), the component (E), the component (F), and the component (G), and also dissolves the component (H), other additives, and the like, which are added if necessary.
Examples of the solvent (C) 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-pentanone, 2-heptanone, gamma-butyrolactone, ethyl 2-hydroxy-propionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and the like.
These solvents may be used singly or in combination of two or more.
Among these solvents (C), propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, and the like are more preferable from the viewpoint of good film coating properties and high safety. These solvents are generally used as solvents for photoresist materials.
Component (D)
Examples of the sensitizer of component (D) include (D-1) a1, 2-quinone diazonium compound, (D-2) a photoradical generator, and (D-3) a photoacid generator.
As the (D-1) 1, 2-quinone diazo compound, a compound having either a hydroxyl group or an amino group, or both a hydroxyl group and an amino group may be used, and among these hydroxyl groups or amino groups (in the case of having both a hydroxyl group and an amino group, the total amount thereof is preferably 10 to 100 mol%, particularly preferably 20 to 95 mol%, of the compound esterified with 1, 2-quinone diazosulfonic acid, or amidated.
Examples of the 1, 2-quinone diazosulfonic acid include 1, 2-naphthoquinone-2-diazo-5-sulfonic acid, 1, 2-naphthoquinone-2-diazo-4-sulfonic acid, and 1, 2-benzoquinone-2-diazo-4-sulfonic acid, and the chloride of the 1, 2-quinone diazosulfonic acid may be used in the reaction with a compound having either one or both of a hydroxyl group and an amino group.
Examples of the compound having a hydroxyl group include, phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, ethyl gallate, 1, 3-tris (4-hydroxyphenyl) butane 4, 4-isopropylidenediphenol, 2-bis (4-hydroxyphenyl) propane, 1-bis (4-hydroxyphenyl) cyclohexane, 4' -dihydroxyphenyl sulfone, 4-hexafluoroisopropylidenediphenol, 4', 4' -Trihydroxyphenylethane, 1-Trihydroxyphenylethane, 4' - [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl ] ethylene ] bisphenol, 2, 4-dihydroxybenzophenone, 2,3, 4-Trihydroxybenzophenone, 2',4,4' -tetrahydroxybenzophenone, 2,3, 4' -tetrahydroxybenzophenone, 2', aliphatic alcohols such as 3, 4' -pentahydroxybenzophenone, 2, 5-bis (2-hydroxy-5-methylbenzyl) methyl phenol compound, ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, and butyl lactate.
Examples of the amino group-containing compound include anilines such as aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4 '-diaminophenylmethane, and 4,4' -diaminodiphenyl ether, and aminocyclohexane.
Examples of the compound containing both hydroxyl and amino groups include aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2, 3-diaminophenol, 2, 4-diaminophenol, 4 '-diamino-4' -hydroxytriphenylmethane, 4-amino-4 ', 4' -dihydroxytriphenylmethane, bis (4-amino-3-carboxyl-5-hydroxyphenyl) ether, bis (4-amino-3-carboxyl-5-hydroxyphenyl) methane, 2-bis (4-amino-3-carboxyl-5-hydroxyphenyl) propane, 2-bis (4-amino-3-carboxyl-5-hydroxyphenyl) hexafluoropropane, and alkanolamines such as 2-aminoethanol, 3-aminopropanol and 4-aminocyclohexanol.
These 1, 2-quinone diazo compounds may be used alone or in combination of 2 or more.
When the photosensitive resin composition of the present invention is a positive photosensitive resin composition, the content of the compound having a quinone diazide group of the component (D-1) is preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, and even more preferably 10 to 40 parts by mass, based on 100 parts by mass of the total of the component (a) and the component (B). When the amount is less than 5 parts by mass, the difference in dissolution rate between the exposed portion and the unexposed portion of the positive photosensitive resin composition in the developer may be small, and it may be difficult to form a pattern by development. In addition, if the amount exceeds 100 parts by mass, the 1, 2-quinone diazonium compound cannot be sufficiently decomposed by short-time exposure, and therefore the sensitivity may be lowered, and the (D-1) component absorbs light to lower the transparency of the cured film.
The photo radical generator (D-2) is not particularly limited as long as it generates radicals by exposure. Specific examples thereof include aromatic ketones such as benzophenone, michler's ketone, 4' -bis (diethylamino) benzophenone, 4-methoxy-4 ' -dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrene, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzoin ether such as methylbenzin, benzoin such as ethylbenzoin, 2- (o-chlorophenyl) -4, 5-phenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-bis (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, 2,4, 5-triarylimidazole dimer, 2- (o-chlorophenyl) -4, 5-bis (m-methylphenyl) imidazole dimer, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -2-trichloromethyl-5-styryl-1, 3, 4-butanoneDiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-Diazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-Halomethyl group such as diazoleHalogenated methyl-s-triazine compounds such as diazole compound, 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2, 4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1, 3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphtho-1-yl) -4, 6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphtho-1-yl) -4, 6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphtho-1-yl) -4, 6-bis-trichloromethyl-s-triazine 2, 2-dimethoxy-1, 2-diphenylethan-1-one, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinoacetone, 1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 1-hydroxy-cyclohexyl-phenyl ketone, benzil, benzoyl benzoic acid methyl ester, 4-benzoyl-4' -methyl diphenyl sulfide, benzil methyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2, 4-diethylthioxanthone, 2, 4-dimethylthioxanthone, isopropylthioxanthone, 1- (4-phenylsulfanylphenyl) -1, 2-octanedione-2- (O-benzoyloxime), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), 4-benzoyl-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenylketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone, α -dimethoxy- α -phenylacetophenone, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-morpholinone, and the like.
The photoradical generator is readily available as a commercially available product, and specific examples thereof include IRGACURE173、IRGACURE 500、IRGACURE 2959、IRGACURE 754、IRGACURE 907、IRGACURE 369、IRGACURE 1300、IRGACURE 819、IRGACURE 819DW、IRGACURE 1880、IRGACURE 1870、DAROCURE TPO、DAROCURE 4265、IRGACURE 784、IRGACURE OXE01、IRGACURE OXE02、IRGACURE 250( or more, manufactured by BASF corporation), KAYACURE DETX-S, KAYACURE CTX, KAYACURE BMS, KAYACURE-EAQ (manufactured by japan chemical corporation, )、TAZ-101、TAZ-102、TAZ-103、TAZ-104、TAZ-106、TAZ-107、TAZ-108、TAZ-110、TAZ-113、TAZ-114、TAZ-118、TAZ-122、TAZ-123、TAZ-140、TAZ-204( or more, manufactured by brake chemical corporation), and the like.
These photo radical generators may be used alone or in combination of two or more.
When the photosensitive resin composition of the present invention contains the component (D-2), the content is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and particularly preferably 1 to 15 parts by mass, relative to 100 parts by mass of the component (a). If the ratio is too small, the exposure portion may be insufficiently cured, and patterning may be impossible, or a film with low reliability may be formed even if patterning is possible. If the ratio is too large, the transmittance of the coating film may be reduced, or development failure may occur in the unexposed portion.
The photoacid generator of (D-3) is not particularly limited as long as it is a compound that generates an acid by photodecomposition upon irradiation with ultraviolet rays. Examples of the acid generated when the photoacid generator is photodegradable include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylene sulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1h,2 h-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethane sulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, and the like, or a hydrate or salt thereof.
Examples of the photoacid generator include diazomethane compounds,Salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzoin tosylate compounds, iron arene complex compounds, halogen-containing triazine compounds, acetophenone derivative compounds, cyano-containing oxime sulfonate compounds, and the like. The photoacid generator known in the past or used in the past can be used in the present invention without any particular limitation. In the present invention, the photoacid generator of component (D) may be used alone or in combination of two or more. Specific examples thereof include compounds represented by the following formulas [ PAG-1] to [ PAG-41 ]. /(I)
When the photosensitive resin composition of the present embodiment contains the component (D-3), the content is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 8 parts by mass, based on 100 parts by mass of the total of the component (a) and the component (B). When the content of the component (D-3) is 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be imparted. However, in the case of more than 20 parts by mass, the unexposed portion may become poor in development or the storage stability of the composition may be lowered.
Component (E)
(E) The component (b) is a crosslinking agent, and is introduced into the photosensitive resin composition of the present invention when the composition satisfies the requirement (Z1). More specifically, the compound has a structure capable of forming a crosslinked structure by thermal reaction with a thermally reactive site (for example, a carboxyl group and/or a phenolic hydroxyl group) of the component (B). Specific examples are given below, but are not limited thereto. The thermal crosslinking agent is preferably, for example, one selected from (E1) crosslinkable compounds having 2 or more substituents selected from alkoxymethyl groups and hydroxymethyl groups, and (E2) crosslinkable compounds represented by the following formula (2). These crosslinking agents may be used alone or in combination of 2 or more.
(E1) The crosslinkable compound having 2 or more substituents selected from the group consisting of alkoxymethyl groups and hydroxymethyl groups in the component (a) undergoes a crosslinking reaction by a dehydration condensation reaction when exposed to a high temperature during heat curing. Examples of such compounds include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenolic compounds.
Specific examples of alkoxymethylated glycolurils include, for example, 1,3,4, 6-tetra (methoxymethyl) glycoluril, 1,3,4, 6-tetra (butoxymethyl) glycoluril, 1,3,4, 6-tetra (hydroxymethyl) glycoluril, 1, 3-bis (hydroxymethyl) urea, 1, 3-tetra (butoxymethyl) urea, 1, 3-tetra (methoxymethyl) urea, 1, 3-bis (hydroxymethyl) -4, 5-dihydroxy-2-imidazolidinone, and 1, 3-bis (methoxymethyl) -4, 5-dimethoxy-2-imidazolidinone. Examples of commercial products include a compound such as a three-well-site sweet urea compound (trade name: relative 1170, relative 1174), a methylated urea resin (trade name: UFR (registered trademark) 65), a butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11 HV), a DIC urea/formaldehyde resin (high condensation type trade name: parts of the company J-300S, parts of the company P-955, parts of the company P-N), and the like.
Specific examples of the alkoxymethylated benzoguanamine include tetramethoxymethyl benzoguanamine and the like. As commercial products, a three-well core (trade name: ct 1123, (strain) three and chemical (trade name: ct) BX-4000, ct BX-37, ct BL-60, ct BX-55H, and the like.
Specific examples of the alkoxymethylated melamine include, for example, hexamethoxymethyl melamine. Examples of the commercial products include a three-well-site methoxymethyl melamine compound (trade name: brand 300, registered trademark) by the three-well-site company, a state 301, a state 303, a state 350, a butoxymethyl melamine compound (trade name: コ, a state 506, a state コ, a state 508, a three-and-a-state methoxymethyl melamine compound (trade name: brand )MW-30、ニカラックMW-22、ニカラックMW-11、ニカラックMW-100LM、ニカラックMS-001、ニカラックMX-002、ニカラックMX-730、ニカラックMX-750、ニカラックMX-035)、, a state of the three-and-a-state methoxymethyl melamine compound (trade name: MX-45, a state of the three-and-a-state methoxymethyl melamine compound (trade name: )MW-30、ニカラックMW-22、ニカラックMW-11、ニカラックMW-100LM、ニカラックMS-001、ニカラックMX-002、ニカラックMX-730、ニカラックMX-750、ニカラックMX-035)、, a state of the three-and-a-state melamine compound (registered trademark: MX-45, a state of the three-and-a-state memory MX-410, a state of the three-and-a-state memory MX-302).
Further, the compound may be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound, in which a hydrogen atom of such an amino group is substituted with a hydroxymethyl group or an alkoxymethyl group. For example, a high molecular weight compound produced from a melamine compound and a benzoguanamine compound as described in U.S. Pat. No. 6323310 can be cited. The melamine compound is commercially available under the trade name: the industrial products of benzoguanamine compound described above, such as the registered trademark 303 (Sanjingyi brand) and the like, include trade names: and a core 1123 (manufactured by tikok corporation).
Specific examples of the phenolic plastic compound include, for example, 2, 6-bis (hydroxymethyl) phenol, 2, 6-bis (hydroxymethyl) cresol, 2, 6-bis (hydroxymethyl) -4-methoxyphenol, 3',5,5' -tetra (hydroxymethyl) biphenyl-4, 4 '-diol, 3' -methylenebis (2-hydroxy-5-methylbenzyl alcohol), 4'- (1-methylethylidene) bis [ 2-methyl-6-hydroxymethylphenol ], 4' -methylenebis [ 2-methyl-6-hydroxymethylphenol ]: 4,4'- (1-methylethylene) bis [2, 6-bis (hydroxymethyl) phenol ], 4' -methylenebis [2, 6-bis (hydroxymethyl) phenol ], 2, 6-bis (methoxymethyl) phenol, 2, 6-bis (methoxymethyl) cresol, 2, 6-bis (methoxymethyl) -4-methoxyphenol, 3',5,5' -tetra (methoxymethyl) biphenyl-4, 4 '-diol, 3' -methylenebis (2-methoxy-5-methylbenzyl alcohol), 4'- (1-methylethylidene) bis [ 2-methyl-6-methoxymethylphenol ], 4' -methylenebis [ 2-methyl-6-methoxymethylphenol ] 4,4'- (1-methylethylene) bis [2, 6-bis (methoxymethyl) phenol ], 4' -methylenebis [2, 6-bis (methoxymethyl) phenol ], and the like. As commercially available products, specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI X-DF, BI25X-TPA (above, manufactured by Asahi organic materials industries, ltd.), and the like.
Further, as the component (E1), a polymer produced using a compound of: acrylamide compounds or methacrylamide compounds substituted with hydroxymethyl or alkoxymethyl such as N-methylolacrylamide, N-methoxymethylolacrylamide, N-ethoxymethylacrylamide and N-butoxymethylolmethacrylamide.
Examples of such polymers include poly (N-butoxymethacrylamide), copolymers of N-butoxymethacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methyl methacrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethacrylamide and benzyl methacrylate and 2-hydroxypropyl methacrylate. The weight average molecular weight of such a polymer is 1,000 to 50,000, preferably 1,500 to 20,000, more preferably 2,000 to 10,000.
The photosensitive resin composition of the present invention may contain a crosslinkable compound represented by the following formula (2) as the component (E2).
(Wherein k represents an integer of 2 to 10, m represents an integer of 0 to 4, and R 11 represents a k-valent organic group)
(E2) The component (c) is not particularly limited as long as it is a compound having an oxidized cycloolefin structure represented by the formula (2). Specific examples thereof include the following formulas E2-1 and E2-2, and commercially available products shown below.
Examples of the commercial products include d-GT-401, d-beta-GT-403, d-beta-GT-301, d-beta-GT-302, d-i 2021, d-i 3000 (product name of the chemical industry of d-i), d-i コ (product name of the ridge of d-i) as an alicyclic epoxy resin, CY175, CY177, CY179 (above), the brand name of CIBA-GEIGY A.G), the brand name of the tatami-CY-182, the brand name of the tatami-CY-192, the brand name of the tatami-CY-184 (above, the brand name of CIBA-GEIGY A.G), the brand name of the tatami-200, the brand name 400 (above, the brand name of DIC), the brand name of the tatami- コ, the brand 871 (above, the brand name of d コ), the brand name 872 (above, the brand name of the oiled tatami-cover), the brand name of ED-5661, the brand name of ED-5662 (above, the brand name of tatami コ), and the like. These crosslinkable compounds may be used singly or in combination of 2 or more.
Among them, compounds represented by the formulas E2-1 and E2-2 having a cyclohexene oxide structure, and compounds represented by the formulas GT-401, d 2, d 403, d 2, d 301, d 302, d 2021, d 2, d 3000 are preferable from the viewpoints of heat resistance, solvent resistance, process resistance such as long-time firing resistance, and transparency.
As the component E, a compound capable of forming a crosslinked structure by thermal reaction with a thermally reactive site (for example, a carboxyl group and/or a phenolic hydroxyl group) of the component (B) other than the component shown as the component (E1) and the component (E2) may be used. Specifically, examples thereof include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2-dibromoneopentyl glycol diglycidyl ether, 1,3,5, 6-tetraglycidyl-2, 4-hexanediol, N, N, N ', N ', -tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane, and N, N, N ', N ', -tetraglycidyl-4, 4' -diaminodiphenylmethane, VESTANAT B/100, VESTAGON BF 1540 (above, produced by Sanchi Kogyo Co., ltd.), po Kogyo B-882N (registered trademark), po B-7075 (above, isocyanurate type modified polyisocyanate, produced by Sanchi Chemie Co., ltd.), and the like.
As the component E, a polymer having a structure in which 2 or more thermally reactive sites (for example, carboxyl groups and/or phenolic hydroxyl groups) of the component (B) can be thermally reacted to form a crosslinked structure can be used. Specifically, examples thereof include polymers produced using compounds having an epoxy group such as glycidyl methacrylate, 3, 4-epoxycyclohexylmethyl methacrylate, and 3, 4-epoxycyclohexylmethyl methacrylate, polymers produced using compounds having an alkoxysilyl group such as 3-methacryloxypropyltrimethoxysilane, and 2-isocyanatoethyl methacrylate (MoI, registered trademark), polymers produced by blocking isocyanate groups such as 2-isocyanatoethyl acrylate (manufactured by Showa electric, inc.), 2- (0- [1' -methylpropyleneamino ] carboxyamino) ethyl methacrylate (manufactured by Showa electric, inc.), 2- [ (3, 5-dimethylpyrazolyl) carbonylamino ] ethyl methacrylate (manufactured by Showa electric, inc.), and 2- (3, 5-dimethylpyrazolyl) carbonylamino ] ethyl methacrylate (manufactured by Showa electric, inc. ], etc. These compounds may be used alone or in combination of two or more to produce a polymer, or may be used in combination with other compounds to produce a polymer.
In the case where the component (B) has a group reactive with at least 1 group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group, a compound having 2 or more groups selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group may be used as the component (E).
These crosslinkable compounds may be used singly or in combination of 2 or more.
When the component (E) is selected as the crosslinking agent in the photosensitive resin composition of the present invention, the content is 1 to 50 parts by mass, preferably 1 to 40 parts by mass, and more preferably 1 to 30 parts by mass, based on 100 parts by mass of the total of the component (a) and the component (B). When the content of the crosslinkable compound is small, the crosslinking density by the crosslinkable compound is insufficient, and thus the effect of improving heat resistance, solvent resistance, resistance to firing for a long time, and the like after pattern formation may not be obtained. On the other hand, when the amount exceeds 50 parts by mass, there is a case where an uncrosslinked crosslinkable compound is present, and heat resistance, solvent resistance, resistance to long-time firing, and the like after patterning are lowered, and further, the storage stability of the photosensitive resin composition is deteriorated.
Component (F)
(F) The component (a) is a compound having 2 or more ethylenically polymerizable groups. The term "compound having 2 or more ethylenically polymerizable groups" as used herein means a compound having 2 or more polymerizable groups in one molecule and these polymerizable groups are located at the molecular terminals, and these polymerizable groups mean at least 1 polymerizable group selected from the group consisting of an acrylate group, a methacrylate group, a vinyl group and an allyl group.
The compound having 2 or more ethylenically polymerizable groups as the component (F) is preferably a compound having a molecular weight (in the case where the compound is a polymer, a weight average molecular weight) of 1,000 or less, from the viewpoint that the compatibility with each component is good and the developability is not affected in the solution of the negative photosensitive resin composition in the photosensitive resin composition of the present invention.
Specific examples of such compounds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, trimethylolpropane tetraacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane trimethacrylate, 1,3, 5-triacryloylhexahydro-s-triazine, 1,3, 5-trimethylacryloylhexahydro-s-triazine, tris (hydroxyethyl acryloyl) isocyanurate, tris (hydroxyethyl methacryloyl) isocyanurate, triacryloyl formal, trimethacryloyl formal, 1, 6-hexanediol acrylate, 1, 6-hexanediol methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 2-hydroxy propylene glycol diacrylate, 2-hydroxy propylene glycol dimethacrylate, diethylene glycol dimethacrylate, isopropyl glycol dimethacrylate, triethylene glycol dimethacrylate, triethylene glycol, N '-bis (acryl) cysteine, N' -bis (methacryl) cysteine, thiodiglycol diacrylate, thiodiglycol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate, bisphenol S dimethacrylate, bisphenol ethyl fluorene diacrylate, bisphenol ethyl fluorene dimethacrylate, diallyl ether bisphenol A, diallyl maleate, triallyl trimellitate and the like.
The above-mentioned polyfunctional acrylate compound is easily available in the form of a commercially available product, and specific examples thereof include KYARAD T-1420、KYARAD DPHA、KYARAD DPHA-2C、KYARAD D-310、KYARAD D-330、KYARAD DPCA-20、KYARAD DPCA-30、KYARAD DPCA-60、KYARAD DPCA-120、KYARAD DN-0075、KYARAD DN-2475、KYARAD R-526、KYARAD NPGDA、KYARAD PEG400DA、KYARAD MANDA、KYARAD R-167、KYARAD HX-220、KYARAD HX620、KYARAD R-551、KYARAD R-712、KYARAD R-604、KYARAD R-684、KYARAD GPO-303、KYARAD TMPTA、KYARAD THE-330、KYARAD TPA-320、KYARAD TPA-330、KYARAD PET-30、KYARAD RP-1040( or more, )、アロニックスM-210、アロニックスM-240、アロニックスM-6200、アロニックスM-309、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-450、アロニックスM-7100、アロニックスM-8030、アロニックスM-8060、アロニックスM-1310、アロニックスM-1600、アロニックスM-1960、アロニックスM-8100、アロニックスM-8530、アロニックスM-8560、アロニックスM-9050( or more available from japan chemical industry (product of eastern chemical industry), コ or more, 300 of level コ, 360 of level コ, コ of GPT, コ of level 3PA, 400 of level コ, 260 of level コ, コ of level 312, コ of level 335HP (product of osaka organic chemical industry (product of high-speed chemical industry)), and )、A-9300、A-GLY-9E、A-GLY-20E、A-TMM-3、A-TMM-3L、A-TMM-3LM-N、A-TMPT、AD-TMP、ATM-35E、A-TMMT、A-9550、A-DPH、TMPT、9PG、701,1206PE、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( or more.
These compounds having 2 or more ethylenically polymerizable groups may be used in 1 or 2 or more in combination.
When the photosensitive resin composition of the present invention contains the component (F), the content is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass, and particularly preferably 50 to 150 parts by mass, relative to 100 parts by mass of the total of the component (a) and the component (B). If the ratio is too small, the exposure portion may be insufficiently cured, and patterning may be impossible, or a film having low reliability may be formed even if patterning is possible. In addition, when the ratio is too large, there is a case where the coating film after the pre-baking becomes tacky or the unexposed portion becomes poorly dissolved at the time of development.
Component (G)
The component (G) used in the photosensitive resin composition of the present invention is a compound having 2 or more functional groups that form covalent bonds by an acid. Examples of such functional groups that form covalent bonds by acid include epoxy groups, alkoxymethyl groups, and hydroxymethyl groups.
Examples of the compound having 2 or more epoxy groups include tris (2, 3-epoxypropyl) isocyanurate, 1, 4-butanediol diglycidyl ether, 1, 2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2, 6-diglycidyl phenyl glycidyl ether, 1, 3-tris [ p- (2, 3-epoxypropoxy) phenyl ] propane, diglycidyl 1, 2-cyclohexanedicarboxylate, 4' -methylenebis (N, N-diglycidyl aniline), 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate, trimethylolethane triglycidyl ether and bisphenol-A-diglycidyl ether, pentaerythritol polyglycidyl ether, and the like.
Further, as the compound having 2 or more epoxy groups, commercially available compounds can be used in view of easy availability. Specific examples (trade names) are given below, but are not limited thereto: epoxy resins having an amino group such as YH-434 and YH434L (manufactured by DONGSHI chemical Co., ltd.); the catalyst may be selected from the group consisting of a group of polyethylene GT-401, a group of polyethylene GT-403, a group of polyethylene GT-301, a group of polyethylene GT-302, a group of polyethylene 2021, a group of polyethylene GT-2, a group of polyethylene GT-302, a group of polyethylene epoxy resins having cyclohexene oxide structure such as2 k 3000 (manufactured by dow chemical industry, ltd.); the bisphenol a type epoxy resins such as "end 1001, end コ, end コ, end 1003, end コ, end 1007, end コ, end 1010, end コ, end 828 (the above oil station) and the like; bisphenol F-type epoxy resins such as "fuzzing" 807 (currently available from "dijj" in the trade); the nuts 152, コ, 154 (above, oil of the current station), EPPN, EPPN, 202 (above, phenol novolac type epoxy resins such as those manufactured by japan chemical, ltd.); cresol novolac type epoxy resins such as EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (manufactured by japan chemical, supra), and d コ d 180S75 (manufactured by oiled d) and d (manufactured by current di tie); the hua コ EX-252 (manufactured by nun, nun) and CY175, CY177, CY179, tatali-lid CY-182, tatali-lid CY-192, tatali-lid CY-184 (above, manufactured by CIBA-GEIGY A.G), tatalin-lid 200, tatalin-lid 400 (above, the large japan industrial chemicals (DIC (strain) at present), the nut コ nut 871, the nut コ nut 872 (above, the oil of the wire (the current wire) is made of ED-5661, ED-5662 (above, seta, strain コ, and the like, and alicyclic epoxy resin ;デナコールEX-611、デナコールEX-612、デナコールEX-614、デナコールEX-622、デナコールEX-411、デナコールEX-512、デナコールEX-522、デナコールEX-421、デナコールEX-313、デナコールEX-314、デナコールEX-321(ナガセケムテックス(, manufactured by the strain) and the like).
In addition, as the compound having 2 or more epoxy groups, a polymer having an epoxy group may be used.
The polymer having an epoxy group can be produced by, for example, addition polymerization using an addition polymerizable monomer having an epoxy group. Examples thereof include addition polymers such as polyglycidyl acrylate, a copolymer of glycidyl methacrylate and ethyl methacrylate, and a copolymer of glycidyl methacrylate and styrene and 2-hydroxyethyl methacrylate, and polycondensates such as epoxy novolac.
Alternatively, the polymer having an epoxy group may be produced by reacting a polymer compound having a hydroxyl group with a compound having an epoxy group such as epichlorohydrin or glycidyl tosylate.
The weight average molecular weight of such a polymer is, for example, 300 to 20,000.
These compounds having 2 or more epoxy groups may be used alone or in combination of 2 or more.
Examples of the compound having 2 or more substituents selected from alkoxymethyl groups and hydroxymethyl groups include alkoxymethylated glycolurils, alkoxymethylated benzoguanamines, alkoxymethylated melamines, and the like, and phenolic compounds.
Specific examples of the alkoxymethylated glycoluril include those described in the above description at page 33, paragraph 2.
Specific examples of the alkoxymethylated benzoguanamine include those described in the above description at page 33, paragraph 3.
Specific examples of the alkoxymethylated melamine include those described in the above description at page 33 and paragraph 4.
Further, the compound may be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound, in which a hydrogen atom of such an amino group is substituted with a hydroxymethyl group or an alkoxymethyl group. Examples thereof include high molecular weight compounds produced from melamine compounds and benzoguanamine compounds as described in U.S. Pat. No. 6323310. The melamine compound is commercially available under the trade name: the industrial products of benzoguanamine compound described above, such as the registered trademark 303 (Sanjingyi brand) and the like, include trade names: and a core 1123 (manufactured by tikok corporation).
Specific examples of the phenolic compound include those described in the above description at page 34, paragraph 2.
Further, as the component (G), the following polymers may be used: polymers produced by using an acrylamide compound or a methacrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-methylolacrylamide, N-methoxymethylolacrylamide, N-ethoxymethylacrylamide, or N-butoxymethylolmethacrylamide.
Examples of such polymers include poly (N-butoxymethacrylamide), copolymers of N-butoxymethacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methyl methacrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethacrylamide and benzyl methacrylate and 2-hydroxypropyl methacrylate. The weight average molecular weight of such a polymer is 1,000 to 50,000, preferably 1,500 to 20,000, more preferably 2,000 to 10,000.
In the case where the photosensitive resin composition of the present invention contains a compound having 2 or more functional groups that form covalent bonds by acid as component (G), the content is preferably 5 to 200 parts by mass, more preferably 50 to 150 parts by mass, based on 100 parts by mass of the total of component (a) and component (B). If the ratio is too small, the photocurability of the negative photosensitive resin composition may be lowered, while if it is too large, the developability of the unexposed portion may be lowered, resulting in a film residue or a residue.
< Other additives >)
Further, the photosensitive resin composition of the present invention may contain a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, an adhesion promoter, a dissolution promoter such as a polyhydric phenol or a polycarboxylic acid, and the like as required, as long as the effect of the present invention is not impaired.
Photosensitive resin composition
The photosensitive resin composition of the present invention is a photosensitive resin composition containing the following component (a), component (B), component (C), solvent (D), and, if necessary, one or more of a crosslinking agent of component (E), a compound having 2 or more ethylenically polymerizable groups of component (F), a compound having 2 or more functional groups forming covalent bonds by acid of component (G), and other additives.
(A) The components are as follows: polymers having the following groups (A1) and (A2), optionally (A3)
(A1) Lyophobic group
(A2) Trialkoxysilyl groups
(A3) At least 1 group selected from the group consisting of hydroxyl group, carboxyl group, amide group and amino group,
(B) The components are as follows: an alkali-soluble resin, a solvent,
(C) The solvent is used for the preparation of the aqueous solution,
(D) The components are as follows: and (3) a sensitizer.
Among them, preferred examples of the photosensitive resin composition of the present invention are as follows.
[1]: A photosensitive resin composition containing 0.1 to 20 parts by mass of a component (A) per 100 parts by mass of a component (B), the components being dissolved in a solvent (C).
[2]: The photosensitive resin composition contains 0.1 to 20 parts by mass of component (A) and 5 to 100 parts by mass of component (D) per 100 parts by mass of component (B), and the components are dissolved in a solvent (C), and the component (D) is further a photosensitive resin composition of component (D-1).
[3]: A photosensitive resin composition comprising 100 parts by mass of a component (B) and 0.1 to 20 parts by mass of a component (A) and 5 to 100 parts by mass of a component (D) dissolved in a solvent (C), wherein the photosensitive resin composition further comprises 1 to 50 parts by mass of a crosslinking agent as a component (E) relative to 100 parts by mass of the total of the component (A) and the component (B), and wherein the component (D) is a component (D-1).
[4]: The photosensitive resin composition comprises 0.1 to 20 parts by mass of component (A) relative to 100 parts by mass of component (B), 5 to 200 parts by mass of component (F) relative to 100 parts by mass of the total of component (A) and component (B), and 0.1 to 30 parts by mass of component (D) relative to 100 parts by mass of the total of component (A), component (B) and component (F), wherein the components are dissolved in a solvent (C), and the component (D) is a component (D-2).
The proportion of the solid component in the 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 mass%, and further, for example, 5 to 60 mass%, or 10 to 50 mass%. The solid component herein means a component in which the solvent (C) is removed from all components of the photosensitive resin composition.
The method for preparing the photosensitive resin composition of the present invention is not particularly limited, and examples of the method include a method in which the component (a) (specific polymer) is dissolved in the solvent (C), and the alkali-soluble resin of the component (B), the photosensitizer of the component (D), the crosslinking agent of the component (E) if necessary, the compound having 2 or more ethylenically polymerizable groups of the component (F), and the compound having 2 or more functional groups forming covalent bonds by acid of the component (G) are mixed in a predetermined ratio in the solution to prepare a uniform solution; or a method of further adding other additives as needed and mixing them at an appropriate stage of the preparation method.
In the preparation of the photosensitive resin composition of the present invention, a solution of the copolymer obtained by polymerization in the solvent (C) may be used as it is, and in this case, the solvent (C) may be further added for the purpose of concentration adjustment when the component (B), the component (D), the component (E) if necessary, the component (F), the component (G) and the like are added to the solution of the component (a) in the same manner as described above to prepare a uniform solution. In this case, the solvent (C) used in the formation of the specific copolymer may be the same as or different from the solvent (C) used for adjusting the concentration in the preparation of the photosensitive resin composition.
The solution of the photosensitive resin composition thus prepared is preferably used after filtration using a filter having a pore diameter of about 0.2 μm or the like.
< Coating film and cured film >
The photosensitive resin composition of the present invention can be applied onto 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) by spin coating, flow coating, roll coating, slit coating, spin coating, inkjet coating, or the like, and then predrying with an electric hot plate, an oven, or the like, to form a coating film. Then, the coated film is subjected to a heat treatment to form a photosensitive resin film.
The heating conditions include, for example, a heating temperature and a heating time appropriately selected from the range of 70 to 160 ℃ and a time of 0.3 to 60 minutes. The heating temperature and heating time are preferably 80 to 140 ℃ and 0.5 to 10 minutes.
The film thickness of the photosensitive resin film formed from the photosensitive resin composition is, for example, 0.1 μm to 30 μm, further, for example, 0.2 μm to 10 μm, and further, for example, 0.3 μm to 8 μm.
A mask having a predetermined pattern is attached to the coating film obtained as described above, and light such as ultraviolet light is irradiated thereto, and the coating film is developed with an alkaline developer, whereby either the exposed portion or the unexposed portion is washed out depending on the material composition, and the remaining patterned film is heated at 80 to 140 ℃ for 0.5 to 10 minutes as necessary, whereby a relief pattern (RELIEF PATTERN) having a sharp end surface is obtained.
Examples of the alkali developer that can be used include aqueous solutions of alkali metal hydroxides such as potassium carbonate, 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 developer solutions.
Among the above, a tetraethylammonium hydroxide aqueous solution of 0.1 to 2.58 mass% is generally used as a developing solution for a photoresist, and the photosensitive resin composition of the present invention can be developed well without causing problems such as swelling of a film.
As the development method, a dipping method, a shaking dipping method, or the like can be used. The development time at this time is usually 15 to 180 seconds.
After development, the photosensitive resin film is washed with running water for, for example, 20 to 120 seconds, and then air-dried using compressed air or compressed nitrogen or by rotation, whereby moisture on the substrate is removed, and a film on which a pattern is formed is obtained.
Then, such a pattern-formed film is post-baked for heat curing, specifically, by heating using a hot plate, an oven, or the like, a film having a good relief pattern excellent in heat resistance, transparency, planarization, low water absorption, chemical resistance, or the like is obtained.
As the post baking, generally, a method of treating for 5 to 30 minutes in the case of a hot plate and for 30 to 90 minutes in the case of an oven at a heating temperature selected from the range of 140 to 270℃is employed.
Further, by such post baking, a cured film having a good pattern shape as a target can be obtained.
As described above, the photosensitive resin composition of the present invention can form a cured film having a high storage stability, a sufficiently high sensitivity, and very little film reduction in the unexposed area during development, and a fine pattern.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples. The number average molecular weight and the weight average molecular weight of the polymer were measured as follows.
[ Determination of number average molecular weight and weight average molecular weight of Polymer ]
The number average molecular weight and the weight average molecular weight of the polymer were measured using a GPC system manufactured by Japanese spectroscopic Co., ltd.) as a device, and Shodex (registered trademark) KF-804L and 803L as columns, under the following conditions.
Column incubator: 40 DEG C
Flow rate: 1 ml/min
The number average molecular weight (hereinafter referred to as Mn.) and the weight average molecular weight (hereinafter referred to as Mw.) are expressed as polystyrene conversion values.
The shorthand notation used in the following examples is as follows.
MMA: methyl methacrylate
HEMA: methacrylic acid 2-hydroxy ethyl ester
HPMA: 4-hydroxy phenyl methacrylate
HPMA-QD: compounds synthesized by condensation of 1mol of 4-hydroxyphenyl methacrylate with 1.1mol of 1, 2-naphthoquinone-2-diazo-5-sulfonyl chloride
CHMI: n-cyclohexylmaleimide
PFHMA: 2- (perfluorohexyl) ethyl methacrylate
TMSSMA: methacryloxypropyl tris (trimethylsiloxy) silane
MAA: methacrylic acid
MAAm: methacrylamide
KBM-503: 3-methacryloxypropyl triethoxysilane
P7: a polymer of 85% hydroxystyrene with 15% styrene, a polymer of 70% hydroxystyrene with 30% styrene was blended with 3:7 styrene Polymer obtained by mixing
AIBN: alpha, alpha' -azobisisobutyronitrile
QD: compounds synthesized by condensation of 1mol of alpha, alpha' -tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene with 2mol of 1, 2-naphthoquinone-2-diazo-5-sulfonyl chloride
GT-401: tetra3, 4-epoxycyclohexylmethyl butane tetracarboxylic acid ester modified epsilon-caprolactone
I907: 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one (IRGACURE 907, manufactured by BASF)
DEAB:4,4' -bis (diethylamino) benzophenone
DPHA: dipentaerythritol hexaacrylate
8KQ:8KQ-2001 (Chengfujin, inc.) alkali-soluble UV-curable acrylic resin
PGME: propylene glycol monomethyl ether
PGMEA: propylene glycol monomethyl ether acetate
CHN: cyclohexanone
MIBK: methyl isobutyl ketone
TMAH: tetramethyl ammonium hydroxide
Synthesis example 1 >
PFHMA 5.00.00 g, KBM-503.87 g, HEMA 1.00g, CHMI 1.38g, AIBN 0.51g were dissolved in 25.14g of PGME, and reacted at 80℃for 20 hours to obtain an acrylic polymer solution (30% by mass of solid content concentration) (P1). The Mn of the resulting acrylic polymer was 4900 and the Mw was 6600.
Synthesis example 2
PFHMA 5.00.00 g, KBM-503.83 g, HEMA 1.51g, AIBN 0.52g were dissolved in 25.32g of PGME, and reacted at 80℃for 20 hours to obtain an acrylic polymer solution (30% by mass of solid content concentration) (P2). The Mn of the resulting acrylic polymer was 4800 and the Mw was 6700.
Synthesis example 3 >
PFHMA 5.00.00 g, MMA 1.16g, HEMA 1.00g, CHMI 1.38g, AIBN 0.43g was dissolved in PGME 20.93g, and reacted at 80℃for 20 hours to obtain an acrylic polymer solution (solid content: 30 mass%) (P3). The Mn of the resulting acrylic polymer was 4800 and the Mw was 6600.
Synthesis example 4 >
PFHMA 5.00.00 g, MAAm 0.98g, HEMA 1.00g, CHMI 1.38g, AIBN 0.42g were dissolved in PGME 20.51g, and reacted at 80℃for 20 hours to obtain an acrylic polymer solution (solid content concentration: 30 mass%) (P4). The Mn of the resulting acrylic polymer was 4900 and the Mw was 6700.
Synthesis example 5 >
90.00G of MAA, 225.00g of HEMA, 45.00g of HPMA, 180.00g of MMA, 360.00g of CHMI and 57.60g of AIBN were dissolved in 1436.40g of PGME and reacted at 80℃for 20 hours to obtain an acrylic polymer solution (40% by mass of solid content) (P5). The Mn of the resulting acrylic polymer was 3100 and the Mw was 6100.
Synthesis example 6 >
MAA (100.00 g), HEMA 188.89g, MMA 190.37g, CHMI 262.96g, AIBN 47.50g were dissolved in PGME 1184.59g and reacted at 80℃for 20 hours to obtain an acrylic polymer solution (solid content: 40 mass%) (P6). The Mn of the resulting acrylic polymer was 3800 and the Mw was 7300.
Synthesis example 7 >
HPMA-QD 2.50g, TMSSMA 2.58g, PFHMA 5.26g, MAA 0.70g, CHMI 1.46g, AIBN 0.33g were dissolved in CHN 51.3g, and the mixture was stirred at 110℃for 20 hours to obtain an acrylic polymer solution (solid content concentration: 20 mass%) (P8). The Mn of the resulting acrylic polymer was 7,200 and the Mw was 11,000.
Synthesis example 8
PFHMA 5.00.00 g, KBM-503.70 g, AIBN 0.59g were dissolved in 28.68g of PGME and reacted at 80℃for 20 hours to obtain an acrylic polymer solution (solid content: 30 mass%) (P9). The Mn of the resulting acrylic polymer was 6700 and the Mw was 9800.
Synthesis example 9 >
TMSSMA 2.29.29 g, 4.67g of PFHMA, 0.47g of MAA, 1.28g of HPMA, 1.29g of CHMI and 0.50g of AIBN were dissolved in 24.50g of PGME and reacted at 80℃for 20 hours to obtain an acrylic polymer solution (30% by mass of solid content) (P10). The Mn of the resulting acrylic polymer was 3000 and the Mw was 4400.
Examples 1 to 11 and comparative examples 1 to 4
The photosensitive resin compositions of examples 1 to 7 and comparative examples 1 to 2 were prepared by mixing the components (a) to (E) with a solvent in the compositions shown in table 1 and adjusting the amount of the solvent added so that the solid content concentration of the final composition became 21.0 mass%. The amounts of solvents added were adjusted so that the solid content concentrations of the final compositions became 17.0 mass%, and photosensitive resin compositions of examples 8 to 11 and comparative examples 3 to 4 were prepared. The composition ratios in table 1 represent ratios in terms of solid components. Examples 1 to 10 and comparative examples 1 to 3 were positive photosensitive resin compositions, and example 11 and comparative example 4 were negative photosensitive resin compositions.
TABLE 1
Evaluation of wettability: examples 1 to 10 and comparative examples 1 to 3
The photosensitive resin composition was coated on ITO-glass using a spin coater, and then prebaked on a hot plate at a temperature of 100 ℃ for 120 seconds, to form a coating film having a film thickness of 1.7 μm. The coating film was irradiated with ultraviolet light having a light intensity of 5.5mW/cm 2 at 365nm for a predetermined period of time by a ultraviolet irradiation device PLA-600FA manufactured by Kuya corporation through a mask formed in a checkerboard shape such that bank width degrees of a rectangular pattern having a length of 50 μm and a width of 100 μm became 30 μm. Then, after development by immersing in 2.58% tmah aqueous solution for 20 seconds, washing with ultrapure water was performed with running water for 20 seconds. The rectangular pattern-formed coating film was then cured by post-baking at 230℃for 30 minutes. A driving waveform was used for the rectangular opening of the obtained cured film by using an Inkjet Designer (ink jet Designer) manufactured by the company of the late: B. repetition frequency: 1kHz, driving voltage: about 20pl of the solution was discharged at 8V. Japanese patent application 2016-141326 was used as the discharge solution, and the solution described in example 1-1 was used. The results obtained are shown in table 2.
Evaluation of wettability: example 11 and comparative example 4]
After the photosensitive resin composition was applied to ITO-glass using a spin coater, it was prebaked on a hot plate at a temperature of 100 ℃ for 120 seconds to form a coating film having a film thickness of 1.2 μm. The coating film was irradiated with ultraviolet light having a light intensity of 5.5mW/cm 2 at 365nm for a predetermined period of time by a UV irradiation device PLA-600FA manufactured by Kiya corporation through a mask formed in a checkered pattern such that bank width degrees of a rectangular pattern (light shielding portion) having a length of 80 μm and a width of 160 μm became 50 μm. Then, after development by immersing in 0.4% tmah aqueous solution for 60 seconds, washing with ultrapure water was performed for 30 seconds. The rectangular pattern-formed coating film was then heated at 230℃for 30 minutes and then baked to cure. A driving waveform was used for the rectangular opening of the obtained cured film by using an injjet Designer manufactured by the company of the same company as the rakust, inc: B. repetition frequency: 1kHz, driving voltage: about 20pl of the solution was discharged at 8V. Japanese patent application 2016-141326 was used as the discharge solution, and the solution described in example 1-1 was used. The results obtained are shown in table 2.
< Evaluation criterion of wettability >
O: the solution was completely wetted and spread in the rectangular opening.
X: a portion where the solution did not wet and spread was observed in the rectangular opening.
TABLE 2
Wettability of
Example 1 ○
Example 2 ○
Example 3 ○
Example 4 ○
Example 5 ○
Example 6 ○
Example 7 ○
Example 8 ○
Example 9 ○
Example 10 ○
Example 11 ○
Comparative example 1 ×
Comparative example 2 ×
Comparative example 3 ×
Comparative example 4 ×
As shown in table 2, the rectangular openings of examples 1 to 11 were excellent in wettability. On the other hand, in comparative examples 1 to 4, sufficient wettability could not be confirmed.

Claims (14)

1. A heat-curable photosensitive resin composition comprising the following component (A), component (B), solvent (C) and component (D),
(A) The components are as follows: a polymer having the following groups (A1) and (A2),
(A1) Lyophobic group
(A2) A trialkoxysilyl group, which is a group,
(B) The components are as follows: an alkali-soluble resin, a solvent,
(C) The solvent is used for the preparation of the aqueous solution,
(D) The components are as follows: the photosensitive agent is used for preparing the photosensitive agent,
(B) N-cyclohexylmaleimide is copolymerized with the alkali-soluble resin of the component (A).
2. The photosensitive resin composition according to claim 1, wherein component (A) is a polymer further comprising (A3),
(A3) : at least 1 group selected from the group consisting of hydroxyl, carboxyl, amide, and amino.
3. The photosensitive resin composition according to claim 1 or 2, which satisfies at least 1 of the following (Z1) to (Z4),
(Z1): also contains a crosslinking agent as component (E);
(Z2): (B) The alkali-soluble resin of the component (a) further has a self-crosslinking group or a group reactive with at least 1 group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group;
(Z3): (D) The component (C) is a photoradical generator, and the photosensitive resin composition further contains a compound having 2 or more olefinic double bonds as component (F);
(Z4): (D) The component (C) is a photoacid generator, and the photosensitive resin composition further contains, as the component (G), a compound having 2 or more functional groups that form covalent bonds with an acid generated by the component (D).
4. The photosensitive resin composition according to any one of claims 1 to 3, wherein component (D) is a quinone diazonium compound.
5. The photosensitive resin composition according to claim 3, wherein component (D) is a quinone diazonium compound, and the photosensitive resin composition satisfies the (Z1) or (Z2).
6. The photosensitive resin composition according to any one of claims 1 to 5, wherein the lyophobic group of component (a) is at least one group selected from the group consisting of a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group, and a polysiloxane group.
7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the polymer of component (a) is an acrylic polymer.
8. The photosensitive resin composition according to claim 7, wherein the number average molecular weight of the acrylic polymer of component (A) is 2,000 ～ 100,000 in terms of polystyrene.
9. The photosensitive resin composition according to any one of claims 1 to 8, wherein the alkali-soluble resin of component (B) has a number average molecular weight of 2,000 to 50,000 in terms of polystyrene.
10. The photosensitive resin composition according to any one of claims 1 to 9, wherein the component (a) is contained in an amount of 0.1 to 20 parts by mass per 100 parts by mass of the component (B).
11. The photosensitive resin composition according to any one of claims 3 to 10, wherein the component (E) is 1 to 50 parts by mass based on 100 parts by mass of the total of the components (a) and (B).
12. A cured film comprising a thermally cured product of the photosensitive resin composition according to any one of claims 1 to 11.
13. A display element having the cured film of claim 12.
14. A display element having the cured film according to claim 12 as a partition wall for image formation.
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