WO2019156000A1 - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

Info

Publication number
WO2019156000A1
WO2019156000A1 PCT/JP2019/003674 JP2019003674W WO2019156000A1 WO 2019156000 A1 WO2019156000 A1 WO 2019156000A1 JP 2019003674 W JP2019003674 W JP 2019003674W WO 2019156000 A1 WO2019156000 A1 WO 2019156000A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
component
resin composition
photosensitive resin
compound
Prior art date
Application number
PCT/JP2019/003674
Other languages
French (fr)
Japanese (ja)
Inventor
大村　浩之
昇志郎 湯川
Original Assignee
日産化学株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 日産化学株式会社 filed Critical 日産化学株式会社
Priority to KR1020207023999A priority Critical patent/KR20200118067A/en
Priority to JP2019570723A priority patent/JP7406181B2/en
Priority to CN201980012042.8A priority patent/CN111684358A/en
Publication of WO2019156000A1 publication Critical patent/WO2019156000A1/en

Links

Classifications

    • 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
    • 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
    • G03F7/0223—Iminoquinonediazides; Para-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
    • G03F7/022—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
    • G03F7/075—Silicon-containing 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • 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 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 radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups

Definitions

  • the present invention relates to a photosensitive resin composition and a cured film obtained therefrom. More specifically, the present invention relates to a photosensitive resin composition capable of forming an image having high water repellency and oil repellency on the surface of the cured film, a cured film thereof, and various materials using the cured film.
  • This photosensitive resin composition is particularly suitable for use as an interlayer insulating film in a liquid crystal display or an EL display, a light shielding material corresponding to an inkjet method, or a partition material.
  • a full color display substrate manufacturing technique using an 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 EL (electroluminescent) element has been actively studied.
  • TFT thin film transistor
  • organic EL electroluminescent
  • a color filter in a liquid crystal display element light is blocked from a section (hereinafter referred to as a bank) that defines pixels that have been patterned in advance, compared to a conventional printing method, electrodeposition method, dyeing method, or pigment dispersion method.
  • Patent Document 2 a method has been proposed (Patent Document 2) in which an organic EL display element is manufactured by preparing a bank in advance and dropping an ink serving as a light emitting layer in the same manner.
  • the substrate has ink-philicity (hydrophilicity, oleophilicity) to prevent the ink droplet from overflowing to the adjacent pixels beyond the bank.
  • the bank surface must be water and oil repellent.
  • the substrate can be made hydrophilic and the bank can be made water repellent by continuous plasma treatment such as oxygen gas plasma treatment and fluorine gas plasma treatment or UV ozone treatment. It has been proposed (Patent Document 3). In addition, a proposal has been made that a fluorine-based surfactant or a fluorine-based polymer is blended with a photosensitive organic thin film (Patent Document 4), but consideration is given not only to photosensitivity but also to coating properties, such as compatibility. Not only is there much to be done, but also the UV ozone treatment during the hydrophilic treatment of the substrate reduces the water repellency of the surface, which is not practical.
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2015-172742
  • Patent Document 6 JP 2012-220860 A
  • JP 2000-187111 A Japanese Patent Laid-Open No. 11-54270 JP 2000-353594 A JP-A-10-197715 Japanese Patent Laying-Open No. 2015-172742 JP 2012-220860 A
  • the present invention has been made in view of the above circumstances, and the problem to be solved is used for liquid crystal display elements, organic EL display elements and the like, and even after UV ozone treatment, the surface of the cured film It is to form an image of a cured film having high water repellency and high oil repellency and high lyophilicity on a substrate without plasma treatment or UV ozone treatment. In particular, it is to form an image of a cured film that can prevent a situation where an ink droplet overflows to an adjacent pixel beyond a bank in manufacturing a substrate using inkjet.
  • the present inventors have formed a cured film from a composition containing polysiloxane having an organic group having a fluorine atom and an organic group having a thermally crosslinkable group.
  • the present inventors have found that even after UV ozone treatment, liquid repellency can be efficiently applied to the film surface, and high lyophilicity can be efficiently imparted to the substrate without plasma treatment or UV ozone treatment. .
  • thermosetting photosensitive resin composition containing the following component (A), component (B), solvent (C) and component (D).
  • A) Component Polysiloxane having the following groups (A1) and (A2) (A1) Organic group having fluorine atom (A2) Organic group having thermally crosslinkable group (B) Component: Alkali-soluble resin (C) solvent , (D) Component: Photosensitizer.
  • 3. 3 The photosensitive resin composition according to 1 or 2 that satisfies at least one of the following (Z1) to (Z4).
  • Composition. 12 The cured film obtained using the photosensitive resin composition as described in any one of said 1 thru
  • the photosensitive resin composition of the present invention has high oil repellency on the cured film surface even after UV ozone treatment, and has high lyophilicity on the substrate without plasma treatment or UV ozone treatment. It is to form an image of the film.
  • the photosensitive resin composition of this invention is a photosensitive resin composition containing the following (A) component, (B) component, (C) solvent, and (D) component.
  • the photosensitive resin composition of the present invention preferably further satisfies at least one of the following (Z1) to (Z4).
  • Z3 The component (D) is a photoradical generator, and further contains a compound having two or more ethylenic polymerizable groups as the component (F).
  • the photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition in which the component (D) is a quinonediazide compound.
  • the polysiloxane (A) used in the present invention is a polysiloxane having the following groups (A1) and (A2).
  • the organic group having a fluorine atom is an organic group bonded to a silicon atom of the polysiloxane main chain, and a part or all of the organic group is substituted with a fluorine atom.
  • the organic group having a fluorine atom is not particularly limited as long as it has a fluorine atom as long as the effects of the present invention are not impaired.
  • an alkyl group in which part or all of the hydrogen atoms are substituted with fluorine atoms, an alkyl group having an ether bond in which some or all of the hydrogen atoms are substituted with fluorine atoms, and the like are preferable.
  • the number of fluorine atoms of the organic group is not particularly limited. More preferred is a perfluoroalkyl group, and still more preferred is an organic group represented by the formula (1). (K represents an integer of 0 to 12)
  • organic group represented by the formula (1) examples include trifluoropropyl group, tridecafluorooctyl group, heptadecafluorodecyl group, 2,2,2-trifluoroethyl group, 2,2,3 , 3,3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluorohexyl) ethyl group, 2- (perfluorooctyl) ethyl group, 2- (perfluorodecyl) ethyl group, Examples include 2- (perfluoro-3-methylbutyl) ethyl group, 2- (perfluoro-5-methylhexyl) ethyl group, 2- (perfluoro-7-methyloctyl) ethyl group, and the like.
  • the organic group which has a fluorine atom which polysiloxane (A) has may be 1 type individual,
  • the organic group having a fluorine atom of the polysiloxane (A) is 0.05% with respect to 1 mol of all silicon atoms of the polysiloxane (A) from the viewpoint of providing both liquid repellency and film hardness and solvent resistance. Is preferably 0.5 mol, more preferably 0.1 mol to 0.4 mol.
  • the heat-crosslinkable group in the organic group having a heat-crosslinkable group is not particularly limited as long as it is a group that forms a covalent bond by heating.
  • a vinyl group, an epoxy group, an amino group, a mercapto group, a block An isocyanate group or an isocyanate group is mentioned.
  • examples of the organic group having an epoxy group include a glycidyloxy group and a 3,4-epoxycyclohexylmethyl group.
  • the organic group having a thermally crosslinkable group of the polysiloxane (A) is 0 with respect to 1 mol of all silicon atoms of the polysiloxane (A) from the viewpoint of providing both liquid repellency and film hardness and solvent resistance. .2 to 0.95 mol is preferable, and 0.3 to 0.8 mol is more preferable.
  • the polysiloxane (A) of the present invention is (A1) not an organic group having a fluorine atom, but (A2) an organic group having no thermally crosslinkable group, and other organic groups are silicon atoms in the polysiloxane main chain. May be bonded to.
  • the other organic group is an organic group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, having no fluorine atom.
  • Examples of such an organic group having no fluorine atom include a saturated hydrocarbon group having a linear or branched structure; an aromatic group having a benzene ring; an organic group having an amino group, a ureido group or a vinyl group; Or the organic group etc. which have an ether bond and an ester bond are mentioned.
  • Specific examples thereof include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, heptyl group, octyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, phenyl group, vinyl group, ⁇ -Aminopropyl group, ⁇ -methacryloxypropyl group and the like.
  • the amount of the organic group having no fluorine atom in the polysiloxane (A) is not particularly limited as long as the effect of the present invention is not impaired, but it is 1 mol of all the silicon atoms in the polysiloxane (A).
  • the amount is preferably 0.01 to 0.75 mol. In such a range, a coating film having an organic solvent contact angle of 50 degrees or more is easily obtained, and a homogeneous polysiloxane (A) solution is easily obtained.
  • the polysiloxane as the component (A) has a number average molecular weight in the range of 1,000 to 100,000. When the number average molecular weight exceeds 100,000, the handling property may be deteriorated, and when the number average molecular weight is less than 1,000, the film of the exposed portion is developed. A considerable amount of reduction may occur, resulting in insufficient liquid repellency.
  • a method for obtaining such a polysiloxane (A) is not particularly limited, but an alkoxysilane represented by the following formula (2), an alkoxysilane having an epoxy group, and an alkoxysilane having another organic group as desired.
  • Polysiloxanes obtained by polycondensation are preferred. (Wherein R 1 is an organic group having a fluorine atom, R 2 and R 3 each independently represents a hydrocarbon group having 1 to 5 carbon atoms, and m represents 0 or 1).
  • R 1 in the formula (2) represents the above-described organic group having a fluorine atom.
  • R 2 and R 3 each independently represent a hydrocarbon group having 1 to 5 carbon atoms, and a saturated hydrocarbon group is particularly preferable.
  • lower alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group are preferable because they are easily available as commercial products.
  • R 2 and R 3 may be the same or different from each other.
  • an alkoxysilane in which R 1 is an organic group represented by the formula (1) is preferable.
  • K represents an integer of 0 to 12
  • alkoxysilane in which R 1 is an organic group represented by the formula (1) include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, and trideca.
  • Examples include fluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, and 2- (perfluorohexyl) ethyltrimethoxysilane.
  • At least one of the alkoxysilanes represented by the formula (2) may be used, but a plurality of types may be used as necessary.
  • the alkoxysilane having an organic group having a thermally crosslinkable group is an alkoxysilane represented by the following formula (3). (Wherein R 4 is an organic group having a thermally crosslinkable group, R 5 and R 6 each independently represent a hydrocarbon group having 1 to 5 carbon atoms, and n represents 0 or 1)
  • R 4 is an organic group having 2 to 12 carbon atoms having a vinyl group, an epoxy group, an amino group, a mercapto group, a blocked isocyanate group, an isocyanate group, a methacryl group, an acrylic group or a ureido group.
  • an organic group having 2 to 12 carbon atoms having a vinyl group, an epoxy group, an amino group, a methacryl group, an acrylic group or a ureido group is preferable from the viewpoint of availability. More preferably, it is an organic group having 2 to 12 carbon atoms having an epoxy group, a methacryl group, an acrylic group or a ureido group. More specifically, an organic group having 2 to 12 carbon atoms having a glycidoxy group or a 3,4-epoxycyclohexylmethyl group is preferable.
  • R 5 and R 6 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.
  • Specific examples of the specific alkoxysilane represented by the formula (3) include allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy).
  • alkoxysilane which has an organic group which has a heat crosslinkable group.
  • alkoxysilane having another organic group examples include alkoxysilanes represented by the formula (4).
  • R 7 is a hydrogen atom or an organic group having 1 to 20 carbon atoms having no fluorine atom
  • R 8 is a hydrocarbon group having 1 to 5 carbon atoms
  • p is 0, 1 or 2; Represents.
  • R 8 represents a hydrocarbon group, but a saturated hydrocarbon group having 1 to 5 carbon atoms is preferable because the reactivity is higher when the number of carbon atoms is smaller. More preferred are a methyl group, an ethyl group, a propyl group, and a butyl group.
  • the alkoxysilane represented by Formula (4) represents tetraalkoxysilane. Specific examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like, and are easily available as commercial products.
  • the alkoxysilane represented by the formula (4) has R 7 having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms not having a hydrogen atom or a fluorine atom
  • R 7 may be the same or different.
  • Examples of the organic group having 1 to 20 carbon atoms not having a fluorine atom include a saturated hydrocarbon group having a linear or branched structure, an aromatic group having a benzene ring, an amino group, a ureido group, or a vinyl group. Or an organic group having an ether bond or an ester bond.
  • R 8 in the formula (4) is a hydrocarbon group having 1 to 5 carbon atoms. when p is 1 or 2, but is generally preferred if R 8 are the same, in the present invention, R 8 may be the same or different. Specific examples of alkoxysilane in the case where p is an integer of 1 to 3 in formula (4) are shown below.
  • the polysiloxane (A) used in the present invention preferably contains 5 to 50 mol% of the alkoxysilane represented by the formula (2) in the total alkoxysilane, and the alkoxysilane represented by the formula (3) The content is preferably 10 to 95 mol%, and the remainder is obtained by polycondensation of the alkoxysilane represented by the above formula (4).
  • the content of the alkoxysilane represented by the formula (2) is more preferably 10 to 40 mol%.
  • the amount of the alkoxysilane represented by the formula (3) is preferably 30 to 80 mol% in the total alkoxysilane.
  • the amount thereof is preferably 5 to 60 mol% in the total alkoxysilane.
  • an alkoxysilane represented by the formula (2) for example, an alkoxysilane represented by the formula (2), an alkoxysilane represented by the formula (3), and an alkoxy represented by the formula (4) as necessary.
  • Examples thereof include a method in which silane and an organic solvent are heated and polycondensed in the presence of an aqueous tetraethylammonium hydroxide solution. More specifically, after adding a tetraethylammonium hydroxide aqueous solution to an organic solvent in advance to obtain a solution of the tetraethylammonium hydroxide aqueous solution, the above-mentioned various alkoxysilanes are mixed while the solution is heated.
  • the amount of the tetraethylammonium hydroxide aqueous solution is preferably 0.01 to 0.2 mol with respect to 1 mol of the total alkoxy group amount of the alkoxysilane used.
  • the heating can be performed at a liquid temperature of preferably 0 to 100 ° C., and preferably several tens of minutes under reflux in a container equipped with a reflux tube so that the liquid does not evaporate or volatilize. It is done for more than 10 hours.
  • the concentration of all the silicon atoms in the charged alkoxysilane converted to oxide (hereinafter referred to as SiO 2 conversion concentration) is 40% by mass or less, particularly preferably 10 to 30% by mass. % Heating is preferable.
  • An organic solvent (hereinafter also referred to as a polymerization solvent) used for polycondensation of the alkoxysilane is an alkoxysilane represented by the formula (2), an alkoxysilane represented by the formula (3), and as necessary.
  • a solvent (C) is preferable.
  • generates by the polycondensation reaction of alkoxysilane the organic solvent favorable with alcohol and alcohol compatibility is used.
  • the polymerization solvent examples include alcohols such as methanol, ethanol, propanol and n-butanol, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether, and tetrahydrofuran.
  • examples include ether.
  • a plurality of the above organic solvents may be mixed and used.
  • the solution of the specific polysiloxane obtained by the above method may be used as it is for the photosensitive resin composition of the present invention, and if necessary, the solution of the specific polysiloxane obtained by the above method may be used. It can be concentrated, diluted by adding a solvent, or substituted with another solvent.
  • the solvent used for dilution by adding the solvent may be a solvent used for a polycondensation reaction or other solvents.
  • the additive solvent is not particularly limited as long as the specific polysiloxane is uniformly dissolved, and one or more kinds can be arbitrarily selected and used.
  • the additive solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester solvents such as methyl acetate, ethyl acetate, and ethyl lactate, in addition to the solvent used in the polycondensation reaction.
  • the alcohol is preferably distilled off at normal pressure or reduced pressure.
  • the component (B) of the present invention is a resin having an alkali-soluble group.
  • the alkali-soluble group include a phenolic hydroxy group, a carboxyl group, an acid anhydride group, an imide group, a sulfonyl group, phosphoric acid, a boronic acid, an active methylene group, and an active methine group.
  • the active methylene group refers to a methylene group (—CH 2 —) having a carbonyl group at an adjacent position and having reactivity with a nucleophile.
  • the active methine group has a structure in which one hydrogen atom of the methylene group is substituted with an alkyl group in the active methylene group and has reactivity with a nucleophile.
  • a group represented by the following formula (b1) is more preferable.
  • R represents an alkyl group, an alkoxy group or a phenyl group, and a broken line represents a bond.
  • examples of the alkyl group represented by R include an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 5 carbon atoms is preferable.
  • examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. Of these, a methyl group, an ethyl group, an n-propyl group, and the like are preferable.
  • examples of the alkoxy group represented by R include an alkoxy group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms is preferable.
  • examples of such an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, and a t-butoxy group. Of these, a methoxy group, an ethoxy group, an n-propoxy group, and the like are preferable.
  • Examples of the group represented by the above formula (b1) include the following structures.
  • the broken line represents a bond.
  • an alkali-soluble resin having at least one organic group selected from the group consisting of a phenolic hydroxy group and a carboxyl group, and having a number average molecular weight of 2,000 to 50,000 Preferably there is.
  • the alkali-soluble resin as the component (B) may be any alkali-soluble resin having such a structure, and is not particularly limited with respect to the main chain skeleton and side chain type of the polymer constituting the resin.
  • the alkali-soluble resin (B) has a number average molecular weight in the range of 2,000 to 50,000. If the number average molecular weight exceeds 50,000, the development residue is likely to be generated, and the sensitivity is greatly reduced. On the other hand, if the number average molecular weight is less than 2,000, the development is insufficient. At this time, there is a case where a considerable amount of film loss occurs in the exposed portion, resulting in insufficient curing.
  • alkali-soluble resin (B) examples include acrylic resins, polyhydroxystyrene resins, polyimide precursors, and polyimides.
  • an alkali-soluble resin composed of a copolymer obtained by polymerizing plural kinds of monomers (hereinafter referred to as a specific copolymer) can also be used as the component (B).
  • the alkali-soluble resin as the component (B) may be a blend of a plurality of types of specific copolymers.
  • the specific copolymer is a monomer that exhibits alkali solubility, that is, a monomer having at least one selected from the group consisting of a carboxyl group and a phenolic hydroxy group, and a group of monomers copolymerizable with these monomers. It is a copolymer formed with at least one selected monomer as an essential constituent unit, and has a number average molecular weight of 2,000 to 50,000. If the number average molecular weight is more than 50,000, a residue may be generated.
  • the above “monomer having at least one selected from the group consisting of a carboxyl group and a phenolic hydroxy group” includes a monomer having a carboxyl group and a monomer having a phenolic hydroxy group. These monomers are not limited to those having one carboxyl group or one phenolic hydroxy group, and may have a plurality of monomers.
  • the monomer having a carboxyl group examples include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl).
  • Maleimide N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.
  • Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide, 4-hydroxyphenyl methacrylate and the like.
  • Examples of the monomer having an imide group include maleimide.
  • the ratio of the unsaturated carboxylic acid derivative and / or the monomer having a phenolic hydroxyl group and a polymerizable unsaturated group in the production of the (B) component alkali-soluble acrylic polymer is the same as that in the production of the (B) component alkali-soluble acrylic polymer.
  • it is preferably 10 to 90 mol%, more preferably 5 to 60 mol%, and most preferably 5 to 30 mol%.
  • the unsaturated carboxylic acid and / or phenolic hydroxy group derivative is less than 10% by weight, the alkali solubility of the polymer is insufficient.
  • the alkali-soluble resin which is the component (B) of the present invention may be further copolymerized with a monomer having a hydroxyalkyl group and a polymerizable unsaturated group from the viewpoint of further 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, Examples thereof include 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerol monomethacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxyl-6-lactone and the like.
  • the ratio of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group in the production of the alkali-soluble acrylic polymer as component (B) is preferably 10 to 60% by weight, more preferably 15 to 50% by weight, and most preferably Is 20 to 40% by weight.
  • the monomer having a hydroxyalkyl group and a polymerizable unsaturated group is less than 10% by weight, the effect of stabilizing the pattern shape of the copolymer may not be obtained.
  • the amount is 60% by weight or more, the alkali-soluble group of the component (B) may be insufficient, and characteristics such as developability may be deteriorated.
  • the alkali-soluble resin which is the component (B) of the present invention may be further copolymerized with an N-substituted maleimide compound from the viewpoint of increasing the Tg of the copolymer.
  • N-substituted maleimide compound maleimide compound examples include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
  • the thing which does not have an aromatic ring from a transparency viewpoint is preferable, and what has an alicyclic skeleton from the point of developability, transparency, and heat resistance is more preferable, and a cyclohexyl maleimide is the most preferable especially.
  • the ratio of N-substituted maleimide in the production of the alkali-soluble acrylic polymer of component (B) is preferably 10 to 60% by weight, more preferably 15 to 50% by weight, and most preferably 20 to 40% by weight.
  • the N-substituted maleimide is less than 10% by weight, the Tg of the copolymer is lowered and the heat resistance may be inferior. If it is 60% by weight or more, the transparency may be lowered.
  • the alkali-soluble resin (B) used in the present invention further has a self-crosslinkable group, or a hydroxy group, a carboxyl group, an amide group, and A copolymer further having a group that reacts with at least one group selected from the group consisting of amino groups (hereinafter also referred to as a crosslinkable group) is preferable.
  • Examples of the self-crosslinking group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, and a blocked isocyanate group.
  • crosslinkable group examples 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 is 0.1 to 0.9 per repeating unit in the resin of the component (B).
  • 0.1 to 0.8 is more preferable.
  • the alkali-soluble resin of component (B) is further composed of an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, a blocked isocyanate group, and an N-alkoxymethyl group.
  • Examples of unsaturated compounds having radical polymerizability and having an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-methylolacrylamide. Etc.
  • Examples of the monomer having radical polymerizability and further having a hydroxymethylamide group include N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide.
  • Examples of the monomer having radical polymerizability and having an alkoxysilyl group include 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane. Can be mentioned.
  • Examples of unsaturated compounds having radical polymerizability and further having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, glycidyl ⁇ -n-propyl acrylate, ⁇ -n-butyl acrylic acid.
  • Glycidyl acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, ⁇ -ethylacrylic acid-6
  • examples thereof include 7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like.
  • glycidyl methacrylate -6,7-epoxyheptyl methacrylate
  • o-vinylbenzyl glycidyl ether o-vinylbenzyl glycidyl ether
  • m-vinylbenzyl glycidyl ether p-vinylbenzyl glycidyl ether
  • 3,4-epoxycyclohexyl methacrylate etc.
  • these may be used alone or in combination.
  • Examples of the unsaturated compound having radical polymerizability and further having an oxetane group include (meth) acrylic acid ester having an oxetane group.
  • monomers 3- (methacryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl) -3- Ethyl-oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyl-oxetane, 3- (Acryloyloxymethyl) -2-phenyl-oxetane, 2- (methacryloyloxymethyl) oxetane
  • Examples of the monomer having radical polymerizability and further having a vinyl group include 2- (2-vinyloxyethoxy) ethyl acrylate and 2- (2-vinyloxyethoxy) ethyl methacrylate.
  • the photosensitive resin composition of the present invention satisfies (Z1), it has radical polymerizability and has an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, and a block.
  • a non-crosslinking group such as an isocyanate group and at least one group selected from a self-crosslinking 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;
  • the constituent unit derived from the saturated compound is preferably contained in an amount of 10 to 70% by weight, particularly preferably 20 to 60% by weight, based on the total of all repeating units of the alkali-soluble resin (B).
  • this structural unit is less than 10% by weight, the heat resistance and surface hardness of the resulting cured film tend to decrease, while when the amount of this structural unit exceeds 70% by weight, the radiation-sensitive resin composition is stored. The stability tends to decrease.
  • the acrylic polymer of component (B) may be a copolymer formed with monomers other than the above-described monomers (hereinafter referred to as other monomers) as constituent units.
  • the other monomer may be any one that can be copolymerized with at least one selected from the group consisting of the above-mentioned monomer having a carboxyl group and a monomer having a phenolic hydroxy group.
  • monomers include acrylic ester compounds, methacrylic ester compounds, acrylamide compounds, acrylonitrile, styrene compounds and vinyl compounds.
  • the specific example of the said other monomer is given, it is not limited to these.
  • acrylic ester compound examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, phenoxyethyl acrylate, 2,2,2- Trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxy Butyl acrylate, 2-methyl-2-adamantyl acrylate, 2 Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate,
  • methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2- Trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxy Butyl methacrylate, 2 Methyl-2-adamantyl methacrylate, ⁇ -butyl
  • acrylamide compound examples include N-methylacrylamide, N-methylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxy.
  • methyl acrylamide and N-butoxymethyl methacrylamide examples include methyl acrylamide and N-butoxymethyl methacrylamide.
  • vinyl compound examples include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2 -Epoxy-5-hexene, 1,7-octadiene monoepoxide and the like.
  • styrene compound examples include styrene having no hydroxy group, such as styrene, ⁇ -methylstyrene, chlorostyrene, and bromostyrene.
  • the ratio of the other monomers is preferably 80% by weight or less, more preferably 50% by weight or less, and further preferably 20% by weight or less. . If the amount exceeds 80% by weight, the essential components are relatively reduced, so that it is difficult to sufficiently obtain the effects of the present invention.
  • the method for obtaining the alkali-soluble acrylic polymer (B) used in the present invention is not particularly limited.
  • a carboxyl group, a phenolic hydroxy group, and a carboxylic acid or a phenolic hydroxy group by the action of heat or acid is not particularly limited.
  • Monomer, other copolymerization if desired It can be obtained by carrying out a polymerization reaction at a temperature of 50 to 110 ° C.
  • the solvent used will not be specifically limited if it dissolves the monomer which comprises an alkali-soluble acrylic polymer, and the acrylic polymer which has a specific functional group.
  • the solvent described in the (C) solvent mentioned later is mentioned.
  • the acrylic polymer having a specific functional group thus obtained is usually in a solution state dissolved in a solvent.
  • the solution of the specific copolymer obtained as described above is re-precipitated by stirring with stirring such as diethyl ether or water, and the generated precipitate is filtered and washed, and then under normal pressure or reduced pressure.
  • the powder of the specific copolymer can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
  • the powder of the specific copolymer may be used as it is, or the powder may be redissolved in a solvent (C) described later and used as a solution.
  • polyimide precursors such as polyamic acid, polyamic acid ester, partially imidized polyamic acid, and polyimide such as carboxylic acid group-containing polyimide can be used. If it is soluble, the kind can be used without particular limitation.
  • the polyamic acid which is a polyimide precursor, can generally be obtained by polycondensation of (a) a tetracarboxylic dianhydride compound and (b) a diamine compound.
  • the (a) tetracarboxylic dianhydride compound is not particularly limited, and specific examples thereof include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′.
  • Aromatic tetracarboxylic acid 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-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetra Carbo Alicyclic tetracarboxylic dianhydrides such as acid dianhydrides, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthal
  • 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-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic 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, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′- Diamino-3,3′-dicarboxy-5,5′-dimethylbiphenyl, 4,4′-diamino-3,3′-dicarboxy-5,
  • Diamine compound 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene 1,4-diamino-2-mercaptobenzene, bis (4-amino-3-mercaptophenyl) ether, 2,2-bis (3-amino-4-mercaptophenyl) hexafluoropropane and the like having a thiophenol group
  • Diamine compounds 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis (4-aminobenzene-3-sulfonic acid) ) Ether, 4,4′-diaminobiphenyl-3,3′-disulfonic acid, 4,4′-diamino-3,3′-dimethylbiphenyl-6,6′-disulfonic acid and the like di
  • the compounding ratio of both compounds that is, (b) the total number of moles of the diamine compound / (a)
  • the total number of moles of the tetracarboxylic dianhydride compound is preferably 0.7 to 1.2.
  • a carboxylic anhydride when it superposes
  • carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid There may be mentioned anhydrides, itaconic anhydride, tetrahydrophthalic anhydride and the like.
  • the reaction temperature of the reaction between the diamine compound and the tetracarboxylic dianhydride compound can be selected from -20 to 150 ° C, preferably -5 to 100 ° C.
  • the reaction temperature is appropriately selected within the range of 5 to 40 ° C. and the reaction time of 1 to 48 hours.
  • the reaction temperature for protecting the terminal amino group with an acid anhydride can be selected from -20 to 150 ° C, preferably -5 to 100 ° C.
  • the reaction of the diamine compound and the tetracarboxylic dianhydride compound can be performed in a solvent.
  • Solvents that can be used in this case include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, Hexamethyl sulfoxide, m-cresol, ⁇ -butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, 3 -Ethyl ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol
  • the solution containing the polyamic acid thus obtained can be used as it is for the preparation of a negative photosensitive resin composition. Further, the polyamic acid may be precipitated and isolated in a poor solvent such as water, methanol, ethanol, etc. and recovered for use.
  • a poor solvent such as water, methanol, ethanol, etc.
  • any polyimide can be used as the component (B).
  • the polyimide used in the present invention is obtained by chemically or thermally imidizing 50% or more of a polyimide precursor such as polyamic acid.
  • the polyimide used in the photosensitive resin composition of the present invention preferably has a group selected from a carboxyl group and a phenolic hydroxy group in order to impart alkali solubility.
  • the method of introducing a carboxyl group or a phenolic hydroxy group into polyimide is a method using a monomer having a carboxyl group or a phenolic hydroxy group, a method of sealing an amine terminal with an acid anhydride having a carboxyl group or a phenolic hydroxy group, Alternatively, a method of setting the imidization rate to 99% or less when imidizing a polyimide precursor such as polyamide acid is used.
  • Such a polyimide can be obtained by synthesizing a polyimide precursor such as the above-mentioned polyamic acid and then performing chemical imidization or thermal imidization.
  • a method of chemical imidization generally, a method of adding excess acetic anhydride and pyridine to a polyimide precursor solution and reacting at room temperature to 100 ° C. is used.
  • a method for thermal imidization generally, a method in which a polyimide precursor solution is heated while being dehydrated at a temperature of 180 ° C. to 250 ° C. is used.
  • a phenol novolac resin can be further used as the alkali-soluble resin of component (B).
  • polyester polycarboxylic acid can also be used as the alkali-soluble resin of component (B).
  • the polyester polycarboxylic acid can be obtained from an acid dianhydride and a diol by the method described in WO2009 / 051186.
  • the acid dianhydride include the above (a) tetracarboxylic dianhydride.
  • the diol include bisphenol A, bisphenol F, 4,4′-dihydroxybiphenyl, aromatic diols such as benzene-1,3-dimethanol, benzene-1,4-dimethanol, hydrogenated bisphenol A, and hydrogenated bisphenol F.
  • 1,4-cyclohexanediol 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and other alicyclic diols, and ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol And the like, and the like.
  • the alkali-soluble resin (B) may be a mixture of a plurality of types of alkali-soluble resins.
  • the ratio of the component (A) to the component (B) is 0.1 to 20 parts by mass of the component (A) with respect to 100 parts by mass of the component (B).
  • the (C) solvent used in the present invention dissolves the component (A), the component (B), and the component (D), the component (E), the component (F), and the component (G) described below, if necessary. And if it dissolves the below-mentioned (H) component added by necessity, other additives, etc., if it is a solvent which has such a solubility, the kind, structure, etc. will not be specifically limited.
  • Examples of such a 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, propylene glycol monomethyl ether, propylene glycol.
  • solvents can be used singly or in combination of two or more.
  • (C) solvents propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, etc. have good coating properties and safety Is preferable from the viewpoint of high.
  • These solvents are generally used as solvents for photoresist materials.
  • ⁇ (D) component examples include (D-1) 1,2-quinonediazide compounds, (D-2) photoradical generators, and (D-3) photoacid generators.
  • the 1,2-quinonediazide compound is a compound having either a hydroxyl group or an amino group, both a hydroxyl group and an amino group, and these hydroxyl groups or amino groups (both hydroxyl groups and amino groups).
  • the total amount thereof preferably 10 to 100 mol%, particularly preferably 20 to 95 mol% is a compound esterified or amidated with 1,2-quinonediazidesulfonic acid. Can do.
  • Examples of the compound having a hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, ethyl gallate, 1,3,3-tris (4-hydroxyphenyl).
  • Examples of the compound containing an amino group include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine.
  • Anilines such as 4,4′-diaminophenylmethane and 4,4′-diaminodiphenyl ether, and aminocyclohexane.
  • examples of the compound containing both a hydroxyl group and an amino group include o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, 2,4-diaminophenol, 4,4′-diamino-4 ′′ -hydroxytriphenylmethane, 4-amino-4 ′, 4 ′′ -dihydroxytriphenylmethane, bis (4-amino-3-carboxy-5-hydroxyphenyl) ether, bis (4-amino-3-carboxy-5-hydroxyphenyl) methane, 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) propane, 2,2-bis (4-amino-3-carboxy) Aminophenols such as -5-hydroxyphenyl) hexafluoropropane, 2-aminoethane Lumpur, 3-aminopropanol, mention may be made of alkanolamines,
  • 1,2-quinonediazide compounds can be used alone or in combination of two or more.
  • the content when the compound having a quinonediazide group as the component (D-1) is included is as follows.
  • the total amount is preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, and still more preferably 10 to 40 parts by mass.
  • 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 becomes small, and patterning by development may be difficult.
  • the amount exceeds 100 parts by mass the 1,2-quinonediazide compound is not sufficiently decomposed by exposure in a short time and sensitivity is lowered, or the component (D-1) absorbs light and the cured film Transparency may be reduced.
  • the photoradical generator is not particularly limited as long as it generates radicals upon exposure.
  • Specific examples include aromatic ketones such as benzophenone, Michler ketone, 4,4′-bisdiethylaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrene, benzoin methyl ether, benzoin ethyl ether, Benzoin ethers such as benzoinphenyl ether, benzoin such as methylbenzoin and ethylbenzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di ( m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-dipheny
  • the above photopolymerization initiator can be easily obtained as a commercial product. Specific examples thereof include IRGACURE 173, 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 (above, manufactured by BASF), KATURE Above, Japan Manufactured by Yakuhin Co., Ltd.), 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 (manufactured by
  • the content when the component (D-2) is contained in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 100 parts by mass of the component (A). Is 0.5 to 20 parts by mass, particularly preferably 1 to 15 parts by mass. If this ratio is too small, the exposed portion may be insufficiently cured, and pattern formation may not be possible, or even if it is possible, a film with low reliability may be formed. Moreover, when this ratio is excessive, the transmittance
  • the photoacid generator (D-3) is not particularly limited as long as it is a compound that generates an acid by photolysis when irradiated with ultraviolet rays.
  • acids generated when the photoacid generator is photolyzed 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, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzene Sulfone such as sulfonic acid, 1H, 1H, 2H, 2H-
  • the photoacid generator examples include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzoin tosylate compounds, iron arene complexes, halogen-containing triazine compounds, and acetophenone derivative compounds. And cyano group-containing oxime sulfonate compounds.
  • Any conventionally known or conventionally used photoacid generator can be applied in the present invention without any particular limitation.
  • the photo-acid generator of (D) component may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples thereof include compounds represented by the following formulas [PAG-1] to [PAG-41].
  • the content when the component (D-3) is contained in the photosensitive resin composition of the present embodiment is preferably 0.01 mass with respect to a total of 100 mass parts of the components (A) and (B). Part to 20 parts by weight, more preferably 0.1 part by weight to 10 parts by weight, still more preferably 0.5 part by weight to 8 parts by weight.
  • the content of the component (D-3) is preferably 0.01 mass with respect to a total of 100 mass parts of the components (A) and (B).
  • Part to 20 parts by weight more preferably 0.1 part by weight to 10 parts by weight, still more preferably 0.5 part by weight to 8 parts by weight.
  • the component (E) is a crosslinking agent, and is introduced into the composition when the photosensitive resin composition of the present invention satisfies the requirement (Z1). More specifically, it is a compound having a structure capable of forming a bridge structure by a thermal reaction with a thermally reactive site (for example, carboxyl group and / or phenolic hydroxyl group) of component (B). Specific examples will be given below, but the present invention is not limited thereto.
  • the thermal crosslinking agent include those selected from (E1) a crosslinkable compound having two or more substituents selected from an alkoxymethyl group and a hydroxymethyl group and (E2) a crosslinkable compound represented by formula (5). preferable. These crosslinking agents can be used alone or in combination of two or more.
  • the crosslinkable compound having two or more substituents selected from the alkoxymethyl group and hydroxymethyl group as the component (E1) undergoes a crosslinking reaction by a dehydration condensation reaction when exposed to a high temperature during thermosetting.
  • examples of such compounds include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast compounds.
  • alkoxymethylated glycoluril examples include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4 , 6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone.
  • glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resins (trade name: UFR (registered trademark) 65) ), Butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin (high-condensation type, product name: Beccamin (trade name) manufactured by DIC Corporation) Registered trademark) J-300S, P-955, N) and the like.
  • methylated urea resins (trade name: UFR (registered trademark) 65)
  • Butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV)
  • urea / formaldehyde resin high-
  • alkoxymethylated benzoguanamine examples include tetramethoxymethylbenzoguanamine.
  • Commercially available products manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), manufactured by Sanwa Chemical Co., Ltd. (trade names: Nicalac (registered trademark) BX-4000, BX-37, BL- 60, BX-55H) and the like.
  • alkoxymethylated melamine examples include, for example, hexamethoxymethylmelamine.
  • methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, 350) manufactured by Mitsui Cytec Co., Ltd., butoxymethyl type melamine compounds (trade name: My Coat (registered trademark)) 506, 508), methoxymethyl type melamine compound manufactured by Sanwa Chemical Co., Ltd.
  • a compound obtained by condensing a melamine compound, urea compound, glycoluril compound and benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group may be used.
  • the high molecular weight compound manufactured from the melamine compound and the benzoguanamine compound which are described in US Patent 6,323,310 is mentioned.
  • Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.).
  • Examples of commercially available products of the benzoguanamine compound include product name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd.).
  • phenoplast compounds include 2,6-bis (hydroxymethyl) phenol, 2,6-bis (hydroxymethyl) cresol, 2,6-bis (hydroxymethyl) -4-methoxyphenol, 3 , 3 ′, 5,5′-tetrakis (hydroxymethyl) biphenyl-4,4′-diol, 3,3′-methylenebis (2-hydroxy-5-methylbenzenemethanol), 4,4 ′-(1-methyl) Ethylidene) bis [2-methyl-6-hydroxymethylphenol], 4,4′-methylenebis [2-methyl-6-hydroxymethylphenol], 4,4 ′-(1-methylethylidene) bis [2,6- Bis (hydroxymethyl) phenol], 4,4′-methylenebis [2,6-bis (hydroxymethyl) phenol], 2, -Bis (methoxymethyl) phenol, 2,6-bis (methoxymethyl) cresol, 2,6-bis (methoxymethyl) -4-methoxyphenol, 3,3 ', 5,5'-tetrakis (methoxymethyl)
  • the acrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or the like
  • a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or the like
  • Polymers produced using methacrylamide compounds can also be used.
  • Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl.
  • Examples thereof include a copolymer of methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, 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 this invention can contain the crosslinkable compound represented by Formula (5) as (E2) component. (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)
  • the component (E2) is not particularly limited as long as it is a compound having a cycloalkene oxide structure represented by the formula (5). Specific examples thereof include the following formulas E2-1 and E2-2, and commercially available products shown below.
  • EX-252 (trade name, manufactured by Nagase Chemmutex Co., Ltd.), CY175, CY177, CY179 (trade name, manufactured by CIBA-GEIGY AG), Araldite CY-182, CY-192, CY-184 ( Above, CIBA-GEIGY AG product name), Epicron 200, 400 (above, DIC Corporation product name), Epicoat 871, 872 (above, Yuka Shell Epoxy Co., Ltd. product name), ED-5661, ED-5661 (above, trade name manufactured by Celanese Coating Co., Ltd.), etc. It is possible. Moreover, these crosslinkable compounds can be used individually or in combination of 2 or more types.
  • the compounds represented by formula C1 and formula C2 having a cyclohexene oxide structure from the viewpoint of heat resistance, solvent resistance, process resistance such as long-term baking resistance, and transparency, Epolide GT-401, GT-403, GT-301, GT-302, Celoxide 2021, and Celoxide 3000 are preferable.
  • E component (E1) component, (E2)
  • the bridge structure by thermal reaction with the heat-reactive part (for example, carboxyl group and / or phenolic hydroxyl group) of component (B) other than what was shown as a component.
  • the heat-reactive part for example, carboxyl group and / or phenolic hydroxyl group
  • Formable compounds can also be used.
  • 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-hexane Diol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′, -Tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, and N, N, N ', N',-tetraglycidyl-4,4'-diame Epoxy compounds such
  • a polymer having two or more structures capable of forming a bridge structure by thermal reaction with the thermally reactive site (for example, carboxyl group and / or phenolic hydroxyl group) of the component (B) is used.
  • the thermally reactive site for example, carboxyl group and / or phenolic hydroxyl group
  • it can.
  • a polymer produced by using a compound having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methacryloxypropyltrimethoxy, etc.
  • component (E) When the component (B) has a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group, a hydroxy group, a carboxyl group, an amide group, A compound having two or more groups represented by an amino group can be used as the component (E).
  • crosslinkable compounds can be used alone or in combination of two or more.
  • the content is 1 to 50 parts by weight, preferably 100 parts by weight in total of the components (A) and (B). 1 to 40 parts by mass, more preferably 1 to 30 parts by mass.
  • the content of the crosslinkable compound is low, the crosslink density formed by the crosslinkable compound is not sufficient, and therefore the effect of improving the heat resistance after the pattern formation, the solvent resistance, the long-term baking resistance, etc. May not be obtained.
  • it exceeds 50 parts by mass there is an uncrosslinked crosslinkable compound, the heat resistance after forming the pattern, the solvent resistance, the resistance to baking for a long time, etc. are reduced, and the photosensitive resin composition The storage stability of may deteriorate.
  • Component (F) is a compound having two or more ethylenic polymerizable groups.
  • the compound having two or more ethylenically polymerizable groups as referred to herein means a compound having two or more polymerizable groups in one molecule and having these polymerizable groups at the molecular terminals.
  • the polymerizable group means at least one polymerizable group selected from the group consisting of an acrylate group, a methacrylate group, a vinyl group, and an allyl group.
  • the compound having two or more ethylenic polymerizable groups as the component (F) has good compatibility with each component in the solution of the negative photosensitive resin composition of the present invention and affects the developability. From the viewpoint of not giving, a compound having a molecular weight (when the compound is a polymer, a weight average molecular weight) of 1,000 or less is preferable.
  • such compounds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, penta Erythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethyl Propanetrimethacryl
  • the above polyfunctional acrylate compounds can be easily obtained as commercial products. Specific examples thereof include KYARAD T-1420, DPHA, DPHA-2C, D-310, D-330, and the like. DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, R-526, NPGDA, PEG400DA, MANDA, R-167, HX -220, HX620, R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-240, M-6200, M-309, M-400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M-1310, M-1310, M-1600, M-1960, M-8100, M-8530, M-8560, M-85
  • the content of the component (F) in the photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass with respect to 100 parts by mass as the total of the components (A) and (B). More preferably, it is 10 to 80 parts by mass, and particularly preferably 20 to 70 parts by mass. If this ratio is too small, the exposed area will be insufficiently cured, and pattern formation may not be possible, or even if possible, the film may be unreliable. Moreover, when this ratio is excessive, tack may generate
  • the component (G) used in the photosensitive resin composition of the present invention is a compound having two or more functional groups that form a covalent bond with an acid.
  • Examples of such a functional group that forms a covalent bond with an acid include an epoxy group and a methylol group.
  • Examples of the compound having two 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-diglycidylphenyl glycidyl ether, 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, diglycidyl 1,2-cyclohexanedicarboxylate Ester, 4,4′-methylenebis (N, N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-di Glycidyl ether, and pentaerythr
  • epoxy resins having amino groups such as YH-434, YH434L (manufactured by Tohto Kasei Co., Ltd.); Epolide GT-401, Epoxy resin having a cyclohexene oxide structure such as GT-403, GT-301, GT-302, Celoxide 2021, Celoxide 3000 (manufactured by Daicel Chemical Industries, Ltd.); Epicoat 1001, 1002, 1003, 1004, Bisphenol A type epoxy resins such as 1007, 1009, 1010, and 828 (manufactured by Yuka Shell Epoxy Co., Ltd.
  • Cresol novolak type epoxy resin such as Denacor EX-252 (manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179, Araldite CY-182, CY-192, CY-184 (above) CIBA-GEIGY A.G), Epicron 200, the same 00 (manufactured by Dainippon Ink & Chemicals, Inc.), Epicoat 871, 872 (manufactured by Yuka Shell Epoxy Co., Ltd.
  • ED-5661 As described above, alicyclic epoxy resin such as Celanese Coating Co., Ltd .; Denacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX -522, aliphatic polyglycidyl ethers such as EX-421, EX-313, EX-314, EX-321 (manufactured by Nagase ChemteX Corporation).
  • the polymer which has an epoxy group can also be used as a compound which has 2 or more of epoxy groups.
  • the polymer having an epoxy group can be produced, for example, by addition polymerization using an addition polymerizable monomer having an epoxy group. Examples include addition polymerization polymers such as polyglycidyl acrylate, copolymers of glycidyl methacrylate and ethyl methacrylate, copolymers of glycidyl methacrylate and styrene and 2-hydroxyethyl methacrylate, and condensation polymerization polymers such as epoxy novolac. .
  • the polymer having an epoxy group can be produced by a reaction between a polymer compound having a hydroxy group and 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.
  • Examples of the compound having two or more methylol groups include 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4 , 6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone.
  • glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resins (trade name: UFR (registered trademark) 65) ), Butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin (high-condensation type, product name: Beccamin (trade name) manufactured by DIC Corporation) Registered trademark) J-300S, P-955, N), tetramethoxymethylbenzoguanamine and the like.
  • methylated urea resins (trade name: UFR (registered trademark) 65)
  • Butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV)
  • methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, 350) manufactured by Mitsui Cytec Co., Ltd., butoxymethyl type melamine compounds (trade name: My Coat (registered trademark)) 506, 508), Sanwa Chemical's methoxymethyl-type melamine compound (trade names: Nicalak (registered trademark) MW-30, MW-22, MW-11, MS-001, MX-002, MX-730, MX-750, MX-035) and butoxymethyl type melamine compounds (trade names: Nicalac (registered trademark) MX-45, MX-410, MX-302).
  • a polymer having a methylol group can also be used as a compound having two or more methylol groups.
  • Examples of the polymer having two or more methylol groups include hydroxy such as N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide.
  • hydroxy such as N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide.
  • the polymer manufactured using the acrylamide compound or the methacrylamide compound substituted by the methyl group or the alkoxymethyl group is mentioned.
  • Such a polymer include, for example, poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, N And a copolymer of ethoxymethyl methacrylamide and benzyl methacrylate, a copolymer of N-butoxymethyl acrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate.
  • the weight average molecular weight of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and still more preferably 3,000 to 50,000.
  • These compounds having two or more methylol groups can be used alone or in combination of two or more.
  • the total content of component (A) and component (B) is 100.
  • the amount is preferably 5 to 200 parts by weight, more preferably 50 to 150 parts by weight based on the parts by weight. If this ratio is too small, the photo-curing property of the negative photosensitive resin composition may be reduced, whereas if it is too large, the developability of the unexposed area will be reduced, resulting in residual film or residue. It may be a cause.
  • the photosensitive resin composition of the present invention is a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, an adhesion promoter, or a polyvalent, as necessary, as long as the effects of the present invention are not impaired. It can contain dissolution promoters such as phenol and polycarboxylic acid.
  • the photosensitive resin composition of the present invention is a photosensitive resin composition containing the following component (A), component (B), component (C) and component (D), and, if desired, component (E) One or more of the crosslinking agent, the compound (F) having two or more polymerizable groups, the compound (G) having two or more functional groups that form a covalent bond with the acid, and other additives It is a composition that can be contained.
  • B) Component: Alkali-soluble resin (C) solvent
  • the preferable example of the photosensitive resin composition of this invention is as follows. [1]: A photosensitive resin composition containing 0.1 to 20 parts by mass of component (A) with respect to 100 parts by mass of component (B), and these components dissolved in solvent (C). [2]: Contains 0.1 to 20 parts by weight of component (A), 5 to 100 parts by weight of component (D) with respect to 100 parts by weight of component (B), and these components are dissolved in solvent (C). Photosensitive resin composition. [3]: 0.1 to 20 parts by weight of component (A), 5 to 100 parts by weight of component (D) are contained in 100 parts by weight of component (B), and these components are dissolved in solvent (C). The photosensitive resin composition further comprising 1 to 50 parts by mass of the crosslinking agent as component (E) for 100 parts by mass of the total of components (A) and (B) Composition.
  • the ratio of the solid content in the photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1 to 80% by mass, and for example, 5 to 60% by mass or 10 to 50% by mass.
  • solid content means what remove
  • the preparation method of the photosensitive resin composition of this invention is not specifically limited, As the preparation method, (A) component (specific polymer) is melt
  • the solution of the copolymer obtained by the polymerization reaction in the solvent (C) can be used as it is, and in this case, the solution of the component (A) Similarly, when (B) component, (D) component, and (E) component, (F) component, (G) component, etc. are added as necessary to obtain a uniform solution, (C) ) Additional solvent may be added. At this time, the (C) solvent used in the process of forming the specific copolymer may be the same as or different from the (C) solvent used for adjusting the concentration when preparing the photosensitive resin composition. Also good.
  • the prepared photosensitive resin composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 ⁇ m.
  • the photosensitive resin composition of the present invention is coated with a semiconductor substrate (for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a metal (for example, aluminum, molybdenum, or chromium)), a glass substrate, a quartz substrate, or an ITO substrate. Etc.) by spin coating, flow coating, roll coating, slit coating, spin coating following slit, ink jet coating, etc., and then pre-dried in a hot plate or oven to form a coating film can do. Then, the photosensitive resin film is formed by heat-treating this coating film.
  • a semiconductor substrate for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a metal (for example, aluminum, molybdenum, or chromium)
  • a glass substrate for example, a quartz substrate, or an ITO substrate.
  • Etc. by spin coating, flow coating, roll coating, slit coating, spin coating following slit,
  • a heating temperature and a heating time appropriately selected from the range of a temperature of 70 ° C. to 160 ° C. and a time of 0.3 to 60 minutes are adopted.
  • the heating temperature and heating time are preferably 80 to 140 ° C. 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 to 30 ⁇ m, is, for example, 0.2 to 10 ⁇ m, and is further, for example, 0.3 to 8 ⁇ m.
  • a mask having a predetermined pattern is attached, irradiated with light such as ultraviolet rays, and developed with an alkali developer, so that either the exposed part or the unexposed part depends on the material composition.
  • a relief pattern having a sharp end face can be obtained by heating the patterned film remaining after washing out at 80 ° C. to 140 ° C. for 0.5 to 10 minutes as necessary.
  • alkaline developer examples include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide, and hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline.
  • alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide
  • hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline.
  • a surfactant or the like can be added to these developers.
  • a tetraethylammonium hydroxide 0.1 to 2.58 mass% aqueous solution is generally used as a photoresist developer, and this alkaline developer is also used in the photosensitive resin composition of the present invention. It can be developed satisfactorily without causing problems such as swelling.
  • any of a liquid piling method, a dipping method, a rocking dipping method and the like can be used as a developing method.
  • the development time at that time is usually 15 to 180 seconds.
  • the photosensitive resin film is washed with running water, for example, for 20 to 120 seconds, and then air-dried with compressed air or compressed nitrogen or by spinning to remove moisture on the substrate and form a pattern. A finished film is obtained.
  • the pattern forming film is subjected to post-baking for thermosetting, specifically by heating using a hot plate, an oven, etc., thereby providing heat resistance, transparency, and flatness.
  • a film having a good relief pattern with excellent water absorption and chemical resistance can be obtained.
  • the post-bake is generally processed at a heating temperature selected from the range of 140 ° C. to 270 ° C. for 5 to 30 minutes when on a hot plate and 30 to 90 minutes when in an oven. The method is taken.
  • a desired cured film having a good pattern shape can be obtained by such post-baking.
  • a coating film having high storage stability, sufficiently high sensitivity, and very small unexposed area film thickness at the time of development and having a fine pattern. can be formed.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • MMA methyl methacrylate
  • HEMA 2-hydroxyethyl methacrylate
  • HPMA 4-hydroxyphenyl methacrylate
  • HPMA-QD condensation reaction of 1 mol of 4-hydroxyphenyl methacrylate and 1.1 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride
  • CHMI N-cyclohexylmaleimide
  • TMSSMA methacryloxypropyltris (trimethylsiloxy) silane
  • PFHMA 2- (perfluorohexyl) ethyl methacrylate
  • MAA methacrylic acid
  • AIBN ⁇ , ⁇ ′-azobisisobutyronitrile
  • QD 1 mol of ⁇ , ⁇ , ⁇ '-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene and 1,2-naphthoquinone-2-d
  • Examples 1 to 5 and Comparative Examples 1 to 4> According to the composition shown in the following Table 1, the solution of the component (A), the solution of the component (B), the component (D), the component (E), and the component (F) are dissolved in the solvent (C) at a predetermined ratio.
  • the photosensitive resin composition of each Example and each comparative example was prepared by stirring at room temperature for 3 hours to make a uniform solution.
  • the photosensitive resin composition was applied onto a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 80 ° C. for 120 seconds to form a coating film having a thickness of 1.2 ⁇ m.
  • This coating film was immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 60 seconds, and then washed with running ultrapure water for 30 seconds. Next, this coating film was post-baked by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a thickness of 1.0 ⁇ m.
  • TMAH tetramethylammonium hydroxide
  • the contact angle of methyl benzoate on the cured film was measured using a Drop Master manufactured by Kyowa Interface Science Co., Ltd. The obtained results are shown in Table 2.
  • the photosensitive resin composition was applied onto a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a thickness of 1.2 ⁇ m.
  • This coating film was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. Next, this coating film was post-baked by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a thickness of 1.0 ⁇ m.
  • the contact angle of methyl benzoate on the cured film was measured using a Drop Master manufactured by Kyowa Interface Science Co., Ltd. The obtained results are shown in Table 2.
  • UV ozone treatment resistance Examples 1 to 3 and Comparative Examples 1 to 3
  • the photosensitive resin composition was applied onto a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 80 ° C. for 120 seconds to form a coating film having a thickness of 1.2 ⁇ m.
  • This coating film was immersed in a 2.38 mass% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. Next, this coating film was post-baked by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a thickness of 1.0 ⁇ m.
  • This coating film was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. Next, this coating film was post-baked by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a thickness of 1.0 ⁇ m. This cured film was subjected to ozone cleaning for 10 minutes using UV-312 manufactured by Technovision. The contact angle of methyl benzoate on the ozone-cleaned membrane was measured using a Drop Master manufactured by Kyowa Interface Science Co., Ltd. The obtained results are shown in Table 2. The difference between post-baking and UV ozone treatment is within 20 °.
  • Example 4 evaluation of wettability: Example 4, Example 5 and Comparative Example 4
  • the photosensitive resin composition was applied onto ITO-glass using a spin coater and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a thickness of 1.2 ⁇ m.
  • This coating film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5.5 mW / cm 2 for a certain period of time by means of an ultraviolet irradiation apparatus PLA-600FA manufactured by Canon Inc. through a rectangular pattern mask having a length of 50 ⁇ m and a width of 100 ⁇ m.
  • Comparative Example 1 and Examples 1 to 5 had good wettability of the rectangular openings. On the other hand, in Comparative Examples 2 to 4, sufficient wettability could not be confirmed.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Theoretical Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Electroluminescent Light Sources (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

[Problem] To provide a photosensitive resin composition which is suitable as a pixel barrier material and a material for forming a patterned insulating film that is used for liquid crystal display elements, organic EL display elements and the like, and which is able to maintain a good image even after curing and is capable of forming an image of a cured film having high lypophilicity on a substrate without requiring oxygen plasma processing or the like, while having high oil repellency even after UV ozone processing. [Solution] A thermally curable photosensitive resin composition which contains component (A), component (B), solvent (C) and component (D) described below. (A): a polysiloxane having the following groups (A1) and (A2) (A1): an organic group having a fluorine atom (A2): an organic group having a thermally crosslinkable group (B): an alkali-soluble resin (C): a solvent (D): a sensitizing agent

Description

感光性樹脂組成物Photosensitive resin composition
　本発明は、感光性樹脂組成物及びそれから得られる硬化膜に関する。
　より詳細には、高い撥水性と撥油性を硬化膜表面に有する画像を形成可能な感光性樹脂組成物及びその硬化膜、並びに該硬化膜を用いた各種材料に関する。この感光性樹脂組成物は、特に液晶ディスプレイやＥＬディスプレイにおける層間絶縁膜、インクジェット方式に対応した遮光材料や隔壁材料として用いるのに好適である。 The present invention relates to a photosensitive resin composition and a cured film obtained therefrom.
More specifically, the present invention relates to a photosensitive resin composition capable of forming an image having high water repellency and oil repellency on the surface of the cured film, a cured film thereof, and various materials using the cured film. This photosensitive resin composition is particularly suitable for use as an interlayer insulating film in a liquid crystal display or an EL display, a light shielding material corresponding to an inkjet method, or a partition material.
薄膜トランジスタ（ＴＦＴ）型液晶表示素子、有機ＥＬ（ｅｌｅｃｔｒｏｌｕｍｉｎｅｓｃｅｎｔ）素子等のディスプレイ素子の作製工程においてインクジェットを用いたフルカラー表示基板作製技術も近年活発に検討されている。たとえば液晶表示素子におけるカラーフィルタ作製に関しては、従来の印刷法、電着法、染色法または顔料分散法に対して、あらかじめパターニングされた画素を規定する区画（以下バンクという）を、光を遮断する感光性樹脂層で形成し、このバンクに囲まれた領域にインク滴を滴下するカラーフィルタおよびその製造方法（特許文献１）などが提案されている。また有機ＥＬ表示素子においてもあらかじめバンクを作製し、同様に発光層となるインクを滴下し、有機ＥＬ表示素子を作製する方法（特許文献２）が提案されている。
　しかしインクジェット法でバンクに囲まれた領域にインク滴を滴下する場合、バンクを超えて隣の画素にインク滴が溢れる事態を防ぐため、基板には親インク性（親水性、親油性）を持たせ、バンク表面には撥水性と撥油性を持たせる必要がある。 In recent years, a full color display substrate manufacturing technique using an 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 EL (electroluminescent) element has been actively studied. For example, with respect to the production of a color filter in a liquid crystal display element, light is blocked from a section (hereinafter referred to as a bank) that defines pixels that have been patterned in advance, compared to a conventional printing method, electrodeposition method, dyeing method, or pigment dispersion method. A color filter that is formed of a photosensitive resin layer and drops ink droplets in a region surrounded by the bank, a manufacturing method thereof (Patent Document 1), and the like have been proposed. Also, a method has been proposed (Patent Document 2) in which an organic EL display element is manufactured by preparing a bank in advance and dropping an ink serving as a light emitting layer in the same manner.
However, when ink droplets are dropped on the area surrounded by the bank by the inkjet method, the substrate has ink-philicity (hydrophilicity, oleophilicity) to prevent the ink droplet from overflowing to the adjacent pixels beyond the bank. The bank surface must be water and oil repellent.
　上記の目的を達成するため、酸素ガスプラズマ処理及びフッ素ガスプラズマ処理などの連続的プラズマ処理やＵＶオゾン処理により、基板に親水性を持たせ、且つバンクには撥水性を持たせることができると提案されている（特許文献３）。また、感光性有機薄膜にフッ素系界面活性剤やフッ素系ポリマーを配合した提案もなされている（特許文献４）が、相溶性や添加量など、感光性のみならず塗膜性も含めて考慮すべき点が多いだけでなく、基板の親水処理の際のＵＶオゾン処理で表面の撥水性が低下するため実用的ではなかった。 In order to achieve the above object, the substrate can be made hydrophilic and the bank can be made water repellent by continuous plasma treatment such as oxygen gas plasma treatment and fluorine gas plasma treatment or UV ozone treatment. It has been proposed (Patent Document 3). In addition, a proposal has been made that a fluorine-based surfactant or a fluorine-based polymer is blended with a photosensitive organic thin film (Patent Document 4), but consideration is given not only to photosensitivity but also to coating properties, such as compatibility. Not only is there much to be done, but also the UV ozone treatment during the hydrophilic treatment of the substrate reduces the water repellency of the surface, which is not practical.
　一方、従来、撥液バンクとして、ネガ型のものとしては特開２０１５－１７２７４２号公報(特許文献５)がある。また、ポジ型のものとしては特開２０１２－２２０８６０号公報(特許文献６)がある。 On the other hand, as a conventional liquid repellent bank, there is a negative type of Japanese Unexamined Patent Application Publication No. 2015-172742 (Patent Document 5). Moreover, as a positive type, there is JP 2012-220860 A (Patent Document 6).
特開２０００－１８７１１１号公報JP 2000-187111 A 特開平１１－５４２７０号公報Japanese Patent Laid-Open No. 11-54270 特開２０００－３５３５９４号公報JP 2000-353594 A 特開平１０－１９７７１５号公報JP-A-10-197715 特開２０１５－１７２７４２号公報Japanese Patent Laying-Open No. 2015-172742 特開２０１２－２２０８６０号公報JP 2012-220860 A
　本発明は、上記の事情に鑑みなされたものであって、その解決しようとする課題は、液晶表示素子、有機ＥＬ表示素子等に使用され、ＵＶオゾン処理をした後であっても硬化膜表面に高い撥水性と高い撥油性を有し、プラズマ処理やＵＶオゾン処理をせずとも基板に高い親液性を有する硬化膜の画像を形成することにある。特に、インクジェットを用いた基板作製において、バンクを超えて隣の画素にインク滴が溢れる事態を防ぐことができる硬化膜の画像を形成することにある。 The present invention has been made in view of the above circumstances, and the problem to be solved is used for liquid crystal display elements, organic EL display elements and the like, and even after UV ozone treatment, the surface of the cured film It is to form an image of a cured film having high water repellency and high oil repellency and high lyophilicity on a substrate without plasma treatment or UV ozone treatment. In particular, it is to form an image of a cured film that can prevent a situation where an ink droplet overflows to an adjacent pixel beyond a bank in manufacturing a substrate using inkjet.
　本発明者らは、上記目的を達成するために鋭意検討した結果、フッ素原子を有する有機基と熱架橋性基を有する有機基とを有するポリシロキサンを含む組成物から硬化膜を形成することにより、ＵＶオゾン処理をした後であっても膜表面に撥液性を、プラズマ処理やＵＶオゾン処理をせずとも基板に高い親液性を効率的に付与できることを見出し、本発明を完成させた。 As a result of intensive investigations to achieve the above object, the present inventors have formed a cured film from a composition containing polysiloxane having an organic group having a fluorine atom and an organic group having a thermally crosslinkable group. The present inventors have found that even after UV ozone treatment, liquid repellency can be efficiently applied to the film surface, and high lyophilicity can be efficiently imparted to the substrate without plasma treatment or UV ozone treatment. .
　即ち、本発明は以下に関する。
１．下記（Ａ）成分、（Ｂ）成分、（Ｃ）溶剤及び（Ｄ）成分を含有する熱硬化可能な感光性樹脂組成物。
（Ａ）成分：下記基（Ａ１）及び（Ａ２）を有するポリシロキサン
（Ａ１）フッ素原子を有する有機基
（Ａ２）熱架橋性基を有する有機基
（Ｂ）成分：アルカリ可溶性樹脂
（Ｃ）溶剤、
（Ｄ）成分：感光剤。
２．（Ａ２）熱架橋性基を有する有機基は、エポキシ基を有する有機基である上記１に記載の感光性樹脂組成物。
３．下記（Ｚ１）乃至（Ｚ４）の少なくともいずれか１つを満足する上記１または２に記載の感光性樹脂組成物。
（Ｚ１）：（Ｅ）成分である架橋剤をさらに含有する、
（Ｚ２）：（Ｂ）成分のアルカリ可溶性樹脂が、自己架橋性基をさらに有するか、又はヒドロキシ基、カルボキシル基、アミド基及びアミノ基からなる群から選ばれる少なくとも１つの基と反応する基をさらに有する。
（Ｚ３）：（Ｄ）成分が光ラジカル発生剤であり、さらに（Ｆ）成分であるエチレン性二重結合を２個以上有する化合物を含有する。
（Ｚ４）：（Ｄ）成分が光酸発生剤であり、さらに（Ｇ）成分である酸により共有結合を形成する官能基を２個以上有する化合物を含有する。
４．（Ｄ）成分がキノンジアジド化合物である上記１または２に記載の感光性樹脂組成物。
５．（Ｄ）成分がキノンジアジド化合物であり、上記（Ｚ１）及び（Ｚ２）の何れかを満足する上記３に記載の感光性樹脂組成物。
６．（Ａ）成分がさらにフェニル基を有する上記１乃至５のいずれかに記載の感光性樹脂組成物。
７．（Ａ）成分のポリシロキサンの数平均分子量がポリスチレン換算で１，０００乃至１００，０００である上記６に記載の感光性樹脂組成物。
８．（Ｂ）成分のアルカリ可溶性樹脂の数平均分子量がポリスチレン換算で２，０００乃至５０，０００である上記１乃至７のいずれか１つに記載の型感光性樹脂組成物。
９．（Ｂ）成分１００質量部に対して０．１～２０質量部の（Ａ）成分を含有することを特徴とする上記１乃至８のいずれか１つに記載の型感光性樹脂組成物。
１０．（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、（Ｄ）成分が５乃至１００質量部であることを特徴とする請求項１乃至９のいずれか一項に記載の感光性樹脂組成物。
１１．（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、（Ｅ）成分が１乃至５０質量部であることを特徴とする上記３乃至１０のいずれか１つに記載の感光性樹脂組成物。
１２．上記１乃至１１のいずれか１つに記載の感光性樹脂組成物を用いて得られる硬化膜。
１３．上記１２に記載の硬化膜を有する表示素子。
１４．上記１２に記載の硬化膜を画像形成用隔壁として有する表示素子。 That is, the present invention relates to the following.
1. A thermosetting photosensitive resin composition containing the following component (A), component (B), solvent (C) and component (D).
(A) Component: Polysiloxane having the following groups (A1) and (A2) (A1) Organic group having fluorine atom (A2) Organic group having thermally crosslinkable group (B) Component: Alkali-soluble resin (C) solvent ,
(D) Component: Photosensitizer.
2. (A2) The photosensitive resin composition according to 1 above, wherein the organic group having a thermally crosslinkable group is an organic group having an epoxy group.
3. 3. The photosensitive resin composition according to 1 or 2 that satisfies at least one of the following (Z1) to (Z4).
(Z1): further containing a crosslinking agent as component (E),
(Z2): The alkali-soluble resin of the component (B) further has a self-crosslinkable group or a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group. Also have.
(Z3): The component (D) is a photoradical generator, and further contains a compound having two or more ethylenic double bonds as the component (F).
(Z4): The component (D) is a photoacid generator, and further contains a compound having two or more functional groups that form a covalent bond with the acid (G).
4). (D) The photosensitive resin composition of said 1 or 2 whose component is a quinonediazide compound.
5. (D) The photosensitive resin composition of said 3 with which a component is a quinonediazide compound and satisfies either of the said (Z1) and (Z2).
6). (A) The photosensitive resin composition in any one of said 1 thru | or 5 in which a component further has a phenyl group.
7). (A) The photosensitive resin composition of said 6 whose number average molecular weight of polysiloxane of a component is 1,000 thru | or 100,000 in polystyrene conversion.
8). The type photosensitive resin composition according to any one of 1 to 7 above, wherein the number average molecular weight of the alkali-soluble resin as the component (B) is 2,000 to 50,000 in terms of polystyrene.
9. The type photosensitive resin composition as described in any one of 1 to 8 above, which comprises 0.1 to 20 parts by mass of the component (A) with respect to 100 parts by mass of the component (B).
10. The photosensitive property according to any one of claims 1 to 9, wherein the component (D) is 5 to 100 parts by mass with respect to 100 parts by mass of the total of the component (A) and the component (B). Resin composition.
11. The photosensitive resin as described in any one of 3 to 10 above, wherein the component (E) is 1 to 50 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B). Composition.
12 The cured film obtained using the photosensitive resin composition as described in any one of said 1 thru | or 11.
13. 13. A display element having the cured film as described in 12 above.
14 13. A display element having the cured film as described in 12 above as an image forming partition.
　本発明の感光性樹脂組成物は、ＵＶオゾン処理をした後であっても硬化膜表面に高い撥油性を有し、プラズマ処理やＵＶオゾン処理をせずとも基板に高い親液性を有する硬化膜の画像を形成することにある。 The photosensitive resin composition of the present invention has high oil repellency on the cured film surface even after UV ozone treatment, and has high lyophilicity on the substrate without plasma treatment or UV ozone treatment. It is to form an image of the film.
　本発明の感光性樹脂組成物は、下記（Ａ）成分、（Ｂ）成分、（Ｃ）溶剤及び（Ｄ）成分を含有する感光性樹脂組成物である。
（Ａ）成分：下記基（Ａ１）及び（Ａ２）を有するポリシロキサン
（Ａ１）フッ素原子を有する有機基
（Ａ２）熱架橋性基を有する有機基
（Ｂ）成分：アルカリ可溶性樹脂；
（Ｃ）溶剤、
（Ｄ）成分：感光剤。 The photosensitive resin composition of this invention is a photosensitive resin composition containing the following (A) component, (B) component, (C) solvent, and (D) component.
(A) Component: Polysiloxane having the following groups (A1) and (A2) (A1) Organic group having fluorine atom (A2) Organic group having thermally crosslinkable group (B) Component: Alkali-soluble resin;
(C) solvent,
(D) Component: Photosensitizer.
　本発明の感光性樹脂組成物は、更に下記（Ｚ１）乃至（Ｚ４）の少なくともいずれか１つを満足することが好ましい。
（Ｚ１）：（Ｅ）成分である架橋剤をさらに含有する、
（Ｚ２）：（Ｂ）成分のアルカリ可溶性樹脂が、自己架橋性基をさらに有するか、又はヒドロキシ基、カルボキシル基、アミド基及びアミノ基からなる群から選ばれる少なくとも１つの基と反応する基をさらに有する。
（Ｚ３）：（Ｄ）成分が光ラジカル発生剤であり、さらに（Ｆ）成分であるエチレン性重合性基を２個以上有する化合物を含有する。
（Ｚ４）：（Ｄ）成分が光酸発生剤であり、さらに（Ｇ）成分である酸により共有結合を形成する官能基を２個以上有する化合物を含有する。 The photosensitive resin composition of the present invention preferably further satisfies at least one of the following (Z1) to (Z4).
(Z1): further containing a crosslinking agent as component (E),
(Z2): The alkali-soluble resin of the component (B) further has a self-crosslinkable group or a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group. Also have.
(Z3): The component (D) is a photoradical generator, and further contains a compound having two or more ethylenic polymerizable groups as the component (F).
(Z4): The component (D) is a photoacid generator, and further contains a compound having two or more functional groups that form a covalent bond with the acid (G).
本発明の感光性樹脂組成物は、（Ｄ）成分がキノンジアジド化合物であるポジ型感光性樹脂組成物であることが好ましい。 The photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition in which the component (D) is a quinonediazide compound.
　以下、各成分の詳細を説明する。
＜（Ａ）成分＞
本発明に用いるポリシロキサン（Ａ）は、下記基（Ａ１）及び（Ａ２）を有するポリシロキサンである。
（Ａ１）フッ素原子を有する有機基
（Ａ２）熱架橋性基を有する有機基 Hereinafter, details of each component will be described.
<(A) component>
The polysiloxane (A) used in the present invention is a polysiloxane having the following groups (A1) and (A2).
(A1) Organic group having fluorine atom (A2) Organic group having thermally crosslinkable group
（Ａ１）フッ素原子を有する有機基は、ポリシロキサン主鎖のケイ素原子に結合した有機基であって、一部又は全部がフッ素原子で置換された有機基のことである。このフッ素原子を有する有機基は、本発明の効果を損なわない限り、フッ素原子を有するものであれば特に限定されない。特に、水素原子の一部若しくは全部がフッ素原子で置換されたアルキル基や、水素原子の一部若しくは全部がフッ素原子で置換されたエーテル結合を含むアルキル基などが好ましい。その際、この有機基が有するフッ素原子の数も特に限定されない。より好ましくは、パーフルオロアルキル基であり、更に好ましくは式（１）で表される有機基である。
Figure JPOXMLDOC01-appb-C000001
 （ｋは０～１２の整数を表す。） (A1) The organic group having a fluorine atom is an organic group bonded to a silicon atom of the polysiloxane main chain, and a part or all of the organic group is substituted with a fluorine atom. The organic group having a fluorine atom is not particularly limited as long as it has a fluorine atom as long as the effects of the present invention are not impaired. In particular, an alkyl group in which part or all of the hydrogen atoms are substituted with fluorine atoms, an alkyl group having an ether bond in which some or all of the hydrogen atoms are substituted with fluorine atoms, and the like are preferable. At that time, the number of fluorine atoms of the organic group is not particularly limited. More preferred is a perfluoroalkyl group, and still more preferred is an organic group represented by the formula (1).
Figure JPOXMLDOC01-appb-C000001
 (K represents an integer of 0 to 12)
式（１）で表される有機基の具体例を示すと、トリフルオロプロピル基、トリデカフルオロオクチル基、ヘプタデカフルオロデシル基、２，２，２－トリフルオロエチル基、２，２，３，３，３－ペンタフルオロプロピル基、２－（パーフルオロブチル）エチル基、２－（パーフルオロヘキシル）エチル基、２－（パーフルオロオクチル）エチル基、２－（パーフルオロデシル）エチル基、２－（パーフルオロ－３－メチルブチル）エチル基、２－（パーフルオロ－５－メチルヘキシル）エチル基、２－（パーフルオロ－７－メチルオクチル）エチル基等が挙げられる。本発明において、ポリシロキサン（Ａ）が有するフッ素原子を有する有機基は、一種単独でも複数種であっても良い。 Specific examples of the organic group represented by the formula (1) include trifluoropropyl group, tridecafluorooctyl group, heptadecafluorodecyl group, 2,2,2-trifluoroethyl group, 2,2,3 , 3,3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluorohexyl) ethyl group, 2- (perfluorooctyl) ethyl group, 2- (perfluorodecyl) ethyl group, Examples include 2- (perfluoro-3-methylbutyl) ethyl group, 2- (perfluoro-5-methylhexyl) ethyl group, 2- (perfluoro-7-methyloctyl) ethyl group, and the like. In this invention, the organic group which has a fluorine atom which polysiloxane (A) has may be 1 type individual, or multiple types.
ポリシロキサン（Ａ）のフッ素原子を有する有機基は、撥液性付与と膜硬度及び溶剤耐性との両立の観点から、ポリシロキサン（Ａ）が有する全ケイ素原子の１モルに対して０．０５～０．５モルが好ましく、０．１～０．４モルがさらに好ましい。 The organic group having a fluorine atom of the polysiloxane (A) is 0.05% with respect to 1 mol of all silicon atoms of the polysiloxane (A) from the viewpoint of providing both liquid repellency and film hardness and solvent resistance. Is preferably 0.5 mol, more preferably 0.1 mol to 0.4 mol.
（Ａ２）熱架橋性基を有する有機基における熱架橋性基としては、加熱により共有結合を形成する基であれば特に限定しないが、例えば、ビニル基、エポキシ基、アミノ基、メルカプト基、ブロックイソシアネート基、またはイソシアネート基が挙げられる。
さらに、熱架橋性基がエポキシ基の場合に、エポキシ基を有する有機基としては、グリシジルオキシ基、３，４－エポキシシクロヘキシルメチル基等が挙げられる。
ポリシロキサン（Ａ）の熱架橋性基を有する有機基は、撥液性付与と膜硬度及び溶剤耐性との両立の観点から、ポリシロキサン（Ａ）が有する全ケイ素原子の１モルに対して０．２～０．９５モルが好ましく、０．３～０．８モルがさらに好ましい。 (A2) The heat-crosslinkable group in the organic group having a heat-crosslinkable group is not particularly limited as long as it is a group that forms a covalent bond by heating. For example, a vinyl group, an epoxy group, an amino group, a mercapto group, a block An isocyanate group or an isocyanate group is mentioned.
Further, when the thermally crosslinkable group is an epoxy group, examples of the organic group having an epoxy group include a glycidyloxy group and a 3,4-epoxycyclohexylmethyl group.
The organic group having a thermally crosslinkable group of the polysiloxane (A) is 0 with respect to 1 mol of all silicon atoms of the polysiloxane (A) from the viewpoint of providing both liquid repellency and film hardness and solvent resistance. .2 to 0.95 mol is preferable, and 0.3 to 0.8 mol is more preferable.
また、本発明のポリシロキサン（Ａ）は、（Ａ１）フッ素原子を有する有機基ではなく、（Ａ２）熱架橋性基を有する有機基でもない、その他の有機基がポリシロキサン主鎖のケイ素原子に結合していてもよい。当該その他の有機基は、フッ素原子を有しない炭素数１～２０、好ましくは１～１０の有機基である。 In addition, the polysiloxane (A) of the present invention is (A1) not an organic group having a fluorine atom, but (A2) an organic group having no thermally crosslinkable group, and other organic groups are silicon atoms in the polysiloxane main chain. May be bonded to. The other organic group is an organic group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, having no fluorine atom.
このようなフッ素原子を有しない有機基の例としては、直鎖状又は分岐構造を有する飽和炭化水素基；ベンゼン環を有する芳香族基；アミノ基、ウレイド基若しくはビニル基などを有する有機基；又は、エーテル結合やエステル結合を有する有機基などが挙げられる。
これらの具体例を挙げると、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘプチル基、オクチル基、ドデシル基、ヘキサデシル基、オクタデシル基、シクロヘキシル基、フェニル基、ビニル基、γ－アミノプロピル基、γ－メタクリロキシプロピル基などが挙げられる。 Examples of such an organic group having no fluorine atom include a saturated hydrocarbon group having a linear or branched structure; an aromatic group having a benzene ring; an organic group having an amino group, a ureido group or a vinyl group; Or the organic group etc. which have an ether bond and an ester bond are mentioned.
Specific examples thereof include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, heptyl group, octyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, phenyl group, vinyl group, γ -Aminopropyl group, γ-methacryloxypropyl group and the like.
本発明において、ポリシロキサン（Ａ）が有するフッ素原子を有しない有機基の量は、本発明の効果を損なわない限りにおいて特に限定されないが、ポリシロキサン（Ａ）が有する全ケイ素原子の１モルに対して、好ましくは０．０１～０．７５モルである。このような範囲の場合、有機溶剤の接触角が５０度以上の被膜が得られやすく、均質なポリシロキサン（Ａ）の溶液が得られやすい。 In the present invention, the amount of the organic group having no fluorine atom in the polysiloxane (A) is not particularly limited as long as the effect of the present invention is not impaired, but it is 1 mol of all the silicon atoms in the polysiloxane (A). On the other hand, the amount is preferably 0.01 to 0.75 mol. In such a range, a coating film having an organic solvent contact angle of 50 degrees or more is easily obtained, and a homogeneous polysiloxane (A) solution is easily obtained.
（Ａ）成分のポリシロキサンは、数平均分子量が１，０００乃至１００，０００の範囲内にあるものである。数平均分子量が１００，０００を超えて過大なものであると、ハンドリング性が悪化する場合があり、数平均分子量が１，０００未満で過小なものであると、現像の際、露光部の膜減りが相当量発生し、撥液性不足になる場合がある。 The polysiloxane as the component (A) has a number average molecular weight in the range of 1,000 to 100,000. When the number average molecular weight exceeds 100,000, the handling property may be deteriorated, and when the number average molecular weight is less than 1,000, the film of the exposed portion is developed. A considerable amount of reduction may occur, resulting in insufficient liquid repellency.
このようなポリシロキサン（Ａ）を得る方法は特に限定されないが、下記の式（２）で表されるアルコキシシランと、エポキシ基を有するアルコキシシランと、所望によりその他有機基を有するアルコキシシランとを重縮合して得られるポリシロキサンが好ましい。
Figure JPOXMLDOC01-appb-C000002
 （式中、Ｒ１はフッ素原子を有する有機基であり、Ｒ２およびＲ３はそれぞれ独立に炭素数１～５の炭化水素基を表し、ｍは０または１を表す。） A method for obtaining such a polysiloxane (A) is not particularly limited, but an alkoxysilane represented by the following formula (2), an alkoxysilane having an epoxy group, and an alkoxysilane having another organic group as desired. Polysiloxanes obtained by polycondensation are preferred.
Figure JPOXMLDOC01-appb-C000002
 (Wherein R 1 is an organic group having a fluorine atom, R 2 and R 3 each independently represents a hydrocarbon group having 1 to 5 carbon atoms, and m represents 0 or 1).
ここで、式（２）のＲ１は、前述のフッ素原子を有する有機基を表す。 Here, R 1 in the formula (2) represents the above-described organic group having a fluorine atom.
また、式（２）において、Ｒ２およびＲ３はそれぞれ独立に炭素数１～５の炭化水素基を表し、特に飽和炭化水素基が好ましい。なかでもメチル基、エチル基、プロピル基、ブチル基などの低級アルキル基の場合、市販品として入手し易いので好ましい。式（２）で表されるアルコキシシランとして、複数のものを使用した場合、それらのＲ２どうし、Ｒ３どうしは、同一でもそれぞれ異なっていてもよい。 In the formula (2), R 2 and R 3 each independently represent a hydrocarbon group having 1 to 5 carbon atoms, and a saturated hydrocarbon group is particularly preferable. Of these, lower alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group are preferable because they are easily available as commercial products. When a plurality of alkoxysilanes represented by the formula (2) are used, R 2 and R 3 may be the same or different from each other.
本発明においては、式（２）で表されるアルコキシシランのなかでも、Ｒ１が式（１）で表される有機基であるアルコキシシランが好ましい。
Figure JPOXMLDOC01-appb-C000003
 （ｋは０～１２の整数を表す。） In the present invention, among the alkoxysilanes represented by the formula (2), an alkoxysilane in which R 1 is an organic group represented by the formula (1) is preferable.
Figure JPOXMLDOC01-appb-C000003
 (K represents an integer of 0 to 12)
このようなＲ１が、式（１）で表される有機基であるアルコキシシランの具体例として、トリフルオロプロピルトリメトキシシラン、トリフルオロプロピルトリエトキシシラン、トリデカフルオロオクチルトリメトキシシラン、トリデカフルオロオクチルトリエトキシシラン、ヘプタデカフルオロデシルトリメトキシシラン、ヘプタデカフルオロデシルトリエトキシシラン、２－（パーフルオロヘキシル）エチルトリメトキシシランなどが挙げられる。 Specific examples of the alkoxysilane in which R 1 is an organic group represented by the formula (1) include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, and trideca. Examples include fluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, and 2- (perfluorohexyl) ethyltrimethoxysilane.
本発明において、式（２）で表されるアルコキシシランのうちの少なくとも１種を用いればよいが、必要に応じて複数種を用いてもよい。 In the present invention, at least one of the alkoxysilanes represented by the formula (2) may be used, but a plurality of types may be used as necessary.
熱架橋性基を有する有機基を有するアルコキシシランは、下記の式（３）で示されるアルコキシシランである。
Figure JPOXMLDOC01-appb-C000004
 （式中、Ｒ４は熱架橋性基を有する有機基であり、Ｒ５およびＲ６はそれぞれ独立に炭素数１～５の炭化水素基を表し、ｎは０または１を表す。） The alkoxysilane having an organic group having a thermally crosslinkable group is an alkoxysilane represented by the following formula (3).
Figure JPOXMLDOC01-appb-C000004
 (Wherein R 4 is an organic group having a thermally crosslinkable group, R 5 and R 6 each independently represent a hydrocarbon group having 1 to 5 carbon atoms, and n represents 0 or 1)
式（３）中、Ｒ４はビニル基、エポキシ基、アミノ基、メルカプト基、ブロックイソシアネート基、イソシアネート基、メタクリル基、アクリル基またはウレイド基を有する炭素数２～１２の有機基である。なかでも、入手の容易さの点から、ビニル基、エポキシ基、アミノ基、メタクリル基、アクリル基またはウレイド基を有する炭素数２～１２の有機基が好ましい。より好ましくは、エポキシ基、メタクリル基、アクリル基またはウレイド基を有する炭素数２～１２の有機基である。
より具体的に、グリシドキシ基または３，４－エポキシシクロヘキシルメチル基を有する炭素数２～１２の有機基が好ましい。 In the formula (3), R 4 is an organic group having 2 to 12 carbon atoms having a vinyl group, an epoxy group, an amino group, a mercapto group, a blocked isocyanate group, an isocyanate group, a methacryl group, an acrylic group or a ureido group. Among these, an organic group having 2 to 12 carbon atoms having a vinyl group, an epoxy group, an amino group, a methacryl group, an acrylic group or a ureido group is preferable from the viewpoint of availability. More preferably, it is an organic group having 2 to 12 carbon atoms having an epoxy group, a methacryl group, an acrylic group or a ureido group.
More specifically, an organic group having 2 to 12 carbon atoms having a glycidoxy group or a 3,4-epoxycyclohexylmethyl group is preferable.
　式（３）中、Ｒ５およびＲ６はそれぞれ独立に水素原子または炭素数１～５のアルキル基である。なかでも、水素原子または炭素数１～３のアルキル基が好ましい。 In formula (3), R 5 and R 6 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.
　式（３）で示される特定アルコキシシランの具体例としては、アリルトリエトキシシラン、アリルトリメトキシシラン、ジエトキシメチルビニルシラン、ジメトキシメチルビニルシラン、トリエトキシビニルシラン、ビニルトリメトキシシラン、ビニルトリス（２－メトキシエトキシ）シラン、ｍ－スチリルエチルトリエトキシシラン、ｐ－スチリルエチルトリエトキシシラン、ｍ－スチリルメチルトリエトキシシラン、ｐ－スチリルメチルトリエトキシシラン、３－（Ｎ－スチリルメチル－２－アミノエチルアミノ）プロピルトリメトキシシラン、ジエトキシ（３－グリシジルオキシプロピル）メチルシラン、３－グリシジルオキシプロピル（ジメトキシ）メチルシラン、３－グリシジルオキシプロピル（ジエトキシ）メチルシラン、３－グリシジルオキシプロピルトリメトキシシラン、３－グリシジルオキシプロピルトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリエトキシシラン、３－（２－アミノエチルアミノ）プロピルジメトキシメチルシラン、３－（２－アミノエチルアミノ）プロピルトリエトキシシラン、３－（２－アミノエチルアミノ）プロピルトリメトキシシラン、３－アミノプロピルジエトキシメチルシラン、３－アミノプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、トリメトキシ［３－（フェニルアミノ）プロピル］シラン、３－メルカプトプロピル（ジメトキシ）メチルシラン、（３－メルカプトプロピル）トリエトキシシラン、（３－メルカプトプロピル）トリメトキシシラン、３－（トリエトキシシリル）プロピルイソシアネート、３－（トリエトキシシリル）プロピルメタクリレート、３－（トリメトキシシリル）プロピルメタクリレート、３－（トリエトキシシリル）プロピルアクリレート、３－（トリメトキシシリル）プロピルアクリレート、２－（トリエトキシシリル）エチルメタクリレート、２－（トリメトキシシリル）エチルメタクリレート、２－（トリエトキシシリル）エチルアクリレート、２－（トリメトキシシリル）エチルアクリレート、（トリエトキシシリル）メチルメタクリレート、（トリメトキシシリル）メチルメタクリレート、（トリエトキシシリル）メチルアクリレート、（トリメトキシシリル）メチルアクリレート、γ－ウレイドプロピルトリエトキシシラン、γ－ウレイドプロピルトリメトキシシラン、γ－ウレイドプロピルトリプロポキシシラン、（Ｒ）－Ｎ－１－フェニルエチル－Ｎ’－トリエトキシシリルプロピルウレア、（Ｒ）－Ｎ－１－フェニルエチル－Ｎ’－トリメトキシシリルプロピルウレア、１－［３－（トリメトキシシリル）プロピル］ウレアなどが挙げられる。
さらに、熱により架橋反応が起こる３－グリシジルオキシプロピル（ジメトキシ）メチルシラン、３－グリシジルオキシプロピル（ジエトキシ）メチルシラン、３－グリシジルオキシプロピルトリメトキシシランまたは２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシランを用いることも好ましい。 Specific examples of the specific alkoxysilane represented by the formula (3) include allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy). ) Silane, m-styrylethyltriethoxysilane, p-styrylethyltriethoxysilane, m-styrylmethyltriethoxysilane, p-styrylmethyltriethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyl Trimethoxysilane, diethoxy (3-glycidyloxypropyl) methylsilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyl (diethoxy) methylsilane, 3- Lysidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- ( 2-aminoethylamino) propyldimethoxymethylsilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3-aminopropyldiethoxymethylsilane, 3- Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, trimethoxy [3- (phenylamino) propyl] silane, 3-mercaptopropyl (dimethoxy) methylsilane, (3-mercaptopropyl) triethoxysilane, 3-mercaptopropyl) trimethoxysilane, 3- (triethoxysilyl) propyl isocyanate, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl acrylate, 3 -(Trimethoxysilyl) propyl acrylate, 2- (triethoxysilyl) ethyl methacrylate, 2- (trimethoxysilyl) ethyl methacrylate, 2- (triethoxysilyl) ethyl acrylate, 2- (trimethoxysilyl) ethyl acrylate, ( (Triethoxysilyl) methyl methacrylate, (trimethoxysilyl) methyl methacrylate, (triethoxysilyl) methyl acrylate, (trimethoxysilyl) methyl acrylate, γ-ureidopro Lutriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (R) -N-1-phenylethyl-N′-triethoxysilylpropylurea, (R) -N-1-phenylethyl -N'-trimethoxysilylpropylurea, 1- [3- (trimethoxysilyl) propyl] urea and the like can be mentioned.
Furthermore, 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyl (diethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane or 2- (3,4-epoxycyclohexyl) ethyltrimethoxy which undergoes a crosslinking reaction by heat It is also preferable to use silane.
その際、熱架橋性基を有する有機基を有するアルコキシシランを複数種用いてもよい。 In that case, you may use multiple types of alkoxysilane which has an organic group which has a heat crosslinkable group.
その他の有機基を有するアルコキシシランとしては、式（４）で表されるアルコキシシランが挙げられる。
Figure JPOXMLDOC01-appb-C000005
 （Ｒ７は、水素原子、又はフッ素原子を有しない炭素数１～２０の有機基であり、Ｒ８は、それぞれ炭素数１～５の炭化水素基であり、ｐは０、１または２を表す。） Examples of the alkoxysilane having another organic group include alkoxysilanes represented by the formula (4).
Figure JPOXMLDOC01-appb-C000005
 (R 7 is a hydrogen atom or an organic group having 1 to 20 carbon atoms having no fluorine atom, R 8 is a hydrocarbon group having 1 to 5 carbon atoms, and p is 0, 1 or 2; Represents.)
式（４）において、Ｒ８は、炭化水素基を表すが、炭素数が少ない方が反応性が高いので、炭素数１～５の飽和炭化水素基が好ましい。より好ましくはメチル基、エチル基、プロピル基、ブチル基である。 In the formula (4), R 8 represents a hydrocarbon group, but a saturated hydrocarbon group having 1 to 5 carbon atoms is preferable because the reactivity is higher when the number of carbon atoms is smaller. More preferred are a methyl group, an ethyl group, a propyl group, and a butyl group.
式（４）においてｐ＝０の場合、式（４）で表されるアルコキシシランは、テトラアルコキシシランを表す。その具体例としては、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシランなどが挙げられ、市販品として容易に入手可能である。 When p = 0 in Formula (4), the alkoxysilane represented by Formula (4) represents tetraalkoxysilane. Specific examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like, and are easily available as commercial products.
式（４）においてｐ＝１～３の整数の場合、式（４）で表されるアルコキシシランは、Ｒ７が水素原子又はフッ素原子を有しない炭素数１～２０、好ましくは１～１０の有機基と、アルコキシ基を有するアルコキシシランである。本発明において、Ｒ７は同一でも、それぞれ異なっていてもよい。 In the case where p is an integer of 1 to 3 in the formula (4), the alkoxysilane represented by the formula (4) has R 7 having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms not having a hydrogen atom or a fluorine atom An alkoxysilane having an organic group and an alkoxy group. In the present invention, R 7 may be the same or different.
フッ素原子を有しない炭素数１～２０の有機基としては、直鎖状又は分岐構造を有する飽和炭化水素基、ベンゼン環を有する芳香族基、アミノ基、ウレイド基若しくはビニル基などを有する有機基、又は、エーテル結合やエステル結合を有する有機基などが挙げられる。 Examples of the organic group having 1 to 20 carbon atoms not having a fluorine atom include a saturated hydrocarbon group having a linear or branched structure, an aromatic group having a benzene ring, an amino group, a ureido group, or a vinyl group. Or an organic group having an ether bond or an ester bond.
式（４）のＲ８は、炭素数１～５の炭化水素基である。ｐが１又は２の場合、一般的にはＲ８が同一の場合が好ましいが、本発明においては、Ｒ８は同一でも、それぞれ異なっていてもよい。このような式（４）のｐ＝１～３の整数の場合の、アルコキシシランの具体例を以下に示す。
例えば、テトラメトキシシラン、テトラエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、プロピルトリメトキシシラン、プロピルトリエトキシシラン、ブチルトリメトキシシラン、ブチルトリエトキシシラン、ペンチルトリメトキシシラン、ペンチルトリエトキシシラン、ヘプチルトリメトキシシラン、ヘプチルトリエトキシシラン、オクチルトリメトキシシラン、オクチルトリエトキシシラン、ドデシルトリメトキシシラン、ドデシルトリエトキシシラン、ヘキサデシルトリメトキシシラン、ヘキサデシルトリエトキシシラン、オクタデシルトリメトキシシラン、オクタデシルトリエトキシシランなどのアルキルトリアルコキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、ベンジルトリメトキシシラン及びベンジルトリエトキシシランなどの芳香族基を有するトリアルコキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシランなどのジアルコキシシラン、シクロヘキシルトリエトキシシラン、シクロヘキシルトリメトキシシラン、アリルトリエトキシシラン、アリルトリメトキシシラン、ジエトキシメチルビニルシラン、ジメトキシメチルビニルシラン、トリエトキシビニルシラン、ビニルトリメトキシシラン、ビニルトリス（２－メトキシエトキシ）シラン、ｍ－スチリルエチルトリエトキシシラン、ｐ－スチリルエチルトリエトキシシラン、ｍ－スチリルメチルトリエトキシシラン、ｐ－スチリルメチルトリエトキシシラン、３－（Ｎ－スチリルメチル－２－アミノエチルアミノ）プロピルトリメトキシシラン、３－（２－アミノエチルアミノ）プロピルジメトキシメチルシラン、３－（２－アミノエチルアミノ）プロピルトリエトキシシラン、３－（２－アミノエチルアミノ）プロピルトリメトキシシラン、３－アミノプロピルジエトキシメチルシラン、３－アミノプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、トリメトキシ［３－（フェニルアミノ）プロピル］シラン、３－メルカプトプロピル（ジメトキシ）メチルシラン、（３－メルカプトプロピル）トリエトキシシラン、（３－メルカプトプロピル）トリメトキシシラン、３－（トリエトキシシリル）プロピルイソシアネート、３－（トリエトキシシリル）プロピルメタクリレート、３－（トリメトキシシリル）プロピルメタクリレート、３－（トリエトキシシリル）プロピルアクリレート、３－（トリメトキシシリル）プロピルアクリレート、２－（トリエトキシシリル）エチルメタクリレート、２－（トリメトキシシリル）エチルメタクリレート、２－（トリエトキシシリル）エチルアクリレート、２－（トリメトキシシリル）エチルアクリレート、（トリエトキシシリル）メチルメタクリレート、（トリメトキシシリル）メチルメタクリレート、（トリエトキシシリル）メチルアクリレート、（トリメトキシシリル）メチルアクリレート、γ－ウレイドプロピルトリエトキシシラン、γ－ウレイドプロピルトリメトキシシラン、γ－ウレイドプロピルトリプロポキシシラン、（Ｒ）－Ｎ－１－フェニルエチル－Ｎ’－トリエトキシシリルプロピルウレア、（Ｒ）－Ｎ－１－フェニルエチル－Ｎ’－トリメトキシシリルプロピルウレア、１－［３－（トリメトキシシリル）プロピル］ウレアなどが挙げられる。 R 8 in the formula (4) is a hydrocarbon group having 1 to 5 carbon atoms. when p is 1 or 2, but is generally preferred if R 8 are the same, in the present invention, R 8 may be the same or different. Specific examples of alkoxysilane in the case where p is an integer of 1 to 3 in formula (4) are shown below.
For example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, Pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxy Alkyltrialkoxysilanes such as silane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimeth Trialkoxysilanes having aromatic groups such as silane, phenyltriethoxysilane, benzyltrimethoxysilane and benzyltriethoxysilane, dialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane, cyclohexyltriethoxysilane, cyclohexyltrimethoxysilane , Allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, m-styrylethyltriethoxysilane, p-styrylethyl Triethoxysilane, m-styrylmethyltriethoxysilane, p-styrylmethyltriethoxysilane, 3- (N-styrylmethyl) -2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propyldimethoxymethylsilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3- (2-aminoethylamino) propyl Trimethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, trimethoxy [3- (phenylamino) propyl] silane, 3-mercaptopropyl (dimethoxy) methylsilane, (3-mercaptopropyl) triethoxysilane, (3-mercaptopropyl) trimethoxysilane, 3- (triethoxysilyl) propyl isocyanate, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilane) Ryl) propyl methacrylate, 3- (triethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl acrylate, 2- (triethoxysilyl) ethyl methacrylate, 2- (trimethoxysilyl) ethyl methacrylate, 2- (triethoxy (Silyl) ethyl acrylate, 2- (trimethoxysilyl) ethyl acrylate, (triethoxysilyl) methyl methacrylate, (trimethoxysilyl) methyl methacrylate, (triethoxysilyl) methyl acrylate, (trimethoxysilyl) methyl acrylate, γ-ureido Propyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (R) -N-1-phenylethyl-N′-triethoxysilylpropi And lurea, (R) —N-1-phenylethyl-N′-trimethoxysilylpropylurea, 1- [3- (trimethoxysilyl) propyl] urea and the like.
本発明で用いるポリシロキサン（Ａ）は、式（２）で表されるアルコキシシランを全アルコキシシラン中の好ましくは５～５０モル％含み、式（３）で表されるアルコキシシランを前アルコキシシラン中の好ましくは１０～９５モル％含み、残余は上記式（４）で表されるアルコキシシランを重縮合して得られる。 The polysiloxane (A) used in the present invention preferably contains 5 to 50 mol% of the alkoxysilane represented by the formula (2) in the total alkoxysilane, and the alkoxysilane represented by the formula (3) The content is preferably 10 to 95 mol%, and the remainder is obtained by polycondensation of the alkoxysilane represented by the above formula (4).
被膜の撥液性及び溶剤耐性を考慮すると、式（２）で表されるアルコキシシランの含有量は、１０～４０モル％がより好ましい。式（３）で表されるアルコキシシランの量は、全アルコキシシラン中の３０～８０モル％が好ましい。 Considering the liquid repellency and solvent resistance of the coating, the content of the alkoxysilane represented by the formula (2) is more preferably 10 to 40 mol%. The amount of the alkoxysilane represented by the formula (3) is preferably 30 to 80 mol% in the total alkoxysilane.
また、上記式（４）で表されるアルコキシシランを含有する場合、その量は、全アルコキシシラン中の５～６０モル％が好ましい。 Further, when the alkoxysilane represented by the above formula (4) is contained, the amount thereof is preferably 5 to 60 mol% in the total alkoxysilane.
ポリシロキサン（Ａ）を得る方法として、例えば、式（２）で表されるアルコキシシランと、式（３）で表されるアルコキシシランと、必要に応じて上記式（４）で表されるアルコキシシランと、有機溶媒とを水酸化テトラエチルアンモニウム水溶液の存在下に加熱して重縮合する方法が挙げられる。具体的には、予め、有機溶媒に水酸化テトラエチルアンモニウム水溶液を加えて水酸化テトラエチルアンモニウム水溶液の溶液とした後、該溶液を加熱した状態で、上記の各種のアルコキシシランを混合する方法である。
上記水酸化テトラエチルアンモニウム水溶液の存在量は、使用するアルコキシシランが有する全アルコキシ基量の１モルに対し、好ましくは０．０１～０．２モルとされる。上記加熱は、液温が好ましくは０～１００℃で行うことができ、また、液の蒸発、揮散などが起こらないように、好ましくは、還流管を備え付けた容器中の還流下で数十分～十数時間行われる。 As a method for obtaining the polysiloxane (A), for example, an alkoxysilane represented by the formula (2), an alkoxysilane represented by the formula (3), and an alkoxy represented by the formula (4) as necessary. Examples thereof include a method in which silane and an organic solvent are heated and polycondensed in the presence of an aqueous tetraethylammonium hydroxide solution. More specifically, after adding a tetraethylammonium hydroxide aqueous solution to an organic solvent in advance to obtain a solution of the tetraethylammonium hydroxide aqueous solution, the above-mentioned various alkoxysilanes are mixed while the solution is heated.
The amount of the tetraethylammonium hydroxide aqueous solution is preferably 0.01 to 0.2 mol with respect to 1 mol of the total alkoxy group amount of the alkoxysilane used. The heating can be performed at a liquid temperature of preferably 0 to 100 ° C., and preferably several tens of minutes under reflux in a container equipped with a reflux tube so that the liquid does not evaporate or volatilize. It is done for more than 10 hours.
アルコキシシランを複数種用いる場合は、アルコキシシランを予め混合した混合物として混合してもよいし、複数種のアルコキシシランを順次混合してもよい。
アルコキシシランを重縮合する際には、仕込んだアルコキシシランの全ケイ素原子を酸化物に換算した濃度（以下、ＳｉＯ２換算濃度と称す。）が、４０質量％以下、特に好ましくは１０～３０質量％の範囲で加熱されることが好ましい。このような濃度範囲で任意の濃度を選択することにより、ゲルの生成を抑え、均質なポリシロキサン含有溶液を得ることができる。 When using multiple types of alkoxysilane, you may mix as a mixture which mixed alkoxysilane previously, and may mix multiple types of alkoxysilane sequentially.
In the polycondensation of alkoxysilane, the concentration of all the silicon atoms in the charged alkoxysilane converted to oxide (hereinafter referred to as SiO 2 conversion concentration) is 40% by mass or less, particularly preferably 10 to 30% by mass. % Heating is preferable. By selecting an arbitrary concentration within such a concentration range, gel formation can be suppressed and a homogeneous polysiloxane-containing solution can be obtained.
アルコキシシランを重縮合する際に用いられる有機溶媒（以下、重合溶媒とも言う。）は、式（２）で表されるアルコキシシランと、式（３）で表されるアルコキシシランと、必要に応じて上記式（４）で表されるアルコキシシランを溶解するものであれば特に限定されないが、溶剤（Ｃ）の使用が好ましい。なかでも、アルコキシシランの重縮合反応によりアルコールが生成するため、アルコール類やアルコール類と相溶性の良好な有機溶媒が用いられる。 An organic solvent (hereinafter also referred to as a polymerization solvent) used for polycondensation of the alkoxysilane is an alkoxysilane represented by the formula (2), an alkoxysilane represented by the formula (3), and as necessary. Although it will not specifically limit if the alkoxysilane represented by the said Formula (4) is melt | dissolved, Use of a solvent (C) is preferable. Especially, since alcohol produces | generates by the polycondensation reaction of alkoxysilane, the organic solvent favorable with alcohol and alcohol compatibility is used.
上記の重合溶媒の具体例としては、メタノール、エタノール、プロパノール、ｎ－ブタノールなどのアルコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルなどのグリコールエーテル、テトラヒドロフランなどのエーテルなどが挙げられる。
本発明においては、上記の有機溶媒を複数種混合して用いてもよい。 Specific examples of the polymerization solvent include alcohols such as methanol, ethanol, propanol and n-butanol, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether, and tetrahydrofuran. Examples include ether.
In the present invention, a plurality of the above organic solvents may be mixed and used.
　本発明においては、前記方法で得られた特定ポリシロキサンの溶液をそのまま本発明の感光性樹脂組成物に用いても良いし、必要に応じて、前記方法で得られた特定ポリシロキサンの溶液を濃縮したり、溶媒を加えて希釈したり、他の溶媒に置換して用いることもできる。 In the present invention, the solution of the specific polysiloxane obtained by the above method may be used as it is for the photosensitive resin composition of the present invention, and if necessary, the solution of the specific polysiloxane obtained by the above method may be used. It can be concentrated, diluted by adding a solvent, or substituted with another solvent.
　前記溶媒を加えて希釈する際に用いる溶媒（添加溶媒ともいう）は、重縮合反応に用いる溶媒やその他の溶媒であってもよい。この添加溶媒は、特定ポリシロキサンが均一に溶解している限りにおいては特に限定されず、１種類または２種類以上を任意に選択して使用することができる。このような添加溶媒としては、前記重縮合反応に用いる溶媒に加え、アセトン、メチルエチルケトンまたはメチルイソブチルケトンなどのケトン系溶媒、酢酸メチル、酢酸エチルまたは乳酸エチルなどのエステル系溶媒などが挙げられる。 The solvent used for dilution by adding the solvent (also referred to as an added solvent) may be a solvent used for a polycondensation reaction or other solvents. The additive solvent is not particularly limited as long as the specific polysiloxane is uniformly dissolved, and one or more kinds can be arbitrarily selected and used. Examples of the additive solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester solvents such as methyl acetate, ethyl acetate, and ethyl lactate, in addition to the solvent used in the polycondensation reaction.
　さらに、本発明において、感光性樹脂組成物中に、特定ポリシロキサン以外の重合体を用いる場合、特定ポリシロキサン以外の重合体を混合する前に、特定ポリシロキサンの重縮合反応の際に発生するアルコールを常圧または減圧で留去しておくことが好ましい。 Further, in the present invention, when a polymer other than the specific polysiloxane is used in the photosensitive resin composition, it occurs during the polycondensation reaction of the specific polysiloxane before mixing the polymer other than the specific polysiloxane. The alcohol is preferably distilled off at normal pressure or reduced pressure.
＜（Ｂ）成分＞
　本発明の（Ｂ）成分は、アルカリ可溶性基を有する樹脂である。アルカリ可溶性基としては、例えば、フェノール性ヒドロキシ基、カルボキシル基、酸無水物基、イミド基、スルホニル基、リン酸、ボロン酸及び活性メチレン基および活性メチン基が挙げられる。 <(B) component>
The component (B) of the present invention is a resin having an alkali-soluble group. Examples of the alkali-soluble group include a phenolic hydroxy group, a carboxyl group, an acid anhydride group, an imide group, a sulfonyl group, phosphoric acid, a boronic acid, an active methylene group, and an active methine group.
活性メチレン基とはメチレン基（－ＣＨ２－）のうち、隣接位置にカルボニル基を持ち、求核試薬に対する反応性を持つものを言う。また、本発明において前記活性メチン基とは前記活性メチレン基においてメチレン基の１個の水素原子がアルキル基で置換された構造を有し、求核試薬に対する反応性を持つものを言う。 The active methylene group refers to a methylene group (—CH 2 —) having a carbonyl group at an adjacent position and having reactivity with a nucleophile. In the present invention, the active methine group has a structure in which one hydrogen atom of the methylene group is substituted with an alkyl group in the active methylene group and has reactivity with a nucleophile.
活性メチレン基および活性メチン基としては下記式（b１）で表される基がより好ましい。
Figure JPOXMLDOC01-appb-C000006
 （式（ｂ１）中、Ｒはアルキル基、アルコキシ基又はフェニル基を表し、破線は結合手を表す。） As the active methylene group and the active methine group, a group represented by the following formula (b1) is more preferable.
Figure JPOXMLDOC01-appb-C000006
 (In the formula (b1), R represents an alkyl group, an alkoxy group or a phenyl group, and a broken line represents a bond.)
　上記式（ｂ１）において、Ｒが表すアルキル基としては、例えば、炭素原子数１乃至２０のアルキル基が挙げられ、炭素原子数１乃至５のアルキル基が好ましい。
　そのようなアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基等が挙げられる。
　その中でも、メチル基、エチル基、ｎ－プロピル基等が好ましい。 In the above formula (b1), examples of the alkyl group represented by R include an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 5 carbon atoms is preferable.
Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group.
Of these, a methyl group, an ethyl group, an n-propyl group, and the like are preferable.
　上記式（ｂ１）において、Ｒが表すアルコキシ基としては、例えば、炭素原子数１乃至２０のアルコキシ基が挙げられ、炭素原子数１乃至５のアルコキシ基が好ましい。
　そのようなアルコキシ基としては、例えば、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉ－プロポキシ基、ｎ－ブトキシ基、ｉ－ブトキシ基、ｓ－ブトキシ基、ｔ－ブトキシ基等が挙げられる。
　その中でも、メトキシ基、エトキシ基及びｎ－プロポキシ基等が好ましい。 In the above formula (b1), examples of the alkoxy group represented by R include an alkoxy group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms is preferable.
Examples of such an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, and a t-butoxy group.
Of these, a methoxy group, an ethoxy group, an n-propoxy group, and the like are preferable.
　上記式（ｂ１）で表される基としては、例えば、以下の構造等が挙げられる。なお、構造式中、破線は結合手を表す。
Figure JPOXMLDOC01-appb-C000007
 Examples of the group represented by the above formula (b1) include the following structures. In the structural formula, the broken line represents a bond.
Figure JPOXMLDOC01-appb-C000007
　上記アルカリ可溶性基の中でも、フェノール性ヒドロキシ基及びカルボキシル基からなる群から選択される少なくとも１種の有機基を有し、且つ、数平均分子量が２，０００乃至５０，０００であるアルカリ可溶性樹脂であることが好ましい。 Among the alkali-soluble groups, an alkali-soluble resin having at least one organic group selected from the group consisting of a phenolic hydroxy group and a carboxyl group, and having a number average molecular weight of 2,000 to 50,000 Preferably there is.
　上記（Ｂ）成分のアルカリ可溶性樹脂は、斯かる構造を有するアルカリ可溶性樹脂であればよく、樹脂を構成する高分子の主鎖の骨格及び側鎖の種類などについて特に限定されない。 The alkali-soluble resin as the component (B) may be any alkali-soluble resin having such a structure, and is not particularly limited with respect to the main chain skeleton and side chain type of the polymer constituting the resin.
　然しながら、（Ｂ）成分のアルカリ可溶性樹脂は、数平均分子量が２，０００乃至５０，０００の範囲内にあるものである。数平均分子量が５０，０００を超えて過大なものであると、現像残渣が発生し易くなり、感度が大きく低下する一方、数平均分子量が２，０００未満で過小なものであると、現像の際、露光部の膜減りが相当量発生し、硬化不足になる場合がある。 However, the alkali-soluble resin (B) has a number average molecular weight in the range of 2,000 to 50,000. If the number average molecular weight exceeds 50,000, the development residue is likely to be generated, and the sensitivity is greatly reduced. On the other hand, if the number average molecular weight is less than 2,000, the development is insufficient. At this time, there is a case where a considerable amount of film loss occurs in the exposed portion, resulting in insufficient curing.
　（Ｂ）成分のアルカリ可溶性樹脂としては、例えばアクリル系樹脂、ポリヒドロキシスチレン系樹脂、あるいはポリイミド前駆体又はポリイミド等が挙げることができる。 Examples of the alkali-soluble resin (B) include acrylic resins, polyhydroxystyrene resins, polyimide precursors, and polyimides.
　また、本発明においては、複数種のモノマーを重合して得られる共重合体（以下、特定共重合体と称す。）からなるアルカリ可溶性樹脂を（Ｂ）成分として用いることもできる。この場合、（Ｂ）成分のアルカリ可溶性樹脂は、複数種の特定共重合体のブレンド物であってもよい。 In the present invention, an alkali-soluble resin composed of a copolymer obtained by polymerizing plural kinds of monomers (hereinafter referred to as a specific copolymer) can also be used as the component (B). In this case, the alkali-soluble resin as the component (B) may be a blend of a plurality of types of specific copolymers.
　すなわち、上記の特定共重合体は、アルカリ可溶性を発現するモノマー、即ちカルボキシル基及びフェノール性ヒドロキシ基からなる群から選択される少なくとも一種を有するモノマーと、これらモノマーと共重合可能なモノマーの群から選択される少なくとも一種のモノマーとを、必須の構成単位として形成された共重合体であって、その数平均分子量が２，０００乃至５０，０００のものである。数平均分子量が５０，０００より過大であると、残渣が生じる場合がある。 That is, the specific copolymer is a monomer that exhibits alkali solubility, that is, a monomer having at least one selected from the group consisting of a carboxyl group and a phenolic hydroxy group, and a group of monomers copolymerizable with these monomers. It is a copolymer formed with at least one selected monomer as an essential constituent unit, and has a number average molecular weight of 2,000 to 50,000. If the number average molecular weight is more than 50,000, a residue may be generated.
　上記の「カルボキシル基及びフェノール性ヒドロキシ基からなる群から選択される少なくとも一種を有するモノマー」は、カルボキシル基を有するモノマー及びフェノール性ヒドロキシ基を有するモノマーが含まれる。これらのモノマーはカルボキシル基、又はフェノール性ヒドロキシ基を一個有するものに限らず、複数個有するものでもよい。 The above “monomer having at least one selected from the group consisting of a carboxyl group and a phenolic hydroxy group” includes a monomer having a carboxyl group and a monomer having a phenolic hydroxy group. These monomers are not limited to those having one carboxyl group or one phenolic hydroxy group, and may have a plurality of monomers.
　以下、上記モノマーの具体例を挙げるが、これらに限定されるものでない。
　カルボキシル基を有するモノマーとしては、例えば、アクリル酸、メタクリル酸、クロトン酸、モノ－（２－（アクリロイルオキシ）エチル）フタレート、モノ－（２－（メタクリロイルオキシ）エチル）フタレート、Ｎ－（カルボキシフェニル）マレイミド、Ｎ－（カルボキシフェニル）メタクリルアミド、Ｎ－（カルボキシフェニル）アクリルアミド等が挙げられる。 Hereinafter, although the specific example of the said monomer is given, it is not limited to these.
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, and N- (carboxyphenyl). ) Maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.
　フェノール性ヒドロキシ基を有するモノマーとしては、例えば、ヒドロキシスチレン、Ｎ－（ヒドロキシフェニル）アクリルアミド、Ｎ－（ヒドロキシフェニル）メタクリルアミド、Ｎ－（ヒドロキシフェニル）マレイミド、４－ヒドロキシフェニルメタクリレート
等が挙げられる。 Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide, 4-hydroxyphenyl methacrylate and the like.
　イミド基を有するモノマーとしては、例えば、マレイミド等が挙げられる。 Examples of the monomer having an imide group include maleimide.
　（Ｂ）成分のアルカリ可溶性アクリル重合体の製造における不飽和カルボン酸誘導体及び／またはフェノール性水酸基と重合性不飽和基を有するモノマーの比率は、（Ｂ）成分のアルカリ可溶性アクリル重合体の製造に用いる全てのモノマーのうち、好ましくは１０～９０モル％、より好ましくは５～６０モル％、最も好ましくは５～３０モル％である。不飽和カルボン酸及び／またはフェノール性ヒドロキシ基誘導体が１０重量％未満の場合には、重合体のアルカリ溶解性が不足する。 The ratio of the unsaturated carboxylic acid derivative and / or the monomer having a phenolic hydroxyl group and a polymerizable unsaturated group in the production of the (B) component alkali-soluble acrylic polymer is the same as that in the production of the (B) component alkali-soluble acrylic polymer. Among all the monomers used, it is preferably 10 to 90 mol%, more preferably 5 to 60 mol%, and most preferably 5 to 30 mol%. When the unsaturated carboxylic acid and / or phenolic hydroxy group derivative is less than 10% by weight, the alkali solubility of the polymer is insufficient.
　本発明の（Ｂ）成分であるアルカリ可溶性樹脂は、硬化後のパターン形状をより安定化させるという点から、さらにヒドロキシアルキル基と重合性不飽和基とを有するモノマーを共重合させてもよい。 The alkali-soluble resin which is the component (B) of the present invention may be further copolymerized with a monomer having a hydroxyalkyl group and a polymerizable unsaturated group from the viewpoint of further stabilizing the pattern shape after curing.
　ヒドロキシアルキル基と重合性不飽和基とを有するモノマーとしては、例えば、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレート、４－ヒドロキシブチルアクリレート、２，３－ジヒドロキシプロピルアクリレート、２－ヒドロキシエチルメタクリレート、２－ヒドロキシプロピルメタクリレート、４－ヒドロキシブチルメタクリレート、２，３－ジヒドロキシプロピルメタクリレート、グリセリンモノメタクリレート、５－アクリロイルオキシ－６－ヒドロキシノルボルネン－２－カルボキシリック－６－ラクトン等が挙げられる。 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, Examples thereof include 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerol monomethacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxyl-6-lactone and the like.
　（Ｂ）成分のアルカリ可溶性アクリル重合体の製造におけるヒドロキシアルキル基と重合性不飽和基とを有するモノマーの比率は、好ましくは１０～６０重量％、より好ましくは１５～５０重量％、最も好ましいのは２０～４０重量％である。ヒドロキシアルキル基と重合性不飽和基とを有するモノマーが１０重量％未満の場合は共重合体のパターン形状の安定化効果が得られない場合がある。６０重量％以上の場合には、（Ｂ）成分のアルカリ可溶性基が不足し、現像性等の特性が低下する場合がある。 The ratio of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group in the production of the alkali-soluble acrylic polymer as component (B) is preferably 10 to 60% by weight, more preferably 15 to 50% by weight, and most preferably Is 20 to 40% by weight. When the monomer having a hydroxyalkyl group and a polymerizable unsaturated group is less than 10% by weight, the effect of stabilizing the pattern shape of the copolymer may not be obtained. When the amount is 60% by weight or more, the alkali-soluble group of the component (B) may be insufficient, and characteristics such as developability may be deteriorated.
　本発明の（Ｂ）成分であるアルカリ可溶性樹脂は、共重合体のＴｇを上げるという点から、さらにＮ置換マレイミド化合物を共重合させてもよい。 The alkali-soluble resin which is the component (B) of the present invention may be further copolymerized with an N-substituted maleimide compound from the viewpoint of increasing the Tg of the copolymer.
　Ｎ置換マレイミド化合物マレイミド化合物としては、例えば、Ｎ－メチルマレイミド、Ｎ－エチルマレイミド、Ｎ－フェニルマレイミド、及びＮ－シクロヘキシルマレイミド等が挙げられる。透明性の観点から芳香環を有さない物が好ましく、現像性、透明性、耐熱性の点から脂環骨格を有するものがより好ましく、中でもシクロヘキシルマレイミドが最も好ましい。 Examples of the N-substituted maleimide compound maleimide compound include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. The thing which does not have an aromatic ring from a transparency viewpoint is preferable, and what has an alicyclic skeleton from the point of developability, transparency, and heat resistance is more preferable, and a cyclohexyl maleimide is the most preferable especially.
　（Ｂ）成分のアルカリ可溶性アクリル重合体の製造におけるＮ－置換マレイミドの比率は、好ましくは１０～６０重量％、より好ましくは１５～５０重量％、最も好ましいのは２０～４０重量％である。Ｎ－置換マレイミドが１０重量％未満の場合は共重合体のＴｇが低くなり、耐熱性に劣る場合がある。６０重量％以上の場合には、透明性が低下する場合がある。 The ratio of N-substituted maleimide in the production of the alkali-soluble acrylic polymer of component (B) is preferably 10 to 60% by weight, more preferably 15 to 50% by weight, and most preferably 20 to 40% by weight. When the N-substituted maleimide is less than 10% by weight, the Tg of the copolymer is lowered and the heat resistance may be inferior. If it is 60% by weight or more, the transparency may be lowered.
　本発明の感光性樹脂組成物が要件（Ｚ２）を満足する場合、本発明で用いられるアルカリ可溶性樹脂（Ｂ）は、自己架橋性基をさらに有するか、又はヒドロキシ基、カルボキシル基、アミド基及びアミノ基からなる群から選ばれる少なくとも１つの基と反応する基（以下、架橋性基ともいう）をさらに有する共重合体であることが好ましい。 When the photosensitive resin composition of the present invention satisfies the requirement (Z2), the alkali-soluble resin (B) used in the present invention further has a self-crosslinkable group, or a hydroxy group, a carboxyl group, an amide group, and A copolymer further having a group that reacts with at least one group selected from the group consisting of amino groups (hereinafter also referred to as a crosslinkable group) is preferable.
　上記自己架橋性基としてはＮ-アルコキシメチル基、Ｎ-ヒドロキシメチル基、アルコキシシリル基、エポキシ基、オキセタン基、ビニル基及びブロックイソシアネート基が挙げられる。 Examples of the self-crosslinking group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, and a blocked isocyanate group.
　上記架橋性基としては、Ｎ-アルコキシメチル基、Ｎ-ヒドロキシメチル基、アルコキシシリル基、エポキシ基、ビニル基、ブロックイソシアネート基等が挙げられる。 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.
　かかる自己架橋性基又は架橋性基を（Ｂ）成分の樹脂に含有させる場合の含有量は、（Ｂ）成分の樹脂における繰り返し単位１単位あたり、０．１乃至０．９個であることが好ましく、現像性と耐溶剤性の観点から、０．１乃至０．８個であることがさらに好ましい。 When the self-crosslinking group or the crosslinkable group is contained in the resin of the component (B), the content is 0.1 to 0.9 per repeating unit in the resin of the component (B). Preferably, from the viewpoint of developability and solvent resistance, 0.1 to 0.8 is more preferable.
　（Ｂ）成分のアルカリ可溶性樹脂が、さらにＮ-アルコキシメチル基、Ｎ-ヒドロキシメチル基、アルコキシシリル基、エポキシ基、オキセタン基、ビニル基及びブロックイソシアネート基等の架橋性基及びＮ-アルコキシメチル基、Ｎ-ヒドロキシメチル基、アルコキシシリル基、エポキシ基、ビニル基、ブロックイソシアネート基等の自己架橋性基から選ばれる少なくとも1種を有する繰り返し単位を有する場合、例えば、ラジカル重合性を有し、エポキシ基、オキセタン基、ビニル基、ブロックイソシアネート基等の架橋性基及びＮ－アルコキシメチル基、Ｎ－ヒドロキシメチル基及びアルコキシシリル基等の自己架橋性基から選ばれる少なくとも1種を有する不飽和化合物を共重合させればよい。 The alkali-soluble resin of component (B) is further composed of an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, a blocked isocyanate group, and an N-alkoxymethyl group. , N-hydroxymethyl group, alkoxysilyl group, epoxy group, vinyl group, having a repeating unit having at least one selected from a self-crosslinkable group such as a blocked isocyanate group, An unsaturated compound having at least one selected from a crosslinkable group such as a group, an oxetane group, a vinyl group, and a blocked isocyanate group, and a self-crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group, and an alkoxysilyl group. What is necessary is just to copolymerize.
　ラジカル重合性を有し、Ｎ－アルコキシメチル基を有する不飽和化合物としては、Ｎ－ブトキシメチルアクリルアミド、Ｎ－イソブトキシメチルアクリルアミド、Ｎ－メトキシメチルアクリルアミド、Ｎ－メトキシメチルメタクリルアミド、Ｎ－メチロールアクリルアミド等が挙げられる。 Examples of unsaturated compounds having radical polymerizability and having an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-methylolacrylamide. Etc.
　ラジカル重合性を有し、さらにヒドロキシメチルアミド基を有するモノマーとしては、Ｎ－ヒドロキシメチルアクリルアミド、Ｎ－ヒドロキシメチルメタクリルアミド等が挙げられる。 Examples of the monomer having radical polymerizability and further having a hydroxymethylamide group include N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide.
　ラジカル重合性を有し、さらにアルコキシシリル基を有するモノマーとしては、３－アクリロイルオキシトリメトキシシラン、３－アクリロイルオキシトリエトキシシラン、３－メタクリロイルオキシトリメトキシシラン、３－メタクリロイルオキシトリエトキシシラン等が挙げられる。 Examples of the monomer having radical polymerizability and having an alkoxysilyl group include 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane. Can be mentioned.
　ラジカル重合性を有し、さらにエポキシ基を有する不飽和化合物としては、例えばアクリル酸グリシジル、メタクリル酸グリシジル、α－エチルアクリル酸グリシジル、α－ｎ－プロピルアクリル酸グリシジル、α－ｎ－ブチルアクリル酸グリシジル、アクリル酸－３，４－エポキシブチル、メタクリル酸－３，４－エポキシブチル、アクリル酸－６，７－エポキシヘプチル、メタクリル酸－６，７－エポキシヘプチル、α－エチルアクリル酸－６，７－エポキシヘプチル、ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテルなどが挙げられる。これらのうち、メタクリル酸グリシジル、メタクリル酸－６，７－エポキシヘプチル、ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル、３，４－エポキシシクロへキシルメタクリレートなどが好ましく用いられる。これらは、単独であるいは組み合わせて用いられる。 Examples of unsaturated compounds having radical polymerizability and further having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n-butyl acrylic acid. Glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6 Examples thereof include 7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like. Among these, glycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, etc. Preferably used. These may be used alone or in combination.
　ラジカル重合性を有し、さらにオキセタン基を有する不飽和化合物としては、例えば、オキセタン基を有する（メタ）アクリル酸エステルなどを挙げることができる。このようなモノマーの中では、３－（メタクリロイルオキシメチル）オキセタン、３－（アクリロイルオキシメチル）オキセタン、３－（メタクリロイルオキシメチル）－３－エチル－オキセタン、３－（アクリロイルオキシメチル）－３－エチル－オキセタン、３－（メタクリロイルオキシメチル）－２－トリフロロメチルオキセタン、３－（アクリロイルオキシメチル）－２－トリフロロメチルオキセタン、３－（メタクリロイルオキシメチル）－２－フェニル－オキセタン、３－（アクリロイルオキシメチル）－２－フェニル－オキセタン、２－（メタクリロイルオキシメチル）オキセタン、２－（アクリロイルオキシメチル）オキセタン、２－（メタクリロイルオキシメチル）－４－トリフロロメチルオキセタン、２－（アクリロイルオキシメチル）－４－トリフロロメチルオキセタンが好ましく、３－（メタクリロイルオキシメチル）－３－エチル－オキセタン、３－（アクリロイルオキシメチル）－３－エチル－オキセタン等が好ましく用いられる。 Examples of the unsaturated compound having radical polymerizability and further having an oxetane group include (meth) acrylic acid ester having an oxetane group. Among such monomers, 3- (methacryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl) -3- Ethyl-oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyl-oxetane, 3- (Acryloyloxymethyl) -2-phenyl-oxetane, 2- (methacryloyloxymethyl) oxetane, 2- (acryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, 2- (acryloyl) Oxymethyl) -4-trifluoromethyl oxetane are preferable, 3- (methacryloyloxy) -3-ethyl - oxetane, 3- (acryloyloxy-methyl) -3-ethyl - oxetane and the like are preferably used.
　ラジカル重合性を有し、さらにビニル基を有するモノマーとしては、アクリル酸２－（２－ビニロキシエトキシ）エチル、メタクリル酸２－（２－ビニロキシエトキシ）エチル等が挙げられる。 Examples of the monomer having radical polymerizability and further having a vinyl group include 2- (2-vinyloxyethoxy) ethyl acrylate and 2- (2-vinyloxyethoxy) ethyl methacrylate.
　ラジカル重合性を有し、さらにブロックイソシアネート基を有するモノマーとしては、メタクリル酸２－（０－（１’－メチルプロピリデンアミノ）カルボキシアミノ）エチル、メタクリル酸２－（３，５－ジメチルピラゾリル）カルボニルアミノ）エチル等が挙げられる。 As monomers having radical polymerizability and further having blocked isocyanate groups, 2- (0- (1′-methylpropylideneamino) carboxyamino) ethyl methacrylate, 2- (3,5-dimethylpyrazolyl) methacrylate Carbonylamino) ethyl and the like.
　本発明の感光性樹脂組成物が（Ｚ１）を満足する場合、ラジカル重合性を有し、Ｎ-アルコキシメチル基、Ｎ-ヒドロキシメチル基、アルコキシシリル基、エポキシ基、オキセタン基、ビニル基及びブロックイソシアネート基等の架橋性基及びＮ-アルコキシメチル基、Ｎ-ヒドロキシメチル基、アルコキシシリル基、エポキシ基、ビニル基、ブロックイソシアネート基等の自己架橋性基から選ばれる少なくとも1種の基を有する不飽和化合物から誘導される構成単位を、アルカリ可溶性樹脂（Ｂ）が有する全ての繰り返し単位の合計に基づいて、好ましくは１０～７０重量％、特に好ましくは２０～６０重量％含有する。この構成単位が１０重量％未満の場合は得られる硬化膜の耐熱性や表面硬度が低下する傾向にあり、一方この構成単位の量が７０重量％を超える場合は感放射線性樹脂組成物の保存安定性が低下する傾向にある。 When the photosensitive resin composition of the present invention satisfies (Z1), it has radical polymerizability and has an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, and a block. A non-crosslinking group such as an isocyanate group and at least one group selected from a self-crosslinking 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; The constituent unit derived from the saturated compound is preferably contained in an amount of 10 to 70% by weight, particularly preferably 20 to 60% by weight, based on the total of all repeating units of the alkali-soluble resin (B). When this structural unit is less than 10% by weight, the heat resistance and surface hardness of the resulting cured film tend to decrease, while when the amount of this structural unit exceeds 70% by weight, the radiation-sensitive resin composition is stored. The stability tends to decrease.
　また、本発明においては、（Ｂ）成分のアクリル重合体は、上述のモノマー以外のモノマー（以下、その他モノマーと称す。）をも構成単位として形成された共重合体であってもよい。その他モノマーは、具体的には、上記カルボキシル基を有するモノマー及びフェノール性ヒドロキシ基を有するモノマーからなる群から選択される少なくとも一種と共重合可能なものであればよく、（Ｂ）成分の特性を損ねない限り、特に限定されるものでない。そのようなモノマーの具体例としては、アクリル酸エステル化合物、メタクリル酸エステル化合物、アクリルアミド化合物、アクリロニトリル、スチレン化合物及びビニル化合物等が挙げられる。
　以下、当該その他モノマーの具体例を挙げるが、これらに限定されるものではない。 In the present invention, the acrylic polymer of component (B) may be a copolymer formed with monomers other than the above-described monomers (hereinafter referred to as other monomers) as constituent units. Specifically, the other monomer may be any one that can be copolymerized with at least one selected from the group consisting of the above-mentioned monomer having a carboxyl group and a monomer having a phenolic hydroxy group. There is no particular limitation as long as it is not impaired. Specific examples of such monomers include acrylic ester compounds, methacrylic ester compounds, acrylamide compounds, acrylonitrile, styrene compounds and vinyl compounds.
Hereinafter, although the specific example of the said other monomer is given, it is not limited to these.
　前記アクリル酸エステル化合物としては、例えば、メチルアクリレート、エチルアクリレート、イソプロピルアクリレート、ベンジルアクリレート、ナフチルアクリレート、アントリルアクリレート、アントリルメチルアクリレート、フェニルアクリレート、グリシジルアクリレート、フェノキシエチルアクリレート、２，２，２－トリフルオロエチルアクリレート、ｔｅｒｔ－ブチルアクリレート、シクロヘキシルアクリレート、イソボルニルアクリレート、２－メトキシエチルアクリレート、メトキシトリエチレングリコールアクリレート、２－エトキシエチルアクリレート、２－アミノエチルアクリレート、テトラヒドロフルフリルアクリレート、３－メトキシブチルアクリレート、２－メチル－２－アダマンチルアクリレート、２－プロピル－２－アダマンチルアクリレート、８－メチル－８－トリシクロデシルアクリレート、及び、８－エチル－８－トリシクロデシルアクリレート、ジエチレングリコールモノアクリレート、カプロラクトン２－（アクリロイルオキシ）エチルエステル、ポリ（エチレングリコール）エチルエーテルアクリレート等が挙げられる。 Examples of the acrylic ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, phenoxyethyl acrylate, 2,2,2- Trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxy Butyl acrylate, 2-methyl-2-adamantyl acrylate, 2 Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate, diethylene glycol monoacrylate, caprolactone 2- (acryloyloxy) ethyl ester, poly (ethylene glycol) Examples include ethyl ether acrylate.
　前記メタクリル酸エステル化合物としては、例えば、メチルメタクリレート、エチルメタクリレート、イソプロピルメタクリレート、ベンジルメタクリレート、ナフチルメタクリレート、アントリルメタクリレート、アントリルメチルメタクリレート、フェニルメタクリレート、グリシジルメタクリレート、フェノキシエチルメタクリレート、２，２，２－トリフルオロエチルメタクリレート、ｔｅｒｔ－ブチルメタクリレート、シクロヘキシルメタクリレート、イソボルニルメタクリレート、２－メトキシエチルメタクリレート、メトキシトリエチレングリコールメタクリレート、２－エトキシエチルメタクリレート、２－アミノメチルメタクリレート、テトラヒドロフルフリルメタクリレート、３－メトキシブチルメタクリレート、２－メチル－２－アダマンチルメタクリレート、γ－ブチロラクトンメタクリレート、２－プロピル－２－アダマンチルメタクリレート、８－メチル－８－トリシクロデシルメタクリレート、及び、８－エチル－８－トリシクロデシルメタクリレート、ジエチレングリコールモノメタクリレート、カプロラクトン２－（メタクリロイルオキシ）エチルエステル、ポリ（エチレングリコール）エチルエーテルメタクリレート等が挙げられる。 Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2- Trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxy Butyl methacrylate, 2 Methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, diethylene glycol monomethacrylate, caprolactone Examples include 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether methacrylate, and the like.
　前記アクリルアミド化合物としては、例えば、Ｎ－メチルアクリルアミド、Ｎ－メチルメタクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジメチルメタクリルアミド、Ｎ－メトキシメチルアクリルアミド、Ｎ－メトキシメチルメタクリルアミド、Ｎ－ブトキシメチルアクリルアミド、Ｎ－ブトキシメチルメタクリルアミド等が挙げられる。 Examples of the acrylamide compound include N-methylacrylamide, N-methylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxy. Examples thereof include methyl acrylamide and N-butoxymethyl methacrylamide.
　前記ビニル化合物としては、例えば、メチルビニルエーテル、ベンジルビニルエーテル、シクロヘキシルビニルエーテル、ビニルナフタレン、ビニルアントラセン、ビニルカルバゾール、アリルグリシジルエーテル、３－エテニル－７－オキサビシクロ［４．１．０］ヘプタン、１，２－エポキシ－５－ヘキセン、及び、１，７－オクタジエンモノエポキサイド等が挙げられる。 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-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2 -Epoxy-5-hexene, 1,7-octadiene monoepoxide and the like.
　前記スチレン化合物としては、ヒドロキシ基を有しないスチレン、例えば、スチレン、α－メチルスチレン、クロロスチレン、ブロモスチレン等が挙げられる。 Examples of the styrene compound include styrene having no hydroxy group, such as styrene, α-methylstyrene, chlorostyrene, and bromostyrene.
　（Ｂ）成分であるアルカリ可溶性アクリル重合体の製造において、上記その他モノマーの比率は８０重量％以下であることが好ましく、より好ましくは５０重量％以下であり、さらに好ましくは２０重量％以下である。８０重量％よりも多くなると相対的に必須成分が減るため、本発明の効果を十分に得ることが困難になる。 In the production of the alkali-soluble acrylic polymer as component (B), the ratio of the other monomers is preferably 80% by weight or less, more preferably 50% by weight or less, and further preferably 20% by weight or less. . If the amount exceeds 80% by weight, the essential components are relatively reduced, so that it is difficult to sufficiently obtain the effects of the present invention.
　本発明に用いる（Ｂ）成分であるアルカリ可溶性アクリル重合体を得る方法は特に限定されないが、例えば、カルボキシル基、フェノール性ヒドロキシ基、及び、熱又は酸の作用によりカルボン酸又はフェノール性ヒドロキシ基を生成する基からなる群から選択される少なくとも一種を有するモノマー、ヒドロキシアルキル基を有するモノマー、所望によりＮ-アルコキシメチル基、Ｎ-ヒドロキシメチル基、アルコキシシリル基、エポキシ基、オキセタン基、ビニル基及びブロックイソシアネート基等の架橋性基及びＮ-アルコキシメチル基、Ｎ-ヒドロキシメチル基、アルコキシシリル基、エポキシ基、ビニル基、ブロックイソシアネート基等の自己架橋性基から選ばれる少なくとも１種の基を有するモノマー、所望によりそれ以外の共重合可能なモノマー及び所望により重合開始剤等を共存させた溶剤中において、５０乃至１１０℃の温度下で重合反応させることにより、得られる。その際、用いられる溶剤は、アルカリ可溶性アクリル重合体を構成するモノマー及び特定官能基を有するアクリル重合体を溶解するものであれば特に限定されない。具体例としては、後述する（Ｃ）溶剤に記載する溶剤が挙げられる。 The method for obtaining the alkali-soluble acrylic polymer (B) used in the present invention is not particularly limited. For example, a carboxyl group, a phenolic hydroxy group, and a carboxylic acid or a phenolic hydroxy group by the action of heat or acid. A monomer having at least one selected from the group consisting of a group to be formed, a monomer having a hydroxyalkyl group, optionally an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, and It has at least one group selected from cross-linkable groups such as blocked isocyanate groups and self-crosslinkable groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, and blocked isocyanate groups. Monomer, other copolymerization if desired It can be obtained by carrying out a polymerization reaction at a temperature of 50 to 110 ° C. in a solvent in which possible monomers and, if desired, a polymerization initiator coexist. In that case, the solvent used will not be specifically limited if it dissolves the monomer which comprises an alkali-soluble acrylic polymer, and the acrylic polymer which has a specific functional group. As a specific example, the solvent described in the (C) solvent mentioned later is mentioned.
　このようにして得られる特定官能基を有するアクリル重合体は、通常、溶剤に溶解した溶液の状態である。 The acrylic polymer having a specific functional group thus obtained is usually in a solution state dissolved in a solvent.
　また、上記のようにして得られた特定共重合体の溶液を、ジエチルエーテルや水等の撹拌下に投入して再沈殿させ、生成した沈殿物を濾過・洗浄した後、常圧又は減圧下で、常温あるいは加熱乾燥することで、特定共重合体の粉体とすることができる。このような操作により、特定共重合体と共存する重合開始剤や未反応モノマーを除去することができ、その結果、精製した特定共重合体の粉体を得られる。一度の操作で充分に精製できない場合は、得られた粉体を溶剤に再溶解して、上記の操作を繰り返し行えば良い。
　本発明においては、上記特定共重合体の粉体をそのまま用いても良く、あるいはその粉体を、たとえば後述する（Ｃ）溶剤に再溶解して溶液の状態として用いても良い。 In addition, the solution of the specific copolymer obtained as described above is re-precipitated by stirring with stirring such as diethyl ether or water, and the generated precipitate is filtered and washed, and then under normal pressure or reduced pressure. Thus, the powder of the specific copolymer can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
In the present invention, the powder of the specific copolymer may be used as it is, or the powder may be redissolved in a solvent (C) described later and used as a solution.
　また、（Ｂ）成分のアルカリ可溶性樹脂としては、ポリアミド酸、ポリアミド酸エステル、一部イミド化したポリアミド酸等のポリイミド前駆体、カルボン酸基含有ポリイミド等のポリイミドを用いることもでき、それらはアルカリ可溶性であれば特にその種類を限定されずに用いることができる。 In addition, as the alkali-soluble resin of component (B), polyimide precursors such as polyamic acid, polyamic acid ester, partially imidized polyamic acid, and polyimide such as carboxylic acid group-containing polyimide can be used. If it is soluble, the kind can be used without particular limitation.
　ポリイミド前駆体である前記ポリアミド酸は、一般的に（ａ）テトラカルボン酸二無水物化合物と（ｂ）ジアミン化合物とを重縮合して得ることができる。 The polyamic acid, which is a polyimide precursor, can generally be obtained by polycondensation of (a) a tetracarboxylic dianhydride compound and (b) a diamine compound.
　上記（ａ）テトラカルボン酸二無水物化合物は特に限定はなく、具体例として、ピロメリット酸二無水物、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルエーテルテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物などの芳香族テトラカルボン酸、１，２，３，４－シクロブタンテトラカルボン酸二無水物、１，２－ジメチル－１，２，３，４－シクロブタンテトラカルボン酸二無水物、１，２，３，４－テトラメチル－１，２，３，４－シクロブタンテトラカルボン酸二無水物、１，２，３，４－シクロペンタンテトラカルボン酸二無水物、１，２，３，４－シクロヘキサンテトラカルボン酸二無水物、３，４－ジカルボキシ－１，２，３，４－テトラヒドロ－１－ナフタレンコハク酸二無水物のような脂環式テトラカルボン酸二無水物、１，２，３，４－ブタンテトラカルボン酸二無水物のような脂肪族テトラカルボン酸二無水物を挙げることができる。
　これらは、１種単独で用いてもよく、又は２種以上の化合物を組み合わせて用いてもよい。 The (a) tetracarboxylic dianhydride compound is not particularly limited, and specific examples thereof include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′. , 4,4′-Benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride Aromatic tetracarboxylic acid 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-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetra Carbo Alicyclic tetracarboxylic dianhydrides such as acid dianhydrides, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1,2,3,4 Mention may be made of aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride.
These may be used alone or in combination of two or more compounds.
　また、上記（ｂ）ジアミン化合物も特に限定されることはなく、例えば、２，４－ジアミノ安息香酸、２，５－ジアミノ安息香酸、３，５－ジアミノ安息香酸、４，６－ジアミノ－１，３－ベンゼンジカルボン酸、２，５－ジアミノ－１，４－ベンゼンジカルボン酸、ビス（４－アミノ－３－カルボキシフェニル）エーテル、ビス（４－アミノ－３，５－ジカルボキシフェニル）エーテル、ビス（４－アミノ－３－カルボキシフェニル）スルホン、ビス（４－アミノ－３，５－ジカルボキシフェニル）スルホン、４，４’－ジアミノ－３，３’－ジカルボキシビフェニル、４，４’－ジアミノ－３，３’－ジカルボキシ－５，５’－ジメチルビフェニル、４，４’－ジアミノ－３，３’－ジカルボキシ－５，５’－ジメトキシビフェニル、１，４－ビス（４－アミノ－３－カルボキシフェノキシ）ベンゼン、１，３－ビス（４－アミノ－３－カルボキシフェノキシ）ベンゼン、ビス［４－（４－アミノ－３－カルボキシフェノキシ）フェニル］スルホン、ビス［４－（４－アミノ－３－カルボキシフェノキシ）フェニル］プロパン、２，２－ビス［４－（４－アミノ－３－カルボキシフェノキシ）フェニル］ヘキサフルオロプロパン、２，４－ジアミノフェノール、３，５－ジアミノフェノール、２，５－ジアミノフェノール、４，６－ジアミノレゾルシノール、２，５－ジアミノハイドロキノン、ビス（３－アミノ－４－ヒドロキシフェニル）エーテル、ビス（４－アミノ－３－ヒドロキシフェニル）エーテル、ビス（４－アミノ－３，５－ジヒドロキシフェニル）エーテル、ビス（３－アミノ－４－ヒドロキシフェニル）メタン、ビス（４－アミノ－３－ヒドロキシフェニル）メタン、ビス（４－アミノ－３，５－ジヒドロキシフェニル）メタン、ビス（３－アミノ－４－ヒドロキシフェニル）スルホン、ビス（４－アミノ－３－ヒドロキシフェニル）スルホン、ビス（４－アミノ－３，５－ジヒドロキシフェニル）スルホン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン、２，２－ビス（４－アミノ－３－ヒドロキシフェニル）ヘキサフルオロプロパン、２，２－ビス（４－アミノ－３，５－ジヒドロキシフェニル）ヘキサフルオロプロパン、４，４’－ジアミノ－３，３’－ジヒドロキシビフェニル、４，４’－ジアミノ－３，３’－ジヒドロキシ－５，５’－ジメチルビフェニル、４，４’－ジアミノ－３，３’－ジヒドロキシ－５，５’－ジメトキシビフェニル、１，４－ビス（３－アミノ－４－ヒドロキシフェノキシ）ベンゼン、１，３－ビス（３－アミノ－４－ヒドロキシフェノキシ）ベンゼン、１，４－ビス（４－アミノ－３－ヒドロキシフェノキシ）ベンゼン、１，３－ビス（４－アミノ－３－ヒドロキシフェノキシ）ベンゼン、ビス［４－（３－アミノ－４－ヒドロキシフェノキシ）フェニル］スルホン、ビス［４－（３－アミノ－４－ヒドロキシフェノキシ）フェニル］プロパン、２，２－ビス［４－（３－アミノ－４－ヒドロキシフェノキシ）フェニル］ヘキサフルオロプロパン等フェノール性ヒドロキシ基を有するジアミン化合物、１，３－ジアミノ－４－メルカプトベンゼン、１，３－ジアミノ－５－メルカプトベンゼン、１，４－ジアミノ－２－メルカプトベンゼン、ビス（４－アミノ－３－メルカプトフェニル）エーテル、２，２－ビス（３－アミノ－４－メルカプトフェニル）ヘキサフルオロプロパン等チオフェノール基を有するジアミン化合物、１，３－ジアミノベンゼン－４－スルホン酸、１，３－ジアミノベンゼン－５－スルホン酸、１，４－ジアミノベンゼン－２－スルホン酸、ビス（４－アミノベンゼン－３－スルホン酸）エーテル、４，４’－ジアミノビフェニル－３，３’－ジスルホン酸、４，４’－ジアミノ－３，３’－ジメチルビフェニル－６，６’－ジスルホン酸等スルホン酸基を有するジアミン化合物が挙げられる。また、ｐ－フェニレンジアミン、ｍ－フェニレンジアミン、４，４’－メチレン－ビス（２，６－エチルアニリン）、４，４’－メチレン－ビス（２－イソプロピル－６－メチルアニリン）、４，４’－メチレン－ビス（２，６－ジイソプロピルアニリン）、２，４，６－トリメチル－１，３－フェニレンジアミン、２，３，５，６－テトラメチル－１，４－フェニレンジアミン、ｏ－トリジン、ｍ－トリジン、３，３’，５，５’－テトラメチルベンジジン、ビス［４－（３－アミノフェノキシ）フェニル］スルホン、２，２－ビス［４－（３－アミノフェノキシ）フェニル］プロパン、２，２－ビス［４－（３－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、４，４’－ジアミノ－３，３’－ジメチルジシクロヘキシルメタン、４，４’－ジアミノジフェニルエーテル、３，４－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルメタン、２，２－ビス（４－アニリノ）ヘキサフルオロプロパン、２，２－ビス（３－アニリノ）ヘキサフルオロプロパン、２，２－ビス（３－アミノ－４－トルイル）ヘキサフルオロプロパン、１，４－ビス（４－アミノフェノキシ）ベンゼン、１，３－ビス（４－アミノフェノキシ）ベンゼン、ビス［４－（４－アミノフェノキシ）フェニル］スルホン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２’－ビス（トリフルオロメチル）ベンジジン等のジアミン化合物を挙げることが出来る。
　これらは、１種単独で用いてもよく、又は２種以上の化合物を組み合わせて用いてもよい。 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-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic 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, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′- Diamino-3,3′-dicarboxy-5,5′-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, 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] hexafluoropropane, 2,4-diaminophenol, 3,5-diamino Phenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis (3-amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ether, bis (4-amino-3,5-dihydroxyphenyl) ether, bis (3-amino No-4-hydroxyphenyl) methane, bis (4-amino-3-hydroxyphenyl) methane, bis (4-amino-3,5-dihydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) sulfone, Bis (4-amino-3-hydroxyphenyl) sulfone, bis (4-amino-3,5-dihydroxyphenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2 -Bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3,5-dihydroxyphenyl) hexafluoropropane, 4,4'-diamino-3,3'-dihydroxy Biphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-dia -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, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] propane, 2,2-bis [4- (3-amino-4-hydroxyphenoxy) phenyl] hexafluoropropane, etc. Diamine compound, 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene 1,4-diamino-2-mercaptobenzene, bis (4-amino-3-mercaptophenyl) ether, 2,2-bis (3-amino-4-mercaptophenyl) hexafluoropropane and the like having a thiophenol group Diamine compounds, 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis (4-aminobenzene-3-sulfonic acid) ) Ether, 4,4′-diaminobiphenyl-3,3′-disulfonic acid, 4,4′-diamino-3,3′-dimethylbiphenyl-6,6′-disulfonic acid and the like diamine compounds having a sulfonic acid group Can be mentioned. P-phenylenediamine, m-phenylenediamine, 4,4′-methylene-bis (2,6-ethylaniline), 4,4′-methylene-bis (2-isopropyl-6-methylaniline), 4, 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, 3,3 ′, 5,5′-tetramethylbenzidine, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] Propane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 4,4 ′ Diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 2,2-bis (4-anilino) hexafluoropropane, 2,2-bis (3-anilino) hexafluoropropane, 2,2- Bis (3-amino-4-toluyl) hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) Phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2′-bis (tri And diamine compounds such as (fluoromethyl) benzidine.
These may be used alone or in combination of two or more compounds.
　本発明で用いられるポリアミド酸が（ａ）テトラカルボン酸二無水物化合物と（ｂ）ジアミン化合物から製造される場合、両化合物の配合比、すなわち（ｂ）ジアミン化合物の総モル数／（ａ）テトラカルボン酸二無水物化合物の総モル数は０．７乃至１．２であることが望ましい。通常の重縮合反応同様、このモル比が１に近いほど生成するポリアミド酸の重合度は大きくなり分子量が増加する。 When 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 both compounds, that is, (b) the total number of moles of the diamine compound / (a) The total number of moles of the tetracarboxylic dianhydride compound is preferably 0.7 to 1.2. As in the normal polycondensation reaction, the closer the molar ratio is to 1, the higher the degree of polymerization of the polyamic acid produced and the higher the molecular weight.
　また、ジアミン化合物を過剰に用いて重合した際、残存するポリアミド酸の末端アミノ基に対してカルボン酸無水物を反応させ末端アミノ基を保護することもできる。
　このようなカルボン酸無水物の例としてはフタル酸無水物、トリメリット酸無水物、無水マレイン酸、ナフタル酸無水物、水素化フタル酸無水物、メチル－５－ノルボルネン－２，３－ジカルボン酸無水物、無水イタコン酸、テトラヒドロフタル酸無水物等を挙げることができる。 Moreover, when it superposes | polymerizes using a diamine compound excessively, a carboxylic anhydride can be made to react with the terminal amino group of the remaining polyamic acid, and a terminal amino group can also be protected.
Examples of such carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid There may be mentioned anhydrides, itaconic anhydride, tetrahydrophthalic anhydride and the like.
　ポリアミド酸の製造において、ジアミン化合物とテトラカルボン酸二無水物化合物との反応の反応温度は－２０乃至１５０℃、好ましくは－５乃至１００℃の任意の温度を選択することができる。高分子量のポリアミド酸を得るには、反応温度５℃乃至４０℃、反応時間１乃至４８時間の範囲にて適宜選択する。低分子量で保存安定性の高く部分的にイミド化されたポリアミド酸を得るには反応温度４０℃乃至９０℃、反応時間１０時間以上から選択することがより好ましい。
　また、末端アミノ基を酸無水物で保護する場合の反応温度は－２０乃至１５０℃、好ましくは－５乃至１００℃の任意の温度を選択することができる。 In the production of the polyamic acid, the reaction temperature of the reaction between the diamine compound and the tetracarboxylic dianhydride compound can be selected from -20 to 150 ° C, preferably -5 to 100 ° C. In order to obtain a high molecular weight polyamic acid, the reaction temperature is appropriately selected within the range of 5 to 40 ° C. and the reaction time of 1 to 48 hours. In order to obtain a partially imidized polyamic acid having a low molecular weight and high storage stability, it is more preferable to select from a reaction temperature of 40 ° C. to 90 ° C. and a reaction time of 10 hours or more.
The reaction temperature for protecting the terminal amino group with an acid anhydride can be selected from -20 to 150 ° C, preferably -5 to 100 ° C.
　ジアミン化合物とテトラカルボン酸二無水物化合物の反応は溶剤中で行なうことができる。その際に使用できる溶剤としては、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン、Ｎ－ビニルピロリドン、Ｎ－メチルカプロラクタム、ジメチルスルホキシド、テトラメチル尿素、ピリジン、ジメチルスルホン、ヘキサメチルスルホキシド、ｍ－クレゾール、γ－ブチロラクトン、酢酸エチル、酢酸ブチル、乳酸エチル、３－メトキシプロピオン酸メチル、２－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、２－メトキシプロピオン酸エチル、３－エトキシプロピオン酸エチル、２－エトキシプロピオン酸エチル、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルエチルエーテル、プロピレングリコールジメチルエーテル、ジプロピレングリコールジメチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート、エチルセロソルブアセテート、シクロヘキサノン、メチルエチルケトン、メチルイソブチルケトン、２－ヘプタノン等を挙げることができる。これらは単独でも、混合して使用しても良い。さらに、ポリアミド酸を溶解しない溶剤であっても、重合反応により生成したポリアミド酸が析出しない範囲で、上記溶剤に混合して使用してもよい。 The reaction of the diamine compound and the tetracarboxylic dianhydride compound can be performed in a solvent. Solvents that can be used in this case include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, Hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, 3 -Ethyl ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ester Ter, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene Examples include glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. These may be used alone or in combination. Furthermore, even if it is a solvent which does not melt | dissolve a polyamic acid, you may mix and use it for the said solvent in the range which does not precipitate the polyamic acid produced | generated by the polymerization reaction.
　このようにして得られたポリアミド酸を含む溶液は、ネガ型感光性樹脂組成物の調製にそのまま用いることができる。また、ポリアミド酸を水、メタノール、エタノール等の貧溶剤に沈殿単離させて回収して用いることもできる。 The solution containing the polyamic acid thus obtained can be used as it is for the preparation of a negative photosensitive resin composition. Further, the polyamic acid may be precipitated and isolated in a poor solvent such as water, methanol, ethanol, etc. and recovered for use.
　また、（Ｂ）成分としては、任意のポリイミドも用いることができる。本発明に用いるポリイミドとは前記ポリアミド酸などのポリイミド前駆体を化学的又は熱的に５０％以上イミド化させたものである。 Also, any polyimide can be used as the component (B). The polyimide used in the present invention is obtained by chemically or thermally imidizing 50% or more of a polyimide precursor such as polyamic acid.
　本発明の感光性樹脂組成物に用いるポリイミドは、アルカリ溶解性を与えるためにカルボキシル基及びフェノール性ヒドロキシ基から選ばれる基を有することが好ましい。
　ポリイミドへのカルボキシル基又はフェノール性ヒドロキシ基の導入方法は、カルボキシル基又はフェノール性ヒドロキシ基を有するモノマーを用いる方法、カルボキシル基又はフェノール性ヒドロキシ基を有する酸無水物でアミン末端を封止する方法、或いは、ポリアミド酸などのポリイミド前駆体をイミド化する際にイミド化率を９９％以下にする方法等が用いられる。 The polyimide used in the photosensitive resin composition of the present invention preferably has a group selected from a carboxyl group and a phenolic hydroxy group in order to impart alkali solubility.
The method of introducing a carboxyl group or a phenolic hydroxy group into polyimide is a method using a monomer having a carboxyl group or a phenolic hydroxy group, a method of sealing an amine terminal with an acid anhydride having a carboxyl group or a phenolic hydroxy group, Alternatively, a method of setting the imidization rate to 99% or less when imidizing a polyimide precursor such as polyamide acid is used.
　このようなポリイミドは上述のポリアミド酸などのポリイミド前駆体を合成した後、化学イミド化もしくは熱イミド化を行うことで得ることができる。
　化学イミド化の方法としては一般的にポリイミド前駆体溶液に過剰の無水酢酸およびピリジンを添加し室温から１００℃で反応させる方法が用いられる。また、熱イミド化の方法としては一般的に、ポリイミド前駆体溶液を温度１８０℃乃至２５０℃で脱水しながら過熱する方法が用いられる。 Such a polyimide can be obtained by synthesizing a polyimide precursor such as the above-mentioned polyamic acid and then performing chemical imidization or thermal imidization.
As a method of chemical imidization, generally, a method of adding excess acetic anhydride and pyridine to a polyimide precursor solution and reacting at room temperature to 100 ° C. is used. As a method for thermal imidization, generally, a method in which a polyimide precursor solution is heated while being dehydrated at a temperature of 180 ° C. to 250 ° C. is used.
　また、（Ｂ）成分のアルカリ可溶性樹脂としては、さらにフェノールノボラック樹脂を用いることができる。 Further, as the alkali-soluble resin of component (B), a phenol novolac resin can be further used.
　また、（Ｂ）成分のアルカリ可溶性樹脂としては、ポリエステルポリカルボン酸を用いることもできる。ポリエステルポリカルボン酸は、酸二無水物とジオールから、ＷＯ２００９／０５１１８６に記載の方法により、得ることができる。
　酸二無水物としては、上記（ａ）テトラカルボン酸二無水物が挙げられる。
　ジオールとしては、ビスフェノールＡ、ビスフェノールＦ、４，４’－ジヒドロキシビフェニル、ベンゼン－１，３－ジメタノール、ベンゼン－１，４－ジメタノール等の芳香族ジオール、水添ビスフェノールＡ、水添ビスフェノールＦ、１，４－シクロヘキサンジオール、１，３－シクロヘキサンジメタノール、１，４－シクロヘキサンジメタノール等の脂環族ジオール、及びエチレングリコール、プロピレングリコール、１，４－ブタンジオール、１，６－ヘキサンジオール等の脂肪族ジオール等が挙げられる。 Further, as the alkali-soluble resin of component (B), polyester polycarboxylic acid can also be used. The polyester polycarboxylic acid can be obtained from an acid dianhydride and a diol by the method described in WO2009 / 051186.
Examples of the acid dianhydride include the above (a) tetracarboxylic dianhydride.
Examples of the diol include bisphenol A, bisphenol F, 4,4′-dihydroxybiphenyl, aromatic diols such as benzene-1,3-dimethanol, benzene-1,4-dimethanol, hydrogenated bisphenol A, and hydrogenated bisphenol F. 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and other alicyclic diols, and ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol And the like, and the like.
　また、本発明においては、（Ｂ）成分のアルカリ可溶性樹脂は、複数種のアルカリ可溶性樹脂の混合物であってもよい。 In the present invention, the alkali-soluble resin (B) may be a mixture of a plurality of types of alkali-soluble resins.
　（Ａ）成分と（Ｂ）成分との比率は、（Ｂ）成分１００質量部に対して（Ａ）成分が０．１～２０質量部である。 The ratio of the component (A) to the component (B) is 0.1 to 20 parts by mass of the component (A) with respect to 100 parts by mass of the component (B).
＜（Ｃ）溶剤＞
　本発明に用いる（Ｃ）溶剤は、（Ａ）成分、（Ｂ）成分、及び必要に応じて後述の（Ｄ）成分、（Ｅ）成分、（Ｆ）成分、（Ｇ）成分を溶解し、且つ所望により添加される後述の（Ｈ）成分やその他添加剤などを溶解するものであり、斯様な溶解能を有する溶剤であれば、その種類及び構造などは特に限定されるものでない。 <(C) Solvent>
The (C) solvent used in the present invention dissolves the component (A), the component (B), and the component (D), the component (E), the component (F), and the component (G) described below, if necessary. And if it dissolves the below-mentioned (H) component added by necessity, other additives, etc., if it is a solvent which has such a solubility, the kind, structure, etc. will not be specifically limited.
　斯様な（Ｃ）溶剤としては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート、トルエン、キシレン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、２－ブタノン、３－メチル－２－ペンタノン、２－ペンタノン、２-ヘプタノン、γ―ブチロラクトン、２－ヒドロキシプロピオン酸エチル、２－ヒドロキシ－２－メチルプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２－ヒドロキシ－３－メチルブタン酸メチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、ピルビン酸メチル、ピルビン酸エチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、及びＮ－メチルピロリドン等が挙げられる。 Examples of such a 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, propylene glycol monomethyl 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, γ-butyrolactone, 2-hydroxypropion Ethyl acetate, ethyl 2-hydroxy-2-methylpropionate, ethoxy vinegar Ethyl, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, pyruvate Examples include ethyl, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.
　これらの溶剤は、一種単独で、または二種以上の組合せで使用することができる。
　これら（Ｃ）溶剤の中、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、２－ヘプタノン、プロピレングリコールプロピルエーテル、プロピレングリコールプロピルエーテルアセテート、乳酸エチル、乳酸ブチル等が、塗膜性が良好で安全性が高いという観点より好ましい。これら溶剤は、一般にフォトレジスト材料のための溶剤として用いられている。 These solvents can be used singly or in combination of two or more.
Among these (C) solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, etc. have good coating properties and safety Is preferable from the viewpoint of high. These solvents are generally used as solvents for photoresist materials.
＜（Ｄ）成分＞
　（Ｄ）成分である感光剤としては、（Ｄ－１）１，２－キノンジアジド化合物、（Ｄ－２）光ラジカル発生剤、（Ｄ－３）光酸発生剤が挙げられる。 <(D) component>
Examples of the photosensitive agent as component (D) include (D-1) 1,2-quinonediazide compounds, (D-2) photoradical generators, and (D-3) photoacid generators.
（Ｄ－１）１，２－キノンジアジド化合物としては、水酸基又はアミノ基のいずれか一方か、水酸基及びアミノ基の両方を有する化合物であって、これらの水酸基又はアミノ基（水酸基とアミノ基の両方を有する場合は、それらの合計量）のうち、好ましくは１０乃至１００モル％、特に好ましくは２０乃至９５モル％が１，２－キノンジアジドスルホン酸でエステル化、またはアミド化された化合物を用いることができる。 (D-1) The 1,2-quinonediazide compound is a compound having either a hydroxyl group or an amino group, both a hydroxyl group and an amino group, and these hydroxyl groups or amino groups (both hydroxyl groups and amino groups). The total amount thereof), preferably 10 to 100 mol%, particularly preferably 20 to 95 mol% is a compound esterified or amidated with 1,2-quinonediazidesulfonic acid. Can do.
　前記水酸基を有する化合物としては例えば、フェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール、ハイドロキノン、レゾルシノール、カテコール、ガリック酸メチル、ガリック酸エチル、１，３，３－トリス（４－ヒドロキシフェニル）ブタン、４，４－イソプロプリデンジフェノール、２，２－ビス（４－ヒドロキシフェニル）プロパン、１，１－ビス（４－ヒドロキシフェニル）シクロヘキサン、４，４’－ジヒドロキシフェニルスルホン、４，４－ヘキサフルオロイソプロピリデンジフェノール、４，４’,４’’―トリスヒドロキシフェニルエタン、１，１，１－トリスヒドロキシフェニルエタン、４，４’－［１－［４－［１－（４－ヒドロキシフェニル）－１－メチルエチル］フェニル］エチリデン］ビスフェノール、２，４－ジヒドロキシベンゾフェノン、２，３，４－トリヒドロキシベンゾフェノン、２，２’，４，４’－テトラヒドロキシベンゾフェノン、２，３，４，４’－テトラヒドロキシベンゾフェノン、２，２’，３，４，４’－ペンタヒドロキシベンゾフェノン、２，５－ビス（２－ヒドロキシ－５－メチルベンジル）メチルなどのフェノール化合物、エタノール、２－プロパノール、４－ブタノール、シクロヘキサノール、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、２－メトキシエタノール、２－ブトキシエタノール、２－メトキシプロパノール、２－ブトキシプロパノール、乳酸エチル、乳酸ブチルなどの脂肪族アルコール類を挙げることができる。 Examples of the compound having a hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, ethyl gallate, 1,3,3-tris (4-hydroxyphenyl). Butane, 4,4-isopropylidene diphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxyphenylsulfone, 4,4- Hexafluoroisopropylidenediphenol, 4,4 ', 4' '-trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4,4'-[1- [4- [1- (4-hydroxy Phenyl) -1-methylethyl] phenyl] ethylidene] bisphenol 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2' , 3,4,4'-pentahydroxybenzophenone, phenol compounds such as 2,5-bis (2-hydroxy-5-methylbenzyl) methyl, ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene Specific examples include aliphatic alcohols such as glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, and butyl lactate.
　また、前記アミノ基を含有する化合物としては、アニリン、ｏ－トルイジン、ｍ－トルイジン、ｐ－トルイジン、４－アミノジフェニルメタン、４－アミノジフェニル、ｏ－フェニレンジアミン、ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、４，４’－ジアミノフェニルメタン、４，４’－ジアミノジフェニルエーテルなどのアニリン類、アミノシクロヘキサンを挙げることができる。 Examples of the compound containing an amino group include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine. Anilines such as 4,4′-diaminophenylmethane and 4,4′-diaminodiphenyl ether, and aminocyclohexane.
　さらに、水酸基とアミノ基両方を含有する化合物としては、例えば、ｏ－アミノフェノール、ｍ－アミノフェノール、ｐ－アミノフェノール、４－アミノレゾルシノール、２，３－ジアミノフェノール、２，４－ジアミノフェノール、４，４’－ジアミノ－４’’－ヒドロキシトリフェニルメタン、４－アミノ－４’，４’’－ジヒドロキシトリフェニルメタン、ビス（４－アミノ－３－カルボキシ－５－ヒドロキシフェニル）エーテル、ビス（４－アミノ－３－カルボキシ－５－ヒドロキシフェニル）メタン、２，２－ビス（４－アミノ－３－カルボキシ－５－ヒドロキシフェニル）プロパン、２，２－ビス（４－アミノ－３－カルボキシ－５－ヒドロキシフェニル）ヘキサフルオロプロパンなどのアミノフェノール類、２－アミノエタノール、３－アミノプロパノール、４－アミノシクロヘキサノールなどのアルカノールアミン類を挙げることができる。 Further, examples of the compound containing both a hydroxyl group and an amino group include o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, 2,4-diaminophenol, 4,4′-diamino-4 ″ -hydroxytriphenylmethane, 4-amino-4 ′, 4 ″ -dihydroxytriphenylmethane, bis (4-amino-3-carboxy-5-hydroxyphenyl) ether, bis (4-amino-3-carboxy-5-hydroxyphenyl) methane, 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) propane, 2,2-bis (4-amino-3-carboxy) Aminophenols such as -5-hydroxyphenyl) hexafluoropropane, 2-aminoethane Lumpur, 3-aminopropanol, mention may be made of alkanolamines, such as 4-amino-cyclohexanol.
　これらの１，２－キノンジアジド化合物は単独または２種以上の組み合わせで使用することができる。 These 1,2-quinonediazide compounds can be used alone or in combination of two or more.
　本発明の感光性樹脂組成物がポジ型感光性樹脂組成物である場合に（Ｄ－１）成分のキノンジアジド基を有する化合物を含有させる場合の含有量は、（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、好ましくは５乃至１００質量部、より好ましくは８乃至５０質量部、更に好ましくは１０乃至４０質量部である。５質量部未満の場合、ポジ型感光性樹脂組成物の露光部と未露光部の現像液への溶解速度差が小さくなり、現像によるパターニングが困難である場合がある。また、１００質量部を超えると、短時間での露光で１，２－キノンジアジド化合物が十分に分解されないため感度が低下する場合や、（Ｄ－１）成分が光を吸収してしまい硬化膜の透明性を低下させてしまう場合がある。 When the photosensitive resin composition of the present invention is a positive photosensitive resin composition, the content when the compound having a quinonediazide group as the component (D-1) is included is as follows. The total amount is preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, and still more preferably 10 to 40 parts by mass. 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 becomes small, and patterning by development may be difficult. When the amount exceeds 100 parts by mass, the 1,2-quinonediazide compound is not sufficiently decomposed by exposure in a short time and sensitivity is lowered, or the component (D-1) absorbs light and the cured film Transparency may be reduced.
（Ｄ－２）光ラジカル発生剤は、露光によりラジカルを発生するものであれば特に制限はない。具体例としては、例えばベンゾフェノン、ミヒラーケトン、４，４’－ビスジエチルアミノベンゾフェノン、４－メトキシ－４’－ジメチルアミノベンゾフェノン、２－エチルアントラキノン、フェナントレン等の芳香族ケトン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインフェニルエーテル等のベンゾインエーテル類、メチルベンゾイン、エチルベンゾイン等のベンゾイン、２－（ｏ－クロロフェニル）－４，５－フェニルイミダゾール２量体、２－（ｏ－クロロフェニル）－４，５－ジ（ｍ－メトキシフェニル）イミダゾール２量体、２－（ｏ－フルオロフェニル）－４，５－ジフェニルイミダゾール２量体、２－（ｏ－メトキシフェニル）－４，５－ジフェニルイミダゾール２量体、２，４，５－トリアリールイミダゾール２量体、２－（ｏ－クロロフェニル）－４，５－ジ（ｍ－メチルフェニル）イミダゾール２量体、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン、２－トリクロロメチル－５－スチリル－１，３，４－オキサジアゾール、２－トリクロロメチル－５－（ｐ－シアノスチリル）－１，３，４－オキサジアゾール、２－トリクロロメチル－５－（ｐ－メトキシスチリル）－１，３，４－オキサジアゾール等のハロメチルオキサジアゾール化合物、２，４－ビス（トリクロロメチル）－６－ｐ－メトキシスチリル－Ｓ－トリアジン、２，４－ビス（トリクロロメチル）－６－（１－ｐ－ジメチルアミノフェニル－１，３－ブタジエニル）－Ｓ－トリアジン、２－トリクロロメチル－４－アミノ－６－ｐ－メトキシスチリル－Ｓ－トリアジン、２－（ナフト－１－イル）－４，６－ビス－トリクロロメチル－Ｓ－トリアジン、２－（４－エトキシ－ナフト－１－イル）－４，６－ビス－トリクロロメチル－Ｓ－トリアジン、２－（４－ブトキシ－ナフト－１－イル）－４，６－ビス－トリクロロメチル－Ｓ－トリアジン等のハロメチル－Ｓ－トリアジン系化合物、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、２－メチル－１－〔４－（メチルチオ）フェニル〕－２－モルフォリノプロパノン、１，２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１，１－ヒドロキシ－シクロヘキシル－フェニルケトン、ベンジル、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、４－ベンゾイル－４’－メチルジフェニルサルファイド、ベンジルメチルケタール、ジメチルアミノベンゾエート、ｐ－ジメチルアミノ安息香酸イソアミル、２－ｎ－ブトキシエチル－４－ジメチルアミノベンゾエート、２－クロロチオキサントン、２，４－ジエチルチオキサントン、２，４－ジメチルチオキサントン、イソプロピルチオキサントン、１－（４－フェニルチオフェニル）－１，２－オクタンジオン－２－（Ｏ－ベンゾイルオキシム）、エタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－１－（Ｏ－アセチルオキシム）、４－ベンゾイル－メチルジフェニルサルファイド、１－ヒドロキシ－シクロヘキシル－フェニルケトン、２－ベンジル－２－（ジメチルアミノ）－１－［４－（４－モルフォリニル）フェニル］－１－ブタノン、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン、α－ジメトキシ－α－フェニルアセトフェノン、フェニルビス（２，４，６－トリメチルベンゾイル）フォスフィンオキサイド、ジフェニル（２，４，６－トリメチルベンゾイル）フォスフィンオキサイド、２－メチル－１－［４－（メチルチオ）フェニル］－２－（４－モルフォリニル）－１－プロパノン等が挙げられる。
　上記の光重合開始剤は、市販品として容易に入手が可能であり、その具体例としては、例えばＩＲＧＡＣＵＲＥ　１７３、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（以上、ＢＡＳＦ社製）、ＫＡＹＡＣＵＲＥ　ＤＥＴＸ－Ｓ、ＫＡＹＡＣＵＲＥ　ＣＴＸ、ＫＡＹＡＣＵＲＥ　ＢＭＳ、ＫＡＹＡＣＵＲＥ　２－ＥＡＱ（以上、日本化薬（株）製）、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（以上みどり化学（株）製）等が挙げられる。
　これらの光ラジカル発生剤単独で使用しても、二種類以上を併用することも可能である。 (D-2) The photoradical generator is not particularly limited as long as it generates radicals upon exposure. Specific examples include aromatic ketones such as benzophenone, Michler ketone, 4,4′-bisdiethylaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrene, benzoin methyl ether, benzoin ethyl ether, Benzoin ethers such as benzoinphenyl ether, benzoin such as methylbenzoin and ethylbenzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di ( m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2, 4,5-triaryl Dazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methylphenyl) imidazole dimer, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- Halomethyloxadiazole compounds such as (p-methoxystyryl) -1,3,4-oxadiazole, 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- (naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis -Halomethyl-S-triazine compounds such as trichloromethyl-S-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy- 1,2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'- Methyl diphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethyl Thioxanthone, isopropylthioxanthone, 1- (4-phenylthiophenyl) -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-phenyl ketone, 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-phenyl Acetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone and the like.
The above photopolymerization initiator can be easily obtained as a commercial product. Specific examples thereof include IRGACURE 173, 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 (above, manufactured by BASF), KATURE Above, Japan Manufactured by Yakuhin Co., Ltd.), 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 (manufactured by Midori Chemical Co., Ltd.) and the like.
These photoradical generators can be used alone or in combination of two or more.
　本発明の感光性樹脂組成物に（Ｄ－２）成分を含有させる場合の含有量は、（Ａ）成分の１００質量部に対して０．１～３０質量部であることが好ましく、より好ましくは０．５～２０質量部であり、特に好ましくは１～１５質量部である。この割合が過小である場合には、露光部が硬化不足となり、パターン形成ができなかったり、できたとしても信頼性の低い膜となる場合がある。また、この割合が過大である場合には、塗膜の透過率が低下したり、未露光部の現像不良が起こる場合がある。 The content when the component (D-2) is contained in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 100 parts by mass of the component (A). Is 0.5 to 20 parts by mass, particularly preferably 1 to 15 parts by mass. If this ratio is too small, the exposed portion may be insufficiently cured, and pattern formation may not be possible, or even if it is possible, a film with low reliability may be formed. Moreover, when this ratio is excessive, the transmittance | permeability of a coating film may fall or the development defect of an unexposed part may arise.
　（Ｄ－３）の光酸発生剤は紫外線照射時に光分解して酸を発生する化合物であれば特に限定されるものではない。光酸発生剤が光分解した際に発生する酸としては、例えば、塩酸、メタンスルホン酸、エタンスルホン酸、プロパンスルホン酸、ブタンスルホン酸、ペンタンスルホン酸、オクタンスルホン酸、ベンゼンスルホン酸、ｐ－トルエンスルホン酸、カンファスルホン酸、トリフルオロメタンスルホン酸、ｐ－フェノールスルホン酸、２－ナフタレンスルホン酸、メシチレンスルホン酸、ｐ－キシレン－２－スルホン酸、ｍ－キシレン－２－スルホン酸、４－エチルベンゼンスルホン酸、１Ｈ，１Ｈ，２Ｈ，２Ｈ－パーフルオロオクタンスルホン酸、パーフルオロ（２－エトキシエタン）スルホン酸、ペンタフルオロエタンスルホン酸、ノナフルオロブタン－１－スルホン酸、ドデシルベンゼンスルホン酸等のスルホン酸又はその水和物や塩等が挙げられる。 The photoacid generator (D-3) is not particularly limited as long as it is a compound that generates an acid by photolysis when irradiated with ultraviolet rays. Examples of acids generated when the photoacid generator is photolyzed 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, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzene Sulfone such as sulfonic acid, 1H, 1H, 2H, 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, etc. Acids or their hydrates and salts It is.
　光酸発生剤としては、例えば、ジアゾメタン化合物、オニウム塩化合物、スルホンイミド化合物、ジスルホン系化合物、スルホン酸誘導体化合物、ニトロベンジル化合物、ベンゾイントシレート化合物、鉄アレーン錯体、ハロゲン含有トリアジン化合物、アセトフェノン誘導体化合物、及び、シアノ基含有オキシムスルホネート化合物などが挙げられる。従来知られ又は従来から使用されている光酸発生剤は、いずれも、特に限定されることなく、本発明において適用することができる。なお、本発明において、（Ｄ）成分の光酸発生剤は、一種単独で用いてもよく、また二種以上を組み合わせて用いてもよい。具体例としては、下記式［ＰＡＧ－１］～式［ＰＡＧ－４１］で表される化合物等を挙げることができる。 Examples of the photoacid generator include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzoin tosylate compounds, iron arene complexes, halogen-containing triazine compounds, and acetophenone derivative compounds. And cyano group-containing oxime sulfonate compounds. Any conventionally known or conventionally used photoacid generator can be applied in the present invention without any particular limitation. In addition, in this invention, the photo-acid generator of (D) component may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples thereof include compounds represented by the following formulas [PAG-1] to [PAG-41].
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　本実施の形態の感光性樹脂組成物に（Ｄ－３）成分を含有させる場合の含有量は、（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、好ましくは０．０１質量部～２０質量部、より好ましくは０．１質量部～１０質量部、更に好ましくは０．５質量部～８質量部である。（Ｄ－３）成分の含有量を０．０１質量部以上とすることで、充分な熱硬化性および溶剤耐性を付与することができる。しかし、２０質量部より多い場合、未露光部が現像不良となったり、組成物の保存安定性が低下する場合がある。 The content when the component (D-3) is contained in the photosensitive resin composition of the present embodiment is preferably 0.01 mass with respect to a total of 100 mass parts of the components (A) and (B). Part to 20 parts by weight, more preferably 0.1 part by weight to 10 parts by weight, still more preferably 0.5 part by weight to 8 parts by weight. By setting the content of the component (D-3) to 0.01 parts by mass or more, sufficient thermosetting and solvent resistance can be imparted. However, when it is more than 20 parts by mass, the unexposed part may be poorly developed or the storage stability of the composition may be lowered.
＜（Ｅ）成分＞
　（Ｅ）成分は架橋剤であり、本発明の感光性樹脂組成物が要件（Ｚ１）を満たす場合に組成物中に導入されるものである。より具体的には、（Ｂ）成分の熱反応性部位（たとえば、カルボキシル基及び／又はフェノール性水酸基）と熱反応により橋架け構造を形成しうる構造を有する化合物である。以下、具体例を挙げるがこれらに限定されるものではない。熱架橋剤は、例えば、（Ｅ１）アルコキシメチル基及びヒドロキシメチル基から選ばれる置換基を２個以上有する架橋性化合物や（Ｅ２）式（５）で表される架橋性化合物から選ばれるものが好ましい。これらの架橋剤は単独または２種以上の組み合わせで使用することができる。 <(E) component>
The component (E) is a crosslinking agent, and is introduced into the composition when the photosensitive resin composition of the present invention satisfies the requirement (Z1). More specifically, it is a compound having a structure capable of forming a bridge structure by a thermal reaction with a thermally reactive site (for example, carboxyl group and / or phenolic hydroxyl group) of component (B). Specific examples will be given below, but the present invention is not limited thereto. Examples of the thermal crosslinking agent include those selected from (E1) a crosslinkable compound having two or more substituents selected from an alkoxymethyl group and a hydroxymethyl group and (E2) a crosslinkable compound represented by formula (5). preferable. These crosslinking agents can be used alone or in combination of two or more.
　（Ｅ１）成分のアルコキシメチル基及びヒドロキシメチル基から選ばれる置換基を２個以上有する架橋性化合物は、熱硬化時の高温に曝されると、脱水縮合反応により架橋反応が進行するものである。このような化合物としては、例えば、アルコキシメチル化グリコールウリル、アルコキシメチル化ベンゾグアナミン、およびアルコキシメチル化メラミン等の化合物、およびフェノプラスト系化合物が挙げられる。 The crosslinkable compound having two or more substituents selected from the alkoxymethyl group and hydroxymethyl group as the component (E1) undergoes a crosslinking reaction by a dehydration condensation reaction when exposed to a high temperature during thermosetting. . Examples of such compounds include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast compounds.
　アルコキシメチル化グリコールウリルの具体例としては、例えば、１，３，４，６－テトラキス（メトキシメチル）グリコールウリル、１，３，４，６－テトラキス（ブトキシメチル）グリコールウリル、１，３，４，６－テトラキス（ヒドロキシメチル）グリコールウリル、１，３－ビス（ヒドロキシメチル）尿素、１，１，３，３－テトラキス（ブトキシメチル）尿素、１，１，３，３－テトラキス（メトキシメチル）尿素、１，３－ビス（ヒドロキシメチル）－４，５－ジヒドロキシ－２－イミダゾリノン、および１，３－ビス（メトキシメチル）－４，５－ジメトキシ－２－イミダゾリノン等が挙げられる。市販品として、三井サイテック（株）製グリコールウリル化合物（商品名：サイメル（登録商標）１１７０、パウダーリンク（登録商標）１１７４）等の化合物、メチル化尿素樹脂（商品名：ＵＦＲ（登録商標）６５）、ブチル化尿素樹脂（商品名：ＵＦＲ（登録商標）３００、Ｕ－ＶＡＮ１０Ｓ６０、Ｕ－ＶＡＮ１０Ｒ、Ｕ－ＶＡＮ１１ＨＶ）、ＤＩＣ（株）製尿素／ホルムアルデヒド系樹脂（高縮合型、商品名：ベッカミン（登録商標）Ｊ－３００Ｓ、同Ｐ－９５５、同Ｎ）等が挙げられる。 Specific examples of the alkoxymethylated glycoluril include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4 , 6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone. As commercially available products, compounds such as glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resins (trade name: UFR (registered trademark) 65) ), Butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin (high-condensation type, product name: Beccamin (trade name) manufactured by DIC Corporation) Registered trademark) J-300S, P-955, N) and the like.
　アルコキシメチル化ベンゾグアナミンの具体例としてはテトラメトキシメチルベンゾグアナミン等が挙げられる。市販品として、三井サイテック（株）製（商品名：サイメル（登録商標）１１２３）、（株）三和ケミカル製（商品名：ニカラック（登録商標）ＢＸ－４０００、同ＢＸ－３７、同ＢＬ－６０、同ＢＸ－５５Ｈ）等が挙げられる。 Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine. Commercially available products manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), manufactured by Sanwa Chemical Co., Ltd. (trade names: Nicalac (registered trademark) BX-4000, BX-37, BL- 60, BX-55H) and the like.
　アルコキシメチル化メラミンの具体例としては、例えば、ヘキサメトキシメチルメラミン等が挙げられる。市販品として、三井サイテック（株）製メトキシメチルタイプメラミン化合物（商品名：サイメル（登録商標）３００、同３０１、同３０３、同３５０）、ブトキシメチルタイプメラミン化合物（商品名：マイコート（登録商標）５０６、同５０８）、三和ケミカル製メトキシメチルタイプメラミン化合物（商品名：ニカラック（登録商標）ＭＷ－３０、同ＭＷ－２２、同ＭＷ－１１、同ＭＷ－１００ＬＭ、同ＭＳ－００１、同ＭＸ－００２、同ＭＸ－７３０、同ＭＸ－７５０、同ＭＸ－０３５）、ブトキシメチルタイプメラミン化合物（商品名：ニカラック（登録商標）ＭＸ－４５、同ＭＸ－４１０、同ＭＸ－３０２）等が挙げられる。 Specific examples of alkoxymethylated melamine include, for example, hexamethoxymethylmelamine. As commercially available products, methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, 350) manufactured by Mitsui Cytec Co., Ltd., butoxymethyl type melamine compounds (trade name: My Coat (registered trademark)) 506, 508), methoxymethyl type melamine compound manufactured by Sanwa Chemical Co., Ltd. (trade names: Nicalac (registered trademark) MW-30, MW-22, MW-11, MW-100LM, MS-001, MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compounds (trade names: Nicalac (registered trademark) MX-45, MX-410, MX-302), etc. Can be mentioned.
　また、このようなアミノ基の水素原子がメチロール基またはアルコキシメチル基で置換されたメラミン化合物、尿素化合物、グリコールウリル化合物及びベンゾグアナミン化合物を縮合させて得られる化合物であってもよい。例えば、米国特許第６３２３３１０号に記載されているメラミン化合物およびベンゾグアナミン化合物から製造される高分子量の化合物が挙げられる。前記メラミン化合物の市販品としては、商品名：サイメル（登録商標）３０３（三井サイテック（株）製）等が挙げられ、前記ベンゾグアナミン化合物の市販品としては、商品名：サイメル（登録商標）１１２３（三井サイテック（株）製）等が挙げられる。 Also, a compound obtained by condensing a melamine compound, urea compound, glycoluril compound and benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group may be used. For example, the high molecular weight compound manufactured from the melamine compound and the benzoguanamine compound which are described in US Patent 6,323,310 is mentioned. Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.). Examples of commercially available products of the benzoguanamine compound include product name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd.).
　フェノプラスト系化合物の具体例としては、例えば、２，６－ビス（ヒドロキシメチル）フェノール、２，６－ビス（ヒドロキシメチル）クレゾール、２，６－ビス（ヒドロキシメチル）－４－メトキシフェノール、３，３’，５，５’－テトラキス（ヒドロキシメチル）ビフェニル－４，４’－ジオール、３，３’－メチレンビス（２－ヒドロキシ－５－メチルベンゼンメタノール）、４，４’－（１－メチルエチリデン）ビス［２－メチル－６－ヒドロキシメチルフェノール］、４，４’－メチレンビス［２－メチル－６－ヒドロキシメチルフェノール］、４，４’－（１－メチルエチリデン）ビス［２，６－ビス（ヒドロキシメチル）フェノール］、４，４’－メチレンビス［２，６－ビス（ヒドロキシメチル）フェノール］、２，６－ビス（メトキシメチル）フェノール、２，６－ビス（メトキシメチル）クレゾール、２，６－ビス（メトキシメチル）－４－メトキシフェノール、３，３’，５，５’－テトラキス（メトキシメチル）ビフェニル－４，４’－ジオール、３，３’－メチレンビス（２－メトキシ－５－メチルベンゼンメタノール）、４，４’－（１－メチルエチリデン）ビス［２－メチル－６－メトキシメチルフェノール］、４，４’－メチレンビス［２－メチル－６－メトキシメチルフェノール］、４，４’－（１－メチルエチリデン）ビス［２，６－ビス（メトキシメチル）フェノール］、４，４’－メチレンビス［２，６－ビス（メトキシメチル）フェノール］等が挙げられる。市販品としても入手が可能であり、その具体例としては、２６ＤＭＰＣ、４６ＤＭＯＣ、ＤＭ－ＢＩＰＣ－Ｆ、ＤＭ－ＢＩＯＣ－Ｆ、ＴＭ－ＢＩＰ－Ａ、ＢＩＳＡ－Ｆ、ＢＩ２５Ｘ－ＤＦ、ＢＩ２５Ｘ－ＴＰＡ（以上、旭有機材工業（株）製）等が挙げられる。 Specific examples of phenoplast compounds include 2,6-bis (hydroxymethyl) phenol, 2,6-bis (hydroxymethyl) cresol, 2,6-bis (hydroxymethyl) -4-methoxyphenol, 3 , 3 ′, 5,5′-tetrakis (hydroxymethyl) biphenyl-4,4′-diol, 3,3′-methylenebis (2-hydroxy-5-methylbenzenemethanol), 4,4 ′-(1-methyl) Ethylidene) bis [2-methyl-6-hydroxymethylphenol], 4,4′-methylenebis [2-methyl-6-hydroxymethylphenol], 4,4 ′-(1-methylethylidene) bis [2,6- Bis (hydroxymethyl) phenol], 4,4′-methylenebis [2,6-bis (hydroxymethyl) phenol], 2, -Bis (methoxymethyl) phenol, 2,6-bis (methoxymethyl) cresol, 2,6-bis (methoxymethyl) -4-methoxyphenol, 3,3 ', 5,5'-tetrakis (methoxymethyl) biphenyl -4,4'-diol, 3,3'-methylenebis (2-methoxy-5-methylbenzenemethanol), 4,4 '-(1-methylethylidene) bis [2-methyl-6-methoxymethylphenol], 4,4′-methylenebis [2-methyl-6-methoxymethylphenol], 4,4 ′-(1-methylethylidene) bis [2,6-bis (methoxymethyl) phenol], 4,4′-methylenebis [ 2,6-bis (methoxymethyl) phenol] and the like. Specific examples are 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, BI25X-TPA ( As mentioned above, Asahi Organic Materials Co., Ltd.) and the like can be mentioned.
　さらに、（Ｅ１）成分としては、Ｎ－ヒドロキシメチルアクリルアミド、Ｎ－メトキシメチルメタクリルアミド、Ｎ－エトキシメチルアクリルアミド、Ｎ－ブトキシメチルメタクリルアミド等のヒドロキシメチル基またはアルコキシメチル基で置換されたアクリルアミド化合物またはメタクリルアミド化合物を使用して製造されるポリマーも用いることができる。 Further, as the component (E1), the acrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or the like Polymers produced using methacrylamide compounds can also be used.
　そのようなポリマーとしては、例えば、ポリ（Ｎ－ブトキシメチルアクリルアミド）、Ｎ－ブトキシメチルアクリルアミドとスチレンとの共重合体、Ｎ－ヒドロキシメチルメタクリルアミドとメチルメタクリレートとの共重合体、Ｎ－エトキシメチルメタクリルアミドとベンジルメタクリレートとの共重合体、及びＮ－ブトキシメチルアクリルアミドとベンジルメタクリレートと２－ヒドロキシプロピルメタクリレートとの共重合体等が挙げられる。このようなポリマーの重量平均分子量は、１，０００乃至５０，０００であり、好ましくは、１，５００乃至２０，０００であり、より好ましくは２，０００乃至１０，０００である。 Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl. Examples thereof include a copolymer of methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, 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.
　また本発明の感光性樹脂組成物は、（Ｅ２）成分として、式（５）で表される架橋性化合物を含有することができる。
Figure JPOXMLDOC01-appb-C000015
 （式中、ｋは２～１０の整数、ｍは０～４の整数を示し、Ｒ１１はｋ価の有機基を表す） Moreover, the photosensitive resin composition of this invention can contain the crosslinkable compound represented by Formula (5) as (E2) component.
Figure JPOXMLDOC01-appb-C000015
 (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）成分は、式（５）で表されるシクロアルケンオキサイド構造を有する化合物であれば特に限定されない。その具体例としては、下記式Ｅ２－１及びＥ２－２や、以下に示す市販品等が挙げられる。
Figure JPOXMLDOC01-appb-C000016
 The component (E2) is not particularly limited as long as it is a compound having a cycloalkene oxide structure represented by the formula (5). Specific examples thereof include the following formulas E2-1 and E2-2, and commercially available products shown below.
Figure JPOXMLDOC01-appb-C000016
　市販品としては、エポリードＧＴ－４０１、同ＧＴ－４０３、同ＧＴ－３０１、同ＧＴ－３０２、セロキサイド２０２１、セロキサイド３０００（ダイセル化学工業（株）製　商品名）、脂環式エポキシ樹脂であるデナコールＥＸ－２５２（ナガセケムッテクス（株）製　商品名）、ＣＹ１７５、ＣＹ１７７、ＣＹ１７９（以上、ＣＩＢＡ－ＧＥＩＧＹ　Ａ．Ｇ製　商品名）、アラルダイトＣＹ－１８２、同ＣＹ－１９２、同ＣＹ－１８４（以上、ＣＩＢＡ－ＧＥＩＧＹ　Ａ．Ｇ製　商品名）、エピクロン２００、同４００（以上、ＤＩＣ（株）製　商品名）、エピコート８７１、同８７２（以上、油化シェルエポキシ（株）製　商品名）、ＥＤ－５６６１、ＥＤ－５６６２（以上、セラニーズコーティング（株）製　商品名）、等を挙げることができる。また、これらの架橋性化合物は、単独または２種類以上を組み合わせて用いることができる。 Commercially available products include Epolide GT-401, GT-403, GT-301, GT-302, Celoxide 2021, Celoxide 3000 (trade name, manufactured by Daicel Chemical Industries, Ltd.), Denacol, an alicyclic epoxy resin. EX-252 (trade name, manufactured by Nagase Chemmutex Co., Ltd.), CY175, CY177, CY179 (trade name, manufactured by CIBA-GEIGY AG), Araldite CY-182, CY-192, CY-184 ( Above, CIBA-GEIGY AG product name), Epicron 200, 400 (above, DIC Corporation product name), Epicoat 871, 872 (above, Yuka Shell Epoxy Co., Ltd. product name), ED-5661, ED-5661 (above, trade name manufactured by Celanese Coating Co., Ltd.), etc. It is possible. Moreover, these crosslinkable compounds can be used individually or in combination of 2 or more types.
　これらのうち、耐熱性、耐溶剤性、耐長時間焼成耐性等の耐プロセス性、および透明性の観点からシクロヘキセンオキサイド構造を有する、式Ｃ１及び式Ｃ２で表される化合物、エポリードＧＴ－４０１、同ＧＴ－４０３、同ＧＴ－３０１、同ＧＴ－３０２、セロキサイド２０２１、セロキサイド３０００が好ましい。 Among these, the compounds represented by formula C1 and formula C2 having a cyclohexene oxide structure from the viewpoint of heat resistance, solvent resistance, process resistance such as long-term baking resistance, and transparency, Epolide GT-401, GT-403, GT-301, GT-302, Celoxide 2021, and Celoxide 3000 are preferable.
　また、Ｅ成分としては（Ｅ１）成分、（Ｅ２）成分として示したもの以外の（Ｂ）成分の熱反応性部位（たとえば、カルボキシル基及び／又はフェノール性水酸基）と熱反応により橋架け構造を形成しうる化合物も用いることができる。具体的には、例えば、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、グリセリンジグリシジルエーテル、２，２－ジブロモネオペンチルグリコールジグリシジルエーテル、１，３，５，６－テトラグリシジル－２，４－ヘキサンジオール、Ｎ，Ｎ，Ｎ’，Ｎ’，－テトラグリシジル－ｍ－キシレンジアミン、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン、及びＮ，Ｎ，Ｎ’，Ｎ’，－テトラグリシジル－４、４’－ジアミノジフェニルメタン等のエポキシ化合物、ＶＥＳＴＡＮＡＴ　Ｂ１３５８／１００、ＶＥＳＴＡＧＯＮ　ＢＦ　１５４０（以上、イソシアヌレート型変性ポリイソシアネート、デグサジャパン（株）製）、タケネート（登録商標）Ｂ－８８２Ｎ、同タケネートＢ―７０７５（以上、イソシアヌレート型変性ポリイソシアネート、三井化学（株）製）等のイソシアネート化合物等が挙げられる。 Moreover, as E component, (E1) component, (E2) The bridge structure by thermal reaction with the heat-reactive part (for example, carboxyl group and / or phenolic hydroxyl group) of component (B) other than what was shown as a component. Formable compounds can also be used. Specifically, for example, 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-hexane Diol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′, -Tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, and N, N, N ', N',-tetraglycidyl-4,4'-diame Epoxy compounds such as diphenylmethane, VESTANAT B1358 / 100, VESTAGON BF 1540 (above, isocyanurate-type modified polyisocyanate, manufactured by Degussa Japan), Takenate (registered trademark) B-882N, Takenate B-7075 (above, Isocyan And isocyanate compounds such as nurate-type modified polyisocyanate, manufactured by Mitsui Chemicals, Inc.
　また、Ｅ成分としては（Ｂ）成分の熱反応性部位（たとえば、カルボキシル基及び／又はフェノール性水酸基）と熱反応により橋架け構造を形成しうる構造を２個以上有する重合体を用いることができる。具体的には、例えば、グリシジルメタクリレート、３，４－エポキシシクロヘキシルメチルメタクリレート、３，４－エポキシシクロヘキシルメチルメタクリレート等のエポキシ基を有する化合物を使用して製造されるポリマー、３－メタクリロキシプロピルトリメトキシシラン等のアルコキシシリル基を有する化合物を使用して製造されるポリマー、２－イソシアナトエチルメタクリレート（カレンズＭＯＩ［登録商標］、昭和電工（株）製）、２－イソシアナトエチルアクリレート（カレンズＡＯＩ［登録商標］、昭和電工（株）製）等のイソシアナート基を有する化合物、または２－（０－［１’－メチルプロピリデンアミノ］カルボキシアミノ）エチルメタクリレート（カレンズＭＯＩ－ＢＭ［登録商標］、昭和電工（株）製）、２－［（３，５－ジメチルピラゾリル）カルボニルアミノ］エチルメタクリレート（カレンズＭＯＩ－ＢＰ［登録商標］、昭和電工（株）製）等のブロック化イソシアナート基を有する化合物を使用して製造されるポリマーが挙げられる。これらの化合物は単独、もしくは複数を組み合わせて使用してポリマーを製造しても良く、そのほかの化合物と組み合わせてポリマーを製造しても良い。 Further, as the E component, a polymer having two or more structures capable of forming a bridge structure by thermal reaction with the thermally reactive site (for example, carboxyl group and / or phenolic hydroxyl group) of the component (B) is used. it can. Specifically, for example, a polymer produced by using a compound having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methacryloxypropyltrimethoxy, etc. Polymers produced using a compound having an alkoxysilyl group such as silane, 2-isocyanatoethyl methacrylate (Karenz MOI [registered trademark], manufactured by Showa Denko KK), 2-isocyanatoethyl acrylate (Karenz AOI [ Registered trademark], a compound having an isocyanate group such as Showa Denko Co., Ltd.), or 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate (Karenz MOI-BM [registered trademark], Showa Denko Co., Ltd.), 2 A polymer produced using a compound having a blocked isocyanate group, such as [(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate (Karenz MOI-BP [registered trademark], manufactured by Showa Denko KK) Can be mentioned. These compounds may be used alone or in combination to produce a polymer, and may be produced in combination with other compounds.
　（Ｂ）成分がヒドロキシ基、カルボキシル基、アミド基、アミノ基で表される基からなる群から選ばれる少なくとも１つの基と反応する基を有する場合には、ヒドロキシ基、カルボキシル基、アミド基、アミノ基で表される基を２つ以上有する化合物を（Ｅ）成分として用いることができる。 When the component (B) has a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group, a hydroxy group, a carboxyl group, an amide group, A compound having two or more groups represented by an amino group can be used as the component (E).
　これらの架橋性化合物は、単独でまたは２種以上を組み合わせて使用することができる。 These crosslinkable compounds can be used alone or in combination of two or more.
　本発明の感光性樹脂組成物における架橋剤として（Ｅ）成分を選択した場合の含有量は、（Ａ）成分と（Ｂ）成分の合計１００質量部に対して１～５０質量部、好ましくは１～４０質量部、より好ましくは１～３０質量部である。架橋性化合物の含有量が少ない場合には、架橋性化合物によって形成される架橋の密度が十分ではないため、パターン形成後の耐熱性、耐溶剤性、長時間の焼成に対する耐性等を向上させる効果が得られない場合がある。一方、５０質量部を超える場合には、未架橋の架橋性化合物が存在し、パターン形成後の耐熱性、耐溶剤性、長時間の焼成に対する耐性等が低下し、また、感光性樹脂組成物の保存安定性が悪くなる場合がある。 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 weight, preferably 100 parts by weight in total of the components (A) and (B). 1 to 40 parts by mass, more preferably 1 to 30 parts by mass. When the content of the crosslinkable compound is low, the crosslink density formed by the crosslinkable compound is not sufficient, and therefore the effect of improving the heat resistance after the pattern formation, the solvent resistance, the long-term baking resistance, etc. May not be obtained. On the other hand, when it exceeds 50 parts by mass, there is an uncrosslinked crosslinkable compound, the heat resistance after forming the pattern, the solvent resistance, the resistance to baking for a long time, etc. are reduced, and the photosensitive resin composition The storage stability of may deteriorate.
＜（Ｆ）成分＞
　（Ｆ）成分はエチレン性重合性基を２個以上有する化合物である。ここで言うところのエチレン性重合性基を２個以上有する化合物とは、一分子中に重合性基を２個以上有し、且つそれらの重合性基が分子末端にある化合物のことを意味し、それらの重合性基とは、アクリレート基、メタクリレート基、ビニル基及びアリル基からなる群より選ばれる少なくとも１種類の重合性基のことを意味する。
　この（Ｆ）成分であるエチレン性重合性基を２個以上有する化合物は、本発明のネガ型感光性樹脂組成物の溶液において、各成分との相溶性が良好で、且つ現像性に影響を与えないという観点から、分子量（該化合物がポリマーである場合、重量平均分子量）が１，０００以下の化合物が好ましい。 <(F) component>
Component (F) is a compound having two or more ethylenic polymerizable groups. The compound having two or more ethylenically polymerizable groups as referred to herein means a compound having two or more polymerizable groups in one molecule and having these polymerizable groups at the molecular terminals. The polymerizable group means at least one polymerizable group selected from the group consisting of an acrylate group, a methacrylate group, a vinyl group, and an allyl group.
The compound having two or more ethylenic polymerizable groups as the component (F) has good compatibility with each component in the solution of the negative photosensitive resin composition of the present invention and affects the developability. From the viewpoint of not giving, a compound having a molecular weight (when the compound is a polymer, a weight average molecular weight) of 1,000 or less is preferable.
　このような化合物の具体例としては、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールヘキサメタクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールペンタメタクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールテトラメタクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールジメタクリレート、テトラメチロールプロパンテトラアクリレート、テトラメチロールプロパンテトラメタクリレート、テトラメチロールメタンテトラアクリレート、テトラメチロールメタンテトラメタクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパントリメタクリレート、１，３，５－トリアクリロイルヘキサヒドロ－Ｓ－トリアジン、１，３，５－トリメタクリロイルヘキサヒドロ－Ｓ－トリアジン、トリス（ヒドロキシエチルアクリロイル）イソシアヌレート、トリス（ヒドロキシエチルメタクリロイル）イソシアヌレート、トリアクリロイルホルマール、トリメタクリロイルホルマール、１，６－ヘキサンジオールアクリレート、１，６－ヘキサンジオールメタクリレート、ネオペンチルグリコールジアクリレート、ネオペンチルグリコールジメタクリレート、エタンジオールジアクリレート、エタンジオールジメタクリレート、２－ヒドロキシプロパンジオールジアクリレート、２－ヒドロキシプロパンジオールジメタクリレート、ジエチレングリコールジアクリレート、ジエチレングリコールジメタクリレート、イソプロピレングリコールジアクリレート、イソプロピレングリコールジメタクリレート、トリエチレングリコールジアクリレート、トリエチレングリコールジメタクリレート、Ｎ，Ｎ’－ビス（アクリロイル）システイン、Ｎ，Ｎ’－ビス（メタクリロイル）システイン、チオジグリコールジアクリレート、チオジグリコールジメタクリレート、ビスフェノールＡジアクリレート、ビスフェノールＡジメタクリレート、ビスフェノールＦジアクリレート、ビスフェノールＦジメタクリレート、ビスフェノールＳジアクリレート、ビスフェノールＳジメタクリレート、ビスフェノキシエタノールフルオレンジアクリレート、ビスフェノキシエタノールフルオレンジメタクリレート、ジアリルエーテルビスフェノールＡ、ｏ―ジアリルビスフェノールＡ、マレイン酸ジアリル、トリアリルトリメリテート等が挙げられる。 Specific examples of such compounds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, penta Erythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethyl Propanetrimethacrylate, 1,3,5-triacryloylhexahydro-S-triazine, 1,3,5-trimethacryloylhexahydro-S-triazine, tris (hydroxyethylacryloyl) isocyanurate, tris (hydroxyethylmethacryloyl) ) Isocyanurate, triacryloyl formal, trimethacryloyl formal, 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethanediol diacrylate, ethanediol dimethacrylate, 2-hydroxypropanediol diacrylate, 2-hydroxypropanediol dimethacrylate, diethylene glycol diacrylate Diethylene glycol dimethacrylate, isopropylene glycol diacrylate, isopropylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, N, N'-bis (acryloyl) cysteine, N, N'-bis (methacryloyl) Cysteine, thiodiglycol diacrylate, thiodiglycol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate, bisphenol S dimethacrylate, bisphenoxyethanol full orange acrylate, Bisphenoxyethanol full orange methacrylate, diallyl Examples thereof include terbisphenol A, o-diallyl bisphenol A, diallyl maleate, triallyl trimellitate and the like.
　上記の多官能アクリレート化合物は、市販品として容易に入手が可能であり、その具体例としては、例えばＫＹＡＲＡＤ　Ｔ－１４２０、同ＤＰＨＡ、同ＤＰＨＡ－２Ｃ、同Ｄ－３１０、同Ｄ－３３０、同ＤＰＣＡ－２０、同ＤＰＣＡ－３０、同ＤＰＣＡ－６０、同ＤＰＣＡ－１２０、同ＤＮ－００７５、同ＤＮ－２４７５、同Ｒ－５２６、同ＮＰＧＤＡ、同ＰＥＧ４００ＤＡ、同ＭＡＮＤＡ、同Ｒ－１６７、同ＨＸ－２２０、同ＨＸ６２０、同Ｒ－５５１、同Ｒ－７１２、同Ｒ－６０４、同Ｒ－６８４、同ＧＰＯ－３０３、同ＴＭＰＴＡ、同ＴＨＥ－３３０、同ＴＰＡ－３２０、同ＴＰＡ－３３０、同ＰＥＴ－３０、同ＲＰ－１０４０（以上、日本化薬（株）製）、アロニックスＭ－２１０、同Ｍ－２４０、同Ｍ－６２００、同Ｍ－３０９、同Ｍ－４００、同Ｍ－４０２、同Ｍ－４０５、同Ｍ－４５０、同Ｍ－７１００、同Ｍ－８０３０、同Ｍ－８０６０、同Ｍ－１３１０、同Ｍ－１６００、同Ｍ－１９６０、同Ｍ－８１００、同Ｍ－８５３０、同Ｍ－８５６０、同Ｍ－９０５０（以上、東亞合成（株）製）、ビスコート２９５、同３００、同３６０、同ＧＰＴ、同３ＰＡ、同４００、同２６０、同３１２、同３３５ＨＰ（以上、大阪有機化学工業（株）製）、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　（以上、新中村化学工業（株）製）等を挙げることができる。
　これらの重エチレン性合性基を２個以上有する化合物は１種または２種以上を組み合わせて用いることができる。 The above polyfunctional acrylate compounds can be easily obtained as commercial products. Specific examples thereof include KYARAD T-1420, DPHA, DPHA-2C, D-310, D-330, and the like. DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, R-526, NPGDA, PEG400DA, MANDA, R-167, HX -220, HX620, R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-240, M-6200, M-309, M-400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M-1310, M-1310, M-1600, M-1960, M-8100, M-8530, M-8560, M-8560, M-9050 (Made by Toagosei Co., Ltd.), Biscote 295, 300, 360, GPT, 3PA, 400, 260 312, 335HP (Osaka Organic Chemical Co., Ltd.), 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, BP -1300N, BPE-900, BPE-200, BPE-100, BPE-80N, 23G, 14G, 9G, 4G, 3G, 2G, 1G (above, manufactured by Shin-Nakamura Chemical Co., Ltd.) .
These compounds having two or more heavy ethylenic compatibility groups can be used alone or in combination of two or more.
　本発明の感光性樹脂組成物に（Ｆ）成分を含有させる場合の含有量は、（Ａ）成分と（Ｂ）成分の合計の１００質量部に対して５～１００質量部であることが好ましく、より好ましくは１０～８０質量部であり、特に好ましくは２０～７０質量部である。この割合が過小である場合には、露光部が硬化不足となり、パターン形成ができなかったり、できたとしても信頼性の低い膜となる可能性がある。また、この割合が過大である場合には、プリベーク後の塗膜にタックが発生したり、現像時に未露光部が溶解不良となる場合がある。 The content of the component (F) in the photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass with respect to 100 parts by mass as the total of the components (A) and (B). More preferably, it is 10 to 80 parts by mass, and particularly preferably 20 to 70 parts by mass. If this ratio is too small, the exposed area will be insufficiently cured, and pattern formation may not be possible, or even if possible, the film may be unreliable. Moreover, when this ratio is excessive, tack may generate | occur | produce in the coating film after a prebaking, or an unexposed part may become a melt | dissolution defect at the time of image development.
＜（Ｇ）成分＞
本発明の感光性樹脂組成物に用いられる（Ｇ）成分は、酸により共有結合を形成する官能基を２個以上有する化合物である。このような酸により共有結合を形成する官能基としてはエポキシ基やメチロール基等が挙げられる。 <(G) component>
The component (G) used in the photosensitive resin composition of the present invention is a compound having two or more functional groups that form a covalent bond with an acid. Examples of such a functional group that forms a covalent bond with an acid include an epoxy group and a methylol group.
エポキシ基を２個以上有する化合物としては、例えば、トリス（２，３－エポキシプロピル）イソシアヌレート、１，４－ブタンジオールジグリシジルエーテル、１，２－エポキシ－４－（エポキシエチル）シクロヘキサン、グリセロールトリグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、２，６－ジグリシジルフェニルグリシジルエーテル、１，１，３－トリス［ｐ－（２，３－エポキシプロポキシ）フェニル］プロパン、１，２－シクロヘキサンジカルボン酸ジグリシジルエステル、４，４’－メチレンビス（Ｎ，Ｎ－ジグリシジルアニリン）、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、トリメチロールエタントリグリシジルエーテル、ビスフェノール－Ａ－ジグリシジルエーテル、及びペンタエリスリトールポリグリシジルエーテル等を挙げることができる。 Examples of the compound having two 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-diglycidylphenyl glycidyl ether, 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, diglycidyl 1,2-cyclohexanedicarboxylate Ester, 4,4′-methylenebis (N, N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-di Glycidyl ether, and and pentaerythritol polyglycidyl ether.
　また、エポキシ基を２個以上有する化合物としては、入手が容易である点から市販品の化合物を用いてもよい。以下にその具体例（商品名）を挙げるが、これらに限定されるものではない：ＹＨ－４３４、ＹＨ４３４Ｌ（東都化成（株）製）等のアミノ基を有するエポキシ樹脂；エポリードＧＴ－４０１、同ＧＴ－４０３、同ＧＴ－３０１、同ＧＴ－３０２、セロキサイド２０２１、セロキサイド３０００（ダイセル化学工業（株）製）等のシクロヘキセンオキサイド構造を有するエポキシ樹脂；エピコート１００１、同１００２、同１００３、同１００４、同１００７、同１００９、同１０１０、同８２８（以上、油化シェルエポキシ（株）（現ジャパンエポキシレジン（株））製）等のビスフェノールＡ型エポキシ樹脂；エピコート８０７（油化シェルエポキシ（株）（現ジャパンエポキシレジン（株））製）等のビスフェノールＦ型エポキシ樹脂；エピコート１５２、同１５４（以上、油化シェルエポキシ（株）（現ジャパンエポキシレジン（株））製）、ＥＰＰＮ２０１、同２０２（以上、日本化薬（株）製）等のフェノールノボラック型エポキシ樹脂；ＥＯＣＮ－１０２、ＥＯＣＮ－１０３Ｓ、ＥＯＣＮ－１０４Ｓ、ＥＯＣＮ－１０２０、ＥＯＣＮ－１０２５、ＥＯＣＮ－１０２７（以上、日本化薬（株）製）、エピコート１８０Ｓ７５（油化シェルエポキシ（株）（現ジャパンエポキシレジン（株））製）等のクレゾールノボラック型エポキシ樹脂；デナコールＥＸ－２５２（ナガセケムテックス（株）製）、ＣＹ１７５、ＣＹ１７７、ＣＹ１７９、アラルダイトＣＹ－１８２、同ＣＹ－１９２、同ＣＹ－１８４（以上、ＣＩＢＡ－ＧＥＩＧＹ Ａ.Ｇ製）、エピクロン２００、同４００（以上、大日本インキ化学工業（株）製）、エピコート８７１、同８７２（以上、油化シェルエポキシ（株）（現ジャパンエポキシレジン（株））製）、ＥＤ－５６６１、ＥＤ－５６６２（以上、セラニーズコーティング（株）製）等の脂環式エポキシ樹脂；デナコールＥＸ－６１１、同ＥＸ－６１２、同ＥＸ－６１４、同ＥＸ－６２２、同ＥＸ－４１１、同ＥＸ－５１２、同ＥＸ－５２２、同ＥＸ－４２１、同ＥＸ－３１３、同ＥＸ－３１４、同ＥＸ－３２１（ナガセケムテックス（株）製）等の脂肪族ポリグリシジルエーテル等。 Further, as a compound having two or more epoxy groups, a commercially available compound may be used because it is easily available. Specific examples (trade names) are listed below, but are not limited to these: epoxy resins having amino groups such as YH-434, YH434L (manufactured by Tohto Kasei Co., Ltd.); Epolide GT-401, Epoxy resin having a cyclohexene oxide structure such as GT-403, GT-301, GT-302, Celoxide 2021, Celoxide 3000 (manufactured by Daicel Chemical Industries, Ltd.); Epicoat 1001, 1002, 1003, 1004, Bisphenol A type epoxy resins such as 1007, 1009, 1010, and 828 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Japan Epoxy Resin Co., Ltd.)); Epicoat 807 (Oyka Shell Epoxy Co., Ltd.) Bisphenol F type epoxy resin (currently Japan Epoxy Resin Co., Ltd.) Epicote 152, 154 (above, Yuka Shell Epoxy Co., Ltd. (currently Japan Epoxy Resins Co., Ltd.)), EPPN 201, 202 (above, Nippon Kayaku Co., Ltd.) and other phenol novolac epoxy resins; EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.), Epikote 180S75 (Oka Shell Shell Epoxy Co., Ltd. (current Japan Epoxy Resin) Cresol novolak type epoxy resin such as Denacor EX-252 (manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179, Araldite CY-182, CY-192, CY-184 (above) CIBA-GEIGY A.G), Epicron 200, the same 00 (manufactured by Dainippon Ink & Chemicals, Inc.), Epicoat 871, 872 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Japan Epoxy Resin Co., Ltd.)), ED-5661, ED-5661 ( As described above, alicyclic epoxy resin such as Celanese Coating Co., Ltd .; Denacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX -522, aliphatic polyglycidyl ethers such as EX-421, EX-313, EX-314, EX-321 (manufactured by Nagase ChemteX Corporation).
　また、エポキシ基を２個以上有する化合物としてはエポキシ基を有するポリマーを使用することもできる。
　上記エポキシ基を有するポリマーは、例えばエポキシ基を有する付加重合性モノマーを用いた付加重合により製造することができる。一例として、ポリグリシジルアクリレート、グリシジルメタクリレートとエチルメタクリレートの共重合体、グリシジルメタクリレートとスチレンと２－ヒドロキシエチルメタクリレートの共重合体等の付加重合ポリマーや、エポキシノボラック等の縮重合ポリマーを挙げることができる。 Moreover, the polymer which has an epoxy group can also be used as a compound which has 2 or more of epoxy groups.
The polymer having an epoxy group can be produced, for example, by addition polymerization using an addition polymerizable monomer having an epoxy group. Examples include addition polymerization polymers such as polyglycidyl acrylate, copolymers of glycidyl methacrylate and ethyl methacrylate, copolymers of glycidyl methacrylate and styrene and 2-hydroxyethyl methacrylate, and condensation polymerization polymers such as epoxy novolac. .
　或いは、上記エポキシ基を有するポリマーは、ヒドロキシ基を有する高分子化合物とエピクロルヒドリン、グリシジルトシレート等のエポキシ基を有する化合物との反応により製造することもできる。 Alternatively, the polymer having an epoxy group can be produced by a reaction between a polymer compound having a hydroxy group and a compound having an epoxy group such as epichlorohydrin or glycidyl tosylate.
　このようなポリマーの重量平均分子量としては、例えば、３００乃至２０，０００である。 The weight average molecular weight of such a polymer is, for example, 300 to 20,000.
　これらのエポキシ基を２個以上有する化合物は、単独または２種以上の組み合わせで使用することができる。 These compounds having two or more epoxy groups can be used alone or in combination of two or more.
　メチロール基を２個以上有する化合物としては、例えば、１，３，４，６－テトラキス（メトキシメチル）グリコールウリル、１，３，４，６－テトラキス（ブトキシメチル）グリコールウリル、１，３，４，６－テトラキス（ヒドロキシメチル）グリコールウリル、１，３－ビス（ヒドロキシメチル）尿素、１，１，３，３－テトラキス（ブトキシメチル）尿素、１，１，３，３－テトラキス（メトキシメチル）尿素、１，３－ビス（ヒドロキシメチル）－４，５－ジヒドロキシ－２－イミダゾリノン、および１，３－ビス（メトキシメチル）－４，５－ジメトキシ－２－イミダゾリノン等が挙げられる。市販品として、三井サイテック（株）製グリコールウリル化合物（商品名：サイメル（登録商標）１１７０、パウダーリンク（登録商標）１１７４）等の化合物、メチル化尿素樹脂（商品名：ＵＦＲ（登録商標）６５）、ブチル化尿素樹脂（商品名：ＵＦＲ（登録商標）３００、Ｕ－ＶＡＮ１０Ｓ６０、Ｕ－ＶＡＮ１０Ｒ、Ｕ－ＶＡＮ１１ＨＶ）、ＤＩＣ（株）製尿素／ホルムアルデヒド系樹脂（高縮合型、商品名：ベッカミン（登録商標）Ｊ－３００Ｓ、同Ｐ－９５５、同Ｎ）、テトラメトキシメチルベンゾグアナミン等が挙げられる。市販品として、三井サイテック（株）製（商品名：サイメル（登録商標）１１２３）、（株）三和ケミカル製（商品名：ニカラック（登録商標）ＢＸ－４０００、同ＢＸ－３７、同ＢＬ－６０、同ＢＸ－５５Ｈ）、ヘキサメトキシメチルメラミン等が挙げられる。市販品として、三井サイテック（株）製メトキシメチルタイプメラミン化合物（商品名：サイメル（登録商標）３００、同３０１、同３０３、同３５０）、ブトキシメチルタイプメラミン化合物（商品名：マイコート（登録商標）５０６、同５０８）、三和ケミカル製メトキシメチルタイプメラミン化合物（商品名：ニカラック（登録商標）ＭＷ－３０、同ＭＷ－２２、同ＭＷ－１１、同ＭＳ－００１、同ＭＸ－００２、同ＭＸ－７３０、同ＭＸ－７５０、同ＭＸ－０３５）、ブトキシメチルタイプメラミン化合物（商品名：ニカラック（登録商標）ＭＸ－４５、同ＭＸ－４１０、同ＭＸ－３０２）を挙げることができる。 Examples of the compound having two or more methylol groups include 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4 , 6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone. As commercially available products, compounds such as glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resins (trade name: UFR (registered trademark) 65) ), Butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin (high-condensation type, product name: Beccamin (trade name) manufactured by DIC Corporation) Registered trademark) J-300S, P-955, N), tetramethoxymethylbenzoguanamine and the like. Commercially available products manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), manufactured by Sanwa Chemical Co., Ltd. (trade names: Nicalac (registered trademark) BX-4000, BX-37, BL- 60, BX-55H), hexamethoxymethylmelamine and the like. As commercially available products, methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, 350) manufactured by Mitsui Cytec Co., Ltd., butoxymethyl type melamine compounds (trade name: My Coat (registered trademark)) 506, 508), Sanwa Chemical's methoxymethyl-type melamine compound (trade names: Nicalak (registered trademark) MW-30, MW-22, MW-11, MS-001, MX-002, MX-730, MX-750, MX-035) and butoxymethyl type melamine compounds (trade names: Nicalac (registered trademark) MX-45, MX-410, MX-302).
　また、メチロール基を２個以上有する化合物としてはメチロール基を有するポリマーを使用することもできる。 In addition, as a compound having two or more methylol groups, a polymer having a methylol group can also be used.
　上記メチロール基を２個以上有するポリマーとしては、Ｎ－ヒドロキシメチル（メタ）アクリルアミド、Ｎ－メトキシメチル（メタ）アクリルアミド、Ｎ－エトキシメチル（メタ）アクリルアミド、Ｎ－ブトキシメチル（メタ）アクリルアミド等のヒドロキシメチル基又はアルコキシメチル基で置換されたアクリルアミド化合物又はメタクリルアミド化合物を使用して製造されるポリマーが挙げられる。 Examples of the polymer having two or more methylol groups include hydroxy such as N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide. The polymer manufactured using the acrylamide compound or the methacrylamide compound substituted by the methyl group or the alkoxymethyl group is mentioned.
　そのようなポリマーの具体例としては、例えば、ポリ（Ｎ－ブトキシメチルアクリルアミド）、Ｎ－ブトキシメチルアクリルアミドとスチレンとの共重合体、Ｎ－ヒドロキシメチルメタクリルアミドとメチルメタクリレートとの共重合体、Ｎ－エトキシメチルメタクリルアミドとベンジルメタクリレートとの共重合体、及びＮ－ブトキシメチルアクリルアミドとベンジルメタクリレートと２－ヒドロキシプロピルメタクリレートとの共重合体等が挙げられる。このようなポリマーの重量平均分子量は、１，０００乃至２００，０００であり、より好ましくは３，０００乃至１５０，０００であり、さらに好ましくは３，０００乃至５０，０００である。 Specific examples of such a polymer include, for example, poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, N And a copolymer of ethoxymethyl methacrylamide and benzyl methacrylate, a copolymer of N-butoxymethyl acrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate. The weight average molecular weight of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and still more preferably 3,000 to 50,000.
　これらのメチロール基を２個以上有する化合物は、単独または２種以上の組み合わせで使用することができる。 These compounds having two or more methylol groups can be used alone or in combination of two or more.
　本発明の感光性樹脂組成物に（Ｇ）成分の酸により共有結合を形成する官能基を２個以上有する化合物を含有させる場合の含有量は、（Ａ）成分と（Ｂ）成分の合計１００質量部に基づいて５乃至２００質量部であることが好ましく、より好ましくは５０乃至１５０質量部である。この割合が過小である場合には、ネガ型感光性樹脂組成物の光硬化性が低下する場合があり、他方、過大である場合には未露光部の現像性が低下し残膜や残渣の原因となる場合がある。 When the photosensitive resin composition of the present invention contains a compound having two or more functional groups that form a covalent bond with the acid of component (G), the total content of component (A) and component (B) is 100. The amount is preferably 5 to 200 parts by weight, more preferably 50 to 150 parts by weight based on the parts by weight. If this ratio is too small, the photo-curing property of the negative photosensitive resin composition may be reduced, whereas if it is too large, the developability of the unexposed area will be reduced, resulting in residual film or residue. It may be a cause.
＜その他添加剤＞
　更に、本発明の感光性樹脂組成物は、本発明の効果を損なわない限りにおいて、必要に応じて、レオロジー調整剤、顔料、染料、保存安定剤、消泡剤、密着促進剤、または多価フェノール、多価カルボン酸等の溶解促進剤等を含有することができる。 <Other additives>
Furthermore, the photosensitive resin composition of the present invention is a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, an adhesion promoter, or a polyvalent, as necessary, as long as the effects of the present invention are not impaired. It can contain dissolution promoters such as phenol and polycarboxylic acid.
＜感光性樹脂組成物＞
　本発明の感光性樹脂組成物は、下記（Ａ）成分、（Ｂ）成分、（Ｃ）溶剤及び（Ｄ）成分を含有する感光性樹脂組成物であり、且つ、所望により、（Ｅ）成分の架橋剤、（Ｆ）成分の重合性基を２個以上有する化合物、（Ｇ）成分の酸により共有結合を形成する官能基を２個以上有する化合物、及びその他添加剤のうち一種以上を更に含有することができる組成物である。
（Ａ）成分：下記基（Ａ１）及び（Ａ２）を有するポリシロキサン
（Ａ１）フッ素原子を有する有機基
（Ａ２）熱架橋性基を有する有機基
（Ｂ）成分：アルカリ可溶性樹脂
（Ｃ）溶剤、
（Ｄ）成分：感光剤。 <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) and component (D), and, if desired, component (E) One or more of the crosslinking agent, the compound (F) having two or more polymerizable groups, the compound (G) having two or more functional groups that form a covalent bond with the acid, and other additives It is a composition that can be contained.
(A) Component: Polysiloxane having the following groups (A1) and (A2) (A1) Organic group having fluorine atom (A2) Organic group having thermally crosslinkable group (B) Component: Alkali-soluble resin (C) solvent ,
(D) Component: Photosensitizer.
　中でも、本発明の感光性樹脂組成物の好ましい例は、以下のとおりである。
［１］：（Ｂ）成分１００質量部に対して０．１～２０質量部の（Ａ）成分を含有し、これら成分が（Ｃ）溶剤に溶解された感光性樹脂組成物。
［２］：（Ｂ）成分１００質量部に対して０．１～２０質量部の（Ａ）成分、５乃至１００質量部の（Ｄ）成分を含有し、これら成分が（Ｃ）溶剤に溶解された感光性樹脂組成物。
［３］：（Ｂ）成分１００質量部に対して０．１～２０質量部の（Ａ）成分、５乃至１００質量部の（Ｄ）成分を含有し、これら成分が（Ｃ）溶剤に溶解された感光性樹脂組成物であって、さらに（Ｅ）成分である架橋剤を、（Ａ）成分と（Ｂ）成分の合計の１００質量部に対して１乃至５０質量部含有する感光性樹脂組成物。 Especially, the preferable example of the photosensitive resin composition of this invention is as follows.
[1]: A photosensitive resin composition containing 0.1 to 20 parts by mass of component (A) with respect to 100 parts by mass of component (B), and these components dissolved in solvent (C).
[2]: Contains 0.1 to 20 parts by weight of component (A), 5 to 100 parts by weight of component (D) with respect to 100 parts by weight of component (B), and these components are dissolved in solvent (C). Photosensitive resin composition.
[3]: 0.1 to 20 parts by weight of component (A), 5 to 100 parts by weight of component (D) are contained in 100 parts by weight of component (B), and these components are dissolved in solvent (C). The photosensitive resin composition further comprising 1 to 50 parts by mass of the crosslinking agent as component (E) for 100 parts by mass of the total of components (A) and (B) Composition.
　本発明の感光性樹脂組成物における固形分の割合は、各成分が均一に溶剤に溶解している限り、特に限定されるものではないが、例えば１乃至８０質量％であり、また例えば５乃至６０質量％であり、または１０乃至５０質量％である。ここで、固形分とは、感光性樹脂組成物の全成分から（Ｃ）溶剤を除いたものをいう。 The ratio of the solid content in the photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1 to 80% by mass, and for example, 5 to 60% by mass or 10 to 50% by mass. Here, solid content means what remove | excluded the (C) solvent from all the components of the photosensitive resin composition.
　本発明の感光性樹脂組成物の調製方法は、特に限定されないが、その調製法としては、例えば、（Ａ）成分（特定重合体）を（Ｃ）溶剤に溶解し、この溶液に（Ｂ）成分のアルカリ可溶性樹脂、（Ｄ）成分の感光剤、必要に応じて（Ｅ）成分の架橋剤、（Ｆ）成分の重合性基を２個以上有する化合物、（Ｇ）成分の酸により共有結合を形成する官能基を２個以上有する化合物を所定の割合で混合し、均一な溶液とする方法、或いは、この調製法の適当な段階において、必要に応じてその他添加剤を更に添加して混合する方法が挙げられる。 Although the preparation method of the photosensitive resin composition of this invention is not specifically limited, As the preparation method, (A) component (specific polymer) is melt | dissolved in (C) solvent, for example, (B) Component, alkali-soluble resin, component (D), photosensitizer, component (E), crosslinker, component (F), compound having two or more polymerizable groups, and covalent bond with component (G), acid A compound having two or more functional groups that form a compound is mixed at a predetermined ratio to form a uniform solution, or, at an appropriate stage of this preparation method, other additives are further added as necessary. The method of doing is mentioned.
　本発明の感光性樹脂組成物の調製にあたっては、（Ｃ）溶剤中における重合反応によって得られる共重合体の溶液をそのまま使用することができ、この場合、この（Ａ）成分の溶液に前記と同様に（Ｂ）成分、（Ｄ）成分、必要に応じて（Ｅ）成分、（Ｆ）成分、（Ｇ）成分などを入れて均一な溶液とする際に、濃度調整を目的としてさらに（Ｃ）溶剤を追加投入してもよい。このとき、特定共重合体の形成過程で用いられる（Ｃ）溶剤と、感光性樹脂組成物の調製時に濃度調整のために用いられる（Ｃ）溶剤とは同一であってもよいし、異なってもよい。 In the preparation of the photosensitive resin composition of the present invention, the solution of the copolymer obtained by the polymerization reaction in the solvent (C) can be used as it is, and in this case, the solution of the component (A) Similarly, when (B) component, (D) component, and (E) component, (F) component, (G) component, etc. are added as necessary to obtain a uniform solution, (C) ) Additional solvent may be added. At this time, the (C) solvent used in the process of forming the specific copolymer may be the same as or different from the (C) solvent used for adjusting the concentration when preparing the photosensitive resin composition. Also good.
　而して、調製された感光性樹脂組成物の溶液は、孔径が０.２μｍ程度のフィルタなどを用いて濾過した後、使用することが好ましい。 Thus, the prepared photosensitive resin composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 μm.
＜塗膜及び硬化膜＞
　本発明の感光性樹脂組成物を半導体基板（例えば、シリコン／二酸化シリコン被覆基板、シリコンナイトライド基板、金属（例えばアルミニウム、モリブデン、クロム）などが被覆された基板、ガラス基板、石英基板、ＩＴＯ基板等）の上に、回転塗布、流し塗布、ロール塗布、スリット塗布、スリットに続いた回転塗布、インクジェット塗布などによって塗布し、その後、ホットプレートまたはオーブン等で予備乾燥することにより、塗膜を形成することができる。その後、この塗膜を加熱処理することにより、感光性樹脂膜が形成される。 <Coating film and cured film>
The photosensitive resin composition of the present invention is coated with a semiconductor substrate (for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a metal (for example, aluminum, molybdenum, or chromium)), a glass substrate, a quartz substrate, or an ITO substrate. Etc.) by spin coating, flow coating, roll coating, slit coating, spin coating following slit, ink jet coating, etc., and then pre-dried in a hot plate or oven to form a coating film can do. Then, the photosensitive resin film is formed by heat-treating this coating film.
　この加熱処理の条件としては、例えば、温度７０℃乃至１６０℃、時間０．３乃至６０分間の範囲の中から適宜選択された加熱温度及び加熱時間が採用される。加熱温度及び加熱時間は、好ましくは８０℃乃至１４０℃、０．５乃至１０分間である。 As the heat treatment conditions, for example, a heating temperature and a heating time appropriately selected from the range of a temperature of 70 ° C. to 160 ° C. and a time of 0.3 to 60 minutes are adopted. The heating temperature and heating time are preferably 80 to 140 ° C. and 0.5 to 10 minutes.
　また、感光性樹脂組成物から形成される感光性樹脂膜の膜厚は、例えば０．１乃至３０μｍであり、また例えば０．２乃至１０μｍであり、更に例えば０．３乃至８μｍである。 The film thickness of the photosensitive resin film formed from the photosensitive resin composition is, for example, 0.1 to 30 μm, is, for example, 0.2 to 10 μm, and is further, for example, 0.3 to 8 μm.
　上記で得られた塗膜上に、所定のパターンを有するマスクを装着して紫外線等の光を照射し、アルカリ現像液で現像することで、材料組成により露光部と未露光部のいずれかが洗い出され、残存するパターン状の膜を必要に応じて８０℃乃至１４０℃、０．５乃至１０分間の加熱を行うことで端面のシャープなレリーフパターンが得られる。 On the coating film obtained above, a mask having a predetermined pattern is attached, irradiated with light such as ultraviolet rays, and developed with an alkali developer, so that either the exposed part or the unexposed part depends on the material composition. A relief pattern having a sharp end face can be obtained by heating the patterned film remaining after washing out at 80 ° C. to 140 ° C. for 0.5 to 10 minutes as necessary.
　使用されうるアルカリ性現像液としては、例えば、炭酸カリウム、炭酸ナトリウム、水酸化カリウム、水酸化ナトリウムなどのアルカリ金属水酸化物の水溶液、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、コリンなどの水酸化第四級アンモニウムの水溶液、エタノールアミン、プロピルアミン、エチレンジアミンなどのアミン水溶液等のアルカリ性水溶液が挙げられる。さらに、これらの現像液には、界面活性剤などを加えることもできる。 Examples of the alkaline developer that can be used include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide, and hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline. Examples include aqueous solutions of quaternary ammonium and alkaline aqueous solutions such as aqueous amine solutions such as ethanolamine, propylamine, and ethylenediamine. Further, a surfactant or the like can be added to these developers.
　上記の中、水酸化テトラエチルアンモニウム０．１乃至２．５８質量％水溶液は、フォトレジストの現像液として一般に使用されており、本発明の感光性樹脂組成物においても、このアルカリ性現像液を用いて、膨潤などの問題をひき起こすことなく良好に現像することができる。 Among the above, a tetraethylammonium hydroxide 0.1 to 2.58 mass% aqueous solution is generally used as a photoresist developer, and this alkaline developer is also used in the photosensitive resin composition of the present invention. It can be developed satisfactorily without causing problems such as swelling.
　また、現像方法としては、液盛り法、ディッピング法、揺動浸漬法など、いずれも用いることができる。その際の現像時間は、通常、１５乃至１８０秒間である。 Further, as a developing method, any of a liquid piling method, a dipping method, a rocking dipping method and the like can be used. The development time at that time is usually 15 to 180 seconds.
　現像後、感光性樹脂膜に対して流水による洗浄を例えば２０乃至１２０秒間行い、続いて圧縮空気もしくは圧縮窒素を用いてまたはスピニングにより風乾することにより、基板上の水分が除去され、そしてパターン形成された膜が得られる。 After development, the photosensitive resin film is washed with running water, for example, for 20 to 120 seconds, and then air-dried with compressed air or compressed nitrogen or by spinning to remove moisture on the substrate and form a pattern. A finished film is obtained.
　続いて、斯かるパターン形成膜に対して、熱硬化のためにポストベークを行うことにより、具体的にはホットプレート、オーブンなどを用いて加熱することにより、耐熱性、透明性、平坦化性、低吸水性、耐薬品性などに優れ、良好なレリーフパターンを有する膜が得られる。 Subsequently, the pattern forming film is subjected to post-baking for thermosetting, specifically by heating using a hot plate, an oven, etc., thereby providing heat resistance, transparency, and flatness. In addition, a film having a good relief pattern with excellent water absorption and chemical resistance can be obtained.
　ポストベークとしては、一般に、温度１４０℃乃至２７０℃の範囲の中から選択された加熱温度にて、ホットプレート上の場合には５乃至３０分間、オーブン中の場合には３０乃至９０分間処理するという方法が採られる。 The post-bake is generally processed at a heating temperature selected from the range of 140 ° C. to 270 ° C. for 5 to 30 minutes when on a hot plate and 30 to 90 minutes when in an oven. The method is taken.
　而して、斯かるポストベークにより、目的とする、良好なパターン形状を有する硬化膜を得ることができる。 Thus, a desired cured film having a good pattern shape can be obtained by such post-baking.
　以上のように、本発明の感光性樹脂組成物により、保存安定性が高く、十分高感度であり且つ現像の際に未露光部の膜減りが非常に小さく、微細なパターンを有する塗膜を形成することができる。 As described above, with the photosensitive resin composition of the present invention, a coating film having high storage stability, sufficiently high sensitivity, and very small unexposed area film thickness at the time of development and having a fine pattern. Can be formed.
　以下、実施例を挙げて本発明をさらに詳しく説明するが、本発明は、これら実施例に限定されるものではない。なお、数平均分子量及び重量平均分子量の測定は以下の通りである。
［数平均分子量及び重量平均分子量の測定］
　以下の合成例に従い得られた共重合体の数平均分子量及び重量平均分子量を、島津製作所製ＧＰＣ装置（ＳｈｏｄｅｘカラムＫＦ－８０４Ｌおよび８０３Ｌ）を用い、溶出溶媒テトラヒドロフランを流量１ｍｌ／分でカラム中に（カラム温度４０℃）流して溶離させるという条件で測定した。なお、下記の数平均分子量（以下、Ｍｎと称す。）及び重量平均分子量（以下、Ｍｗと称す。）は、ポリスチレン換算値にて表される。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these Examples. In addition, the measurement of a number average molecular weight and a weight average molecular weight is as follows.
[Measurement of number average molecular weight and weight average molecular weight]
The number average molecular weight and the weight average molecular weight of the copolymer obtained in accordance with the following synthesis example were measured using a GPC apparatus (Shodex columns KF-804L and 803L) manufactured by Shimadzu Corporation, and the elution solvent tetrahydrofuran was introduced into the column at a flow rate of 1 ml / min. (Column temperature: 40 ° C.) The measurement was performed under the condition of flowing and eluting. The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.
　以下の実施例で用いる略記号の意味は、次の通りである。
ＭＭＡ：メチルメタクリレート
ＨＥＭＡ：２－ヒドロキシエチルメタクリレート
ＨＰＭＡ：４－ヒドロキシフェニルメタクリレート
ＨＰＭＡ－ＱＤ：４－ヒドロキシフェニルメタクリレート１ｍｏｌと１，２－ナフトキノン－２－ジアジド－５－スルホニルクロリド１．１ｍｏｌとの縮合反応によって合成される化合物
ＣＨＭＩ：Ｎ－シクロヘキシルマレイミド
ＴＭＳＳＭＡ：メタクリルオキシプロピルトリス（トリメチルシロキシ）シラン
ＰＦＨＭＡ：２－（パーフルオロヘキシル）エチルメタクリレート
ＭＡＡ：メタクリル酸
ＡＩＢＮ：α、α’－アゾビスイソブチロニトリル
ＱＤ：α、α、α’－トリス（４－ヒドロキシフェニル）－１－エチル－４－イソプロピルベンゼン１ｍｏｌと１，２－ナフトキノン－２－ジアジド－５－スルホニルクロリド２ｍｏｌとの縮合反応によって合成される化合物
ＧＴ－４０１：ブタンテトラカルボン酸 テトラ（3,4-エポキシシクロヘキシルメチル) 修飾ε-カプロラクトン
Ｐ２：ヒドロキシスチレン８５％とスチレン１５％の重合体と、ヒドロキシスチレン７０％とスチレン３０％の重合体とを２：８で混合したスチレン重合体
ＰＦＨＴＭＯＳ：２－（パーフルオロヘキシル）エチルトリメトキシシラン
ＫＢＭ－５０３：３-メタクリロキシプロピルトリメトキシシラン
ＫＢＭ－４０３：３－グリシドキシプロピルトリメトキシシラン
ＫＢＭ－３０３：２－(３,４－エポキシシクロヘキシル)エチルトリメトキシシラン
３５ｗｔ％ＴＥＡＨ：３５ｗｔ％水酸化テトラエチルアンモニウム水溶液
ＰＴＭＯＳ：フェニルトリメトキシシラン
１５ＪＷＥＴ：オルガノ社製イオン交換樹脂
Ｉ９０７：２－メチルー１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパンー１－オン（ＩＲＧＡＣＵＲＥ　９０７、ＢＡＳＦ製）
ＤＥＡＢ：４，４’－ビス（ジエチルアミノ）ベンゾフェノン
ＤＰＨＡ：ジペンタエリスリトールヘキサアクリレート
８ＫＱ：８ＫＱ－２００１（大成ファインケミカル（株）製　アルカリ可溶ＵＶ硬化型アクリル樹脂）（Ｐ８)
ＰＧＭＥ：プロピレングリコールモノメチルエーテル
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
ＣＨＮ：シクロヘキサノン
ＴＨＦ：テトラヒドロフラン The meanings of the abbreviations used in the following examples are as follows.
MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate HPMA: 4-hydroxyphenyl methacrylate HPMA-QD: condensation reaction of 1 mol of 4-hydroxyphenyl methacrylate and 1.1 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride CHMI: N-cyclohexylmaleimide TMSSMA: methacryloxypropyltris (trimethylsiloxy) silane PFHMA: 2- (perfluorohexyl) ethyl methacrylate MAA: methacrylic acid AIBN: α, α′-azobisisobutyronitrile QD: 1 mol of α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene and 1,2-naphthoquinone-2-diazide-5-sulfonyl Compound GT-401 synthesized by condensation reaction with 2 mol of lolide: Butanetetracarboxylic acid tetra (3,4-epoxycyclohexylmethyl) modified ε-caprolactone P2: polymer of 85% hydroxystyrene and 15% styrene, hydroxystyrene Styrene polymer PFHTMOS in which 70% polymer and 30% styrene polymer were mixed at 2: 8: 2- (perfluorohexyl) ethyltrimethoxysilane KBM-503: 3-methacryloxypropyltrimethoxysilane KBM-403: 3 -Glycidoxypropyltrimethoxysilane KBM-303: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 35wt% TEAH: 35wt% tetraethylammonium hydroxide aqueous solution PTMOS: phenyltrimethoxysilane 15JWET: o Ion exchange resin I907 manufactured by Lugano: 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 (alkali-soluble UV curable acrylic resin manufactured by Taisei Fine Chemical Co., Ltd.) (P8)
PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate CHN: Cyclohexanone THF: Tetrahydrofuran
＜合成例１＞
　ＭＡＡ　７０．００ｇ、ＨＥＭＡ　２１８．７５ｇ、ＨＰＭＡ　４３．７５ｇ、ＭＭＡ　１９２・５０ｇ、ＣＨＭＩ　３５０．００ｇ、ＡＩＢＮ　５６．００ｇをＰＧＭＥ　１３９６．５０ｇに溶解し、９０℃にて２０時間反応させることによりアクリル重合体溶液（固形分濃度４０質量％）を得た（Ｐ１）。得られたアクリル重合体のＭｎは２，８００、Ｍｗは４，９００であった。 <Synthesis Example 1>
70.00 g of MAA, 21.75 g of HEMA, 43.75 g of HPMA, 350.00 g of MMA, 350.00 g of CHMI, and 56.00 g of AIBN were dissolved in 1396.50 g of PGME and reacted at 90 ° C. for 20 hours to obtain acrylic weight. A coalesced solution (solid concentration 40% by mass) was obtained (P1). Mn of the obtained acrylic polymer was 2,800 and Mw was 4,900.
＜合成例２＞
　ＰＦＨＴＭＯＳ　２．３４ｇ、ＫＢＭ－３０３　４．９３ｇ、３５ｗｔ％ＴＥＡＨ　０．２１ｇ、水　０．６８ｇをＴＨＦ　９．７９ｇに溶解し、４０℃にて４時間撹拌した。続いて、ＴＨＦで洗浄した１５ＪＷＥＴ　０．７３ｇを添加し、２５℃にて１時間撹拌した。次いで、廃１５ＪＷＥＴをろ過しシロキサン重合体溶液を得た（Ｐ３）。得られたシロキサン重合体のＭｎは１，９００、Ｍｗは２，２００であった。 <Synthesis Example 2>
2.34 g of PFHTMOS, 4.93 g of KBM-303, 0.21 g of 35 wt% TEAH, and 0.68 g of water were dissolved in 9.79 g of THF, and the mixture was stirred at 40 ° C. for 4 hours. Subsequently, 0.73 g of 15 JWET washed with THF was added, and the mixture was stirred at 25 ° C. for 1 hour. Next, waste 15 JWET was filtered to obtain a siloxane polymer solution (P3). Mn of the obtained siloxane polymer was 1,900 and Mw was 2,200.
＜合成例３＞
　ＰＦＨＴＭＯＳ　２．３４ｇ、ＫＢＭ－４０３　４．４５ｇ、３５ｗｔ％ＴＥＡＨ　０．２１ｇ、水　０．６８ｇをＴＨＦ　９．２１ｇに溶解し、４０℃にて４時間撹拌した。続いて、ＴＨＦで洗浄した１５ＪＷＥＴ　０．６８ｇを添加し、２５℃にて１時間撹拌した。次いで、廃１５ＪＷＥＴをろ過しシロキサン重合体溶液を得た（Ｐ４）。得られたシロキサン重合体のＭｎは２，４００、Ｍｗは２，９００であった。 <Synthesis Example 3>
2.34 g of PFHTMOS, 4.45 g of KBM-403, 0.21 g of 35 wt% TEAH and 0.68 g of water were dissolved in 9.21 g of THF and stirred at 40 ° C. for 4 hours. Subsequently, 0.68 g of 15JWET washed with THF was added and stirred at 25 ° C. for 1 hour. Next, the waste 15JWET was filtered to obtain a siloxane polymer solution (P4). Mn of the obtained siloxane polymer was 2,400 and Mw was 2,900.
＜合成例４＞
　ＰＦＨＴＭＯＳ　２．３４ｇ、ＫＢＭ－３０３　２．４６ｇ、ＰＴＭＯＳ　１．９８ｇ、３５ｗｔ％ＴＥＡＨ　０．２１ｇ、水　０．６８ｇをＴＨＦ　９．２１ｇに溶解し、４０℃にて４時間撹拌した。続いて、ＴＨＦで洗浄した１５ＪＷＥＴ　０．４８ｇを添加し、２５℃にて１時間撹拌した。次いで、廃１５ＪＷＥＴをろ過しシロキサン重合体溶液を得た（Ｐ５）。得られたシロキサン重合体のＭｎは１，９００、Ｍｗは２，４００であった。 <Synthesis Example 4>
2.34 g of PFHTMOS, 2.46 g of KBM-303, 1.98 g of PTMOS, 0.21 g of 35 wt% TEAH and 0.68 g of water were dissolved in 9.21 g of THF and stirred at 40 ° C. for 4 hours. Subsequently, 0.48 g of 15 JWET washed with THF was added and stirred at 25 ° C. for 1 hour. Next, the waste 15JWET was filtered to obtain a siloxane polymer solution (P5). Mn of the obtained siloxane polymer was 1,900 and Mw was 2,400.
＜合成例５＞
　ＨＰＭＡ－ＱＤ　２．５０ｇ、ＴＭＳＳＭＡ　２．５８ｇ、ＰＦＨＭＡ　５．２６ｇ、ＭＡＡ　０．７０ｇ、ＣＨＭＩ　１．４６ｇ、ＡＩＢＮ　０．３３ｇをＣＨＮ　５１．３ｇに溶解し、１１０℃にて２０時間撹拌させることによりアクリル重合体溶液（固形分濃度２０質量％）を得た（Ｐ６）。得られたアクリル重合体のＭｎは７，２００、Ｍｗは１１，０００であった。 <Synthesis Example 5>
By dissolving HPMA-QD 2.50 g, TMSSMA 2.58 g, PFHMA 5.26 g, MAA 0.70 g, CHMI 1.46 g, AIBN 0.33 g in CHN 51.3 g and stirring at 110 ° C. for 20 hours. An acrylic polymer solution (solid concentration 20% by mass) was obtained (P6). Mn of the obtained acrylic polymer was 7,200 and Mw was 11,000.
＜合成例６＞
　ＰＦＨＴＭＯＳ　２．３４ｇ、ＫＢＭ－５０３　４．９７ｇ、３５ｗｔ％ＴＥＡＨ　０．２１ｇ、水　０．６８ｇをＴＨＦ　９．８３ｇに溶解し、４０℃にて４時間撹拌した。続いて、ＴＨＦで洗浄した１５ＪＷＥＴ　０．７３ｇを添加し、２５℃にて１時間撹拌した。次いで、廃１５ＪＷＥＴをろ過しシロキサン重合体溶液を得た（Ｐ７）。得られたシロキサン重合体のＭｎは２，０００、Ｍｗは２，１００であった。 <Synthesis Example 6>
2.34 g of PFHTMOS, 4.97 g of KBM-503, 0.21 g of 35 wt% TEAH and 0.68 g of water were dissolved in 9.83 g of THF and stirred at 40 ° C. for 4 hours. Subsequently, 0.73 g of 15 JWET washed with THF was added, and the mixture was stirred at 25 ° C. for 1 hour. Next, waste 15 JWET was filtered to obtain a siloxane polymer solution (P7). Mn of the obtained siloxane polymer was 2,000 and Mw was 2,100.
＜実施例１乃至５及び比較例１乃至４＞
　次の表１に示す組成に従い、（Ａ）成分の溶液、（Ｂ）成分の溶液、（Ｄ）成分、（Ｅ）成分、（Ｆ）成分を所定の割合で（Ｃ）溶剤に溶解し、室温で３時間撹拌して均一な溶液とすることにより、各実施例及び各比較例の感光性樹脂組成物を調製した。 <Examples 1 to 5 and Comparative Examples 1 to 4>
According to the composition shown in the following Table 1, the solution of the component (A), the solution of the component (B), the component (D), the component (E), and the component (F) are dissolved in the solvent (C) at a predetermined ratio. The photosensitive resin composition of each Example and each comparative example was prepared by stirring at room temperature for 3 hours to make a uniform solution.
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
［接触角の評価：実施例１乃至３及び比較例１乃至３］
　感光性樹脂組成物をシリコンウェハ上にスピンコーターを用いて塗布した後、温度８０℃で１２０秒間ホットプレート上においてプリベークを行い、膜厚１．２μｍの塗膜を形成した。この塗膜を２．３８質量％の水酸化テトラメチルアンモニウム（以下、ＴＭＡＨと称す）水溶液に６０秒間浸漬した後、超純水で３０秒間流水洗浄を行った。次いでこの塗膜を温度２３０℃で３０分間加熱することによりポストベークを行い、膜厚１．０μｍの硬化膜を形成した。この硬化膜上の安息香酸メチルの接触角を協和界面科学（株）製Ｄｒｏｐ　Ｍａｓｔｅｒを用いて測定した。得られた結果を表２に示す。
［接触角の評価：実施例４、実施例５及び比較例４］
　感光性樹脂組成物をシリコンウェハ上にスピンコーターを用いて塗布した後、温度１００℃で１２０秒間ホットプレート上においてプリベークを行い、膜厚１．２μｍの塗膜を形成した。この塗膜を０．４質量％ＴＭＡＨ水溶液に６０秒間浸漬した後、超純水で３０秒間流水洗浄を行った。次いでこの塗膜を温度２３０℃で３０分間加熱することによりポストベークを行い、膜厚１．０μｍの硬化膜を形成した。この硬化膜上の安息香酸メチルの接触角を協和界面科学（株）製Ｄｒｏｐ　Ｍａｓｔｅｒを用いて測定した。得られた結果を表２に示す。 [Evaluation of Contact Angle: Examples 1 to 3 and Comparative Examples 1 to 3]
The photosensitive resin composition was applied onto a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 80 ° C. for 120 seconds to form a coating film having a thickness of 1.2 μm. This coating film was immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 60 seconds, and then washed with running ultrapure water for 30 seconds. Next, this coating film was post-baked by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a thickness of 1.0 μm. The contact angle of methyl benzoate on the cured film was measured using a Drop Master manufactured by Kyowa Interface Science Co., Ltd. The obtained results are shown in Table 2.
[Evaluation of Contact Angle: Example 4, Example 5 and Comparative Example 4]
The photosensitive resin composition was applied onto a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a thickness of 1.2 μm. This coating film was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. Next, this coating film was post-baked by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a thickness of 1.0 μm. The contact angle of methyl benzoate on the cured film was measured using a Drop Master manufactured by Kyowa Interface Science Co., Ltd. The obtained results are shown in Table 2.
［ＵＶオゾン処理耐性の評価：実施例１乃至３及び比較例１乃至３］
　感光性樹脂組成物をシリコンウェハ上にスピンコーターを用いて塗布した後、温度８０℃で１２０秒間ホットプレート上においてプリベークを行い、膜厚１．２μｍの塗膜を形成した。この塗膜を２．３８質量％ＴＭＡＨ水溶液に６０秒間浸漬した後、超純水で３０秒間流水洗浄を行った。次いでこの塗膜を温度２３０℃で３０分間加熱することによりポストベークを行い、膜厚１．０μｍの硬化膜を形成した。この硬化膜を（株）テクノビジョン製ＵＶ－３１２を用いて１０分間オゾン洗浄した。オゾン洗浄処理した膜上の安息香酸メチルの接触角を協和界面科学（株）製Ｄｒｏｐ　Ｍａｓｔｅｒを用いて測定した。得られた結果を表２に示す。ポストベーク後とUVオゾン処理後の差が20°以内のものを良好とする。
［ＵＶオゾン処理耐性の評価：実施例４、実施例５及び比較例４］
　感光性樹脂組成物をシリコンウェハ上にスピンコーターを用いて塗布した後、温度１００℃で１２０秒間ホットプレート上においてプリベークを行い、膜厚１．２μｍの塗膜を形成した。この塗膜を０．４質量％ＴＭＡＨ水溶液に６０秒間浸漬した後、超純水で３０秒間流水洗浄を行った。次いでこの塗膜を温度２３０℃で３０分間加熱することによりポストベークを行い、膜厚１．０μｍの硬化膜を形成した。この硬化膜を（株）テクノビジョン製ＵＶ－３１２を用いて１０分間オゾン洗浄した。オゾン洗浄処理した膜上の安息香酸メチルの接触角を協和界面科学（株）製Ｄｒｏｐ　Ｍａｓｔｅｒを用いて測定した。得られた結果を表２に示す。ポストベーク後とUVオゾン処理後の差が20°以内のものを良好とする。 [Evaluation of UV ozone treatment resistance: Examples 1 to 3 and Comparative Examples 1 to 3]
The photosensitive resin composition was applied onto a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 80 ° C. for 120 seconds to form a coating film having a thickness of 1.2 μm. This coating film was immersed in a 2.38 mass% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. Next, this coating film was post-baked by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a thickness of 1.0 μm. This cured film was subjected to ozone cleaning for 10 minutes using UV-312 manufactured by Technovision. The contact angle of methyl benzoate on the ozone-cleaned membrane was measured using a Drop Master manufactured by Kyowa Interface Science Co., Ltd. The obtained results are shown in Table 2. The difference between post-baking and UV ozone treatment is within 20 °.
[Evaluation of UV ozone treatment resistance: Example 4, Example 5 and Comparative Example 4]
The photosensitive resin composition was applied onto a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a thickness of 1.2 μm. This coating film was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. Next, this coating film was post-baked by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a thickness of 1.0 μm. This cured film was subjected to ozone cleaning for 10 minutes using UV-312 manufactured by Technovision. The contact angle of methyl benzoate on the ozone-cleaned membrane was measured using a Drop Master manufactured by Kyowa Interface Science Co., Ltd. The obtained results are shown in Table 2. The difference between post-baking and UV ozone treatment is within 20 °.
［濡れ性の評価：実施例１乃至３及び比較例１乃至３］
　感光性樹脂組成物をＩＴＯ－ガラス上にスピンコーターを用いて塗布した後、温度８０℃で１２０秒間ホットプレート上においてプリベークを行い、膜厚１．２μｍの塗膜を形成した。この塗膜に長さ５０μｍ、幅１００μｍの長方形パターンのマスクを介しキヤノン（株）製紫外線照射装置ＰＬＡ－６００ＦＡにより３６５ｎｍにおける光強度が５．５ｍＷ／ｃｍ２の紫外線を一定時間照射した。その後２．３８質量％ＴＭＡＨ水溶液に６０秒間浸漬することで現像を行った後、超純水で３０秒間流水洗浄を行った。次いでこの長方形パターンが形成された塗膜を温度２３０℃で３０分間加熱することによりポストベークを行い硬化させた。得られた硬化膜の長方形開口部上にクラスターテクノロジー(株)製　Ｉｎｋｊｅｔ　Ｄｅｓｉｇｎｅｒを用いて駆動波形：Ａ、繰り返し周波数：１ｋＨｚ、駆動電圧：４Ｖで約２０ｐｌの溶液を吐出した。吐出溶液は安息香酸メチルを使用した。得られた結果を表３に示す。
［濡れ性の評価：実施例４、実施例５及び比較例４］
　感光性樹脂組成物をＩＴＯ－ガラス上にスピンコーターを用いて塗布した後、温度１００℃で１２０秒間ホットプレート上においてプリベークを行い、膜厚１．２μｍの塗膜を形成した。この塗膜に長さ５０μｍ、幅１００μｍの長方形パターンのマスクを介しキヤノン（株）製紫外線照射装置ＰＬＡ－６００ＦＡにより３６５ｎｍにおける光強度が５．５ｍＷ／ｃｍ２の紫外線を一定時間照射した。その後０．４質量％ＴＭＡＨ水溶液に６０秒間浸漬することで現像を行った後、超純水で３０秒間流水洗浄を行った。次いでこの長方形パターンが形成された塗膜を温度２３０℃で３０分間加熱することによりポストベークを行い硬化させた。得られた硬化膜の長方形開口部上にクラスターテクノロジー(株)製　Ｉｎｋｊｅｔ　Ｄｅｓｉｇｎｅｒを用いて駆動波形：Ａ、繰り返し周波数：１ｋＨｚ、駆動電圧：４Ｖで約２０ｐｌの溶液を吐出した。吐出溶液は安息香酸メチルを使用した。得られた結果を表３に示す。 [Evaluation of wettability: Examples 1 to 3 and Comparative Examples 1 to 3]
The photosensitive resin composition was applied onto ITO-glass using a spin coater and then prebaked on a hot plate at a temperature of 80 ° C. for 120 seconds to form a coating film having a thickness of 1.2 μm. This coating film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5.5 mW / cm 2 for a certain period of time by means of an ultraviolet irradiation apparatus PLA-600FA manufactured by Canon Inc. through a rectangular pattern mask having a length of 50 μm and a width of 100 μm. Thereafter, development was performed by immersing in a 2.38 mass% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. Next, the coating film on which the rectangular pattern was formed was heated at 230 ° C. for 30 minutes to be post-baked and cured. About 20 pl of solution was discharged onto the rectangular opening of the obtained cured film using an Inkjet Designer manufactured by Cluster Technology Co., Ltd. with a drive waveform: A, a repetition frequency: 1 kHz, and a drive voltage: 4V. The discharge solution was methyl benzoate. The obtained results are shown in Table 3.
[Evaluation of wettability: Example 4, Example 5 and Comparative Example 4]
The photosensitive resin composition was applied onto ITO-glass using a spin coater and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a thickness of 1.2 μm. This coating film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5.5 mW / cm 2 for a certain period of time by means of an ultraviolet irradiation apparatus PLA-600FA manufactured by Canon Inc. through a rectangular pattern mask having a length of 50 μm and a width of 100 μm. Thereafter, development was performed by immersing in a 0.4% by mass TMAH aqueous solution for 60 seconds, followed by washing with running ultrapure water for 30 seconds. Next, the coating film on which the rectangular pattern was formed was heated at 230 ° C. for 30 minutes to be post-baked and cured. About 20 pl of solution was discharged onto the rectangular opening of the obtained cured film using an Inkjet Designer manufactured by Cluster Technology Co., Ltd. with a drive waveform: A, a repetition frequency: 1 kHz, and a drive voltage: 4V. The discharge solution was methyl benzoate. The obtained results are shown in Table 3.
＜濡れ性の評価基準＞
○：長方形開口部に溶液が完全に濡れ広がっている。
×：長方形開口部に溶液が濡れ広がっていない部分が観察される。
Figure JPOXMLDOC01-appb-T000018
 <Evaluation criteria for wettability>
○: The solution completely spreads out in the rectangular opening.
X: The part where the solution does not spread wet in the rectangular opening is observed.
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000019
　表２に示すように、比較例２、実施例１乃至実施例５においては、ＵＶオゾン処理後も高い接触角を示した。一方、比較例１、３、４においては、ＵＶオゾン処理後の接触角低下が大きく、十分な安息香酸メチルの撥液性が得られなかった。 As shown in Table 2, in Comparative Example 2 and Examples 1 to 5, a high contact angle was exhibited even after UV ozone treatment. On the other hand, in Comparative Examples 1, 3, and 4, the contact angle decrease after UV ozone treatment was large, and sufficient liquid repellency of methyl benzoate was not obtained.
　表３に示すように、比較例１、実施例１乃至実施例５は長方形開口部の濡れ性が良好であった。一方、比較例２乃至比較例４においては十分な濡れ性を確認することはできなかった。
  As shown in Table 3, Comparative Example 1 and Examples 1 to 5 had good wettability of the rectangular openings. On the other hand, in Comparative Examples 2 to 4, sufficient wettability could not be confirmed.

Claims (14)

  1. 下記（Ａ）成分、（Ｂ）成分、（Ｃ）溶剤及び（Ｄ）成分を含有する熱硬化可能な感光性樹脂組成物。
    （Ａ）成分：下記基（Ａ１）及び（Ａ２）を有するポリシロキサン
    （Ａ１）フッ素原子を有する有機基
    （Ａ２）熱架橋性基を有する有機基
    （Ｂ）成分：アルカリ可溶性樹脂
    （Ｃ）溶剤、
    （Ｄ）成分：感光剤。     A thermosetting photosensitive resin composition containing the following component (A), component (B), solvent (C) and component (D).
    (A) Component: Polysiloxane having the following groups (A1) and (A2) (A1) Organic group having fluorine atom (A2) Organic group having thermally crosslinkable group (B) Component: Alkali-soluble resin (C) solvent ,
    (D) Component: Photosensitizer.
  2. （Ａ２）熱架橋性基を有する有機基は、エポキシ基を有する有機基である請求項１に記載の感光性樹脂組成物。 (A2) The photosensitive resin composition according to claim 1, wherein the organic group having a thermally crosslinkable group is an organic group having an epoxy group.
  3. 下記（Ｚ１）乃至（Ｚ４）の少なくともいずれか１つを満足する請求項１または請求項２に記載の感光性樹脂組成物。
    （Ｚ１）：（Ｅ）成分である架橋剤をさらに含有する、
    （Ｚ２）：（Ｂ）成分のアルカリ可溶性樹脂が、自己架橋性基をさらに有するか、又はヒドロキシ基、カルボキシル基、アミド基及びアミノ基からなる群から選ばれる少なくとも１つの基と反応する基をさらに有する。
    （Ｚ３）：（Ｄ）成分が光ラジカル発生剤であり、さらに（Ｆ）成分であるエチレン性二重結合を２個以上有する化合物を含有する。
    （Ｚ４）：（Ｄ）成分が光酸発生剤であり、さらに（Ｇ）成分である（Ｄ）成分より発生した酸により共有結合を形成する官能基を２個以上有する化合物を含有する。     The photosensitive resin composition of Claim 1 or Claim 2 which satisfies at least any one of following (Z1) thru | or (Z4).
    (Z1): further containing a crosslinking agent as component (E),
    (Z2): The alkali-soluble resin of the component (B) further has a self-crosslinkable group or a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group. Also have.
    (Z3): The component (D) is a photoradical generator, and further contains a compound having two or more ethylenic double bonds as the component (F).
    (Z4): The component (D) is a photoacid generator, and further contains a compound having two or more functional groups that form a covalent bond with an acid generated from the component (D) which is the component (G).
  4. （Ｄ）成分がキノンジアジド化合物である請求項１または請求項２に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the component (D) is a quinonediazide compound.
  5. （Ｄ）成分がキノンジアジド化合物であり、上記（Ｚ１）及び（Ｚ２）の何れかを満足する請求項３に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 3, wherein the component (D) is a quinonediazide compound and satisfies any one of the above (Z1) and (Z2).
  6. （Ａ）成分がさらにフェニル基を有する請求項１乃至５のいずれか一項に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the component (A) further has a phenyl group.
  7. （Ａ）成分のポリシロキサンの数平均分子量がポリスチレン換算で１，０００乃至１００，０００である上記６に記載の感光性樹脂組成物。 (A) The photosensitive resin composition of said 6 whose number average molecular weight of polysiloxane of a component is 1,000 thru | or 100,000 in polystyrene conversion.
  8. （Ｂ）成分のアルカリ可溶性樹脂の数平均分子量がポリスチレン換算で２，０００乃至５０，０００である請求項１乃至７のいずれか一項に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (B) has a number average molecular weight of 2,000 to 50,000 in terms of polystyrene.
  9. （Ｂ）成分１００質量部に対して０．１～２０質量部の（Ａ）成分を含有することを特徴とする請求項１乃至８のいずれか一項に記載の感光性樹脂組成物。 9. The photosensitive resin composition according to any one of claims 1 to 8, which comprises 0.1 to 20 parts by mass of component (A) with respect to 100 parts by mass of component (B).
  10. （Ａ）成分と（Ｂ）成分の合計１００質量部に対して、（Ｄ）成分が５乃至１００質量部であることを特徴とする請求項１乃至９のいずれか一項に記載の感光性樹脂組成物。 The photosensitive property according to any one of claims 1 to 9, wherein the component (D) is 5 to 100 parts by mass with respect to 100 parts by mass of the total of the component (A) and the component (B). Resin composition.
  11. （Ａ）成分と（Ｂ）成分の合計１００質量部に対して、（Ｅ）成分が１乃至５０質量部であることを特徴とする請求項３乃至１０のいずれか一項に記載の感光性樹脂組成物。 The photosensitive property according to any one of claims 3 to 10, wherein the component (E) is 1 to 50 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B). Resin composition.
  12. 請求項１乃至１１のいずれか一項に記載の感光性樹脂組成物を用いて得られる硬化膜。 The cured film obtained using the photosensitive resin composition as described in any one of Claims 1 thru | or 11.
  13. 請求項１２に記載の硬化膜を有する表示素子。 A display element having the cured film according to claim 12.
  14. 請求項１２に記載の硬化膜を画像形成用隔壁として有する表示素子。 A display element comprising the cured film according to claim 12 as an image forming partition.
PCT/JP2019/003674 2018-02-08 2019-02-01 Photosensitive resin composition WO2019156000A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020207023999A KR20200118067A (en) 2018-02-08 2019-02-01 Photosensitive resin composition
JP2019570723A JP7406181B2 (en) 2018-02-08 2019-02-01 Photosensitive resin composition
CN201980012042.8A CN111684358A (en) 2018-02-08 2019-02-01 Photosensitive resin composition

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2018021121 2018-02-08
JP2018-021120 2018-02-08
JP2018-021121 2018-02-08
JP2018021120 2018-02-08

Publications (1)

Publication Number Publication Date
WO2019156000A1 true WO2019156000A1 (en) 2019-08-15

Family

ID=67549356

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/003674 WO2019156000A1 (en) 2018-02-08 2019-02-01 Photosensitive resin composition

Country Status (5)

Country Link
JP (1) JP7406181B2 (en)
KR (1) KR20200118067A (en)
CN (1) CN111684358A (en)
TW (1) TW201940553A (en)
WO (1) WO2019156000A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021182329A1 (en) * 2020-03-13 2021-09-16 東レ・ファインケミカル株式会社 Method for producing silicone polymer
WO2022181351A1 (en) * 2021-02-24 2022-09-01 東レ株式会社 Multilayer body, display device and method for producing display device
WO2022224826A1 (en) * 2021-04-23 2022-10-27 Jsr株式会社 Photosensitive composition
KR20220149672A (en) 2020-03-04 2022-11-08 에이지씨 가부시키가이샤 Positive photosensitive resin composition
WO2023119900A1 (en) * 2021-12-21 2023-06-29 株式会社レゾナック Photosensitive resin composition and color filter

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09208704A (en) * 1996-01-31 1997-08-12 Toshiba Corp Production of organosilicon polymeric material and colored member
JP2008107529A (en) * 2006-10-25 2008-05-08 Toray Ind Inc Photosensitive siloxane composition, cured film formed from the same and element with cured film
JP2012118354A (en) * 2010-12-01 2012-06-21 Jsr Corp Radiation-sensitive resin composition, interlayer insulating film, and method for forming interlayer insulting film
WO2013161829A1 (en) * 2012-04-27 2013-10-31 旭硝子株式会社 Partial hydrolysis condensation product, ink-repellent agent, negative-type photosensitive resin composition, cured film, partition wall, and optical element
WO2015163379A1 (en) * 2014-04-25 2015-10-29 旭硝子株式会社 Negative photosensitive resin composition, partition, and optical element

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10197715A (en) 1997-01-10 1998-07-31 Canon Inc Production of color filter for liquid crystal, color filter for liquid crystal and liquid crystal panel produced by the same method
JP3911775B2 (en) 1997-07-30 2007-05-09 セイコーエプソン株式会社 Manufacturing method of organic EL element
CN100530758C (en) 1998-03-17 2009-08-19 精工爱普生株式会社 Thin film pattering substrate and surface treatment
JP4138117B2 (en) 1998-12-21 2008-08-20 セイコーエプソン株式会社 Manufacturing method of color filter substrate
JP4687315B2 (en) 2005-08-04 2011-05-25 東レ株式会社 Photosensitive resin composition, cured film formed therefrom, and element having cured film
JP5516484B2 (en) 2011-04-13 2014-06-11 ダイキン工業株式会社 Positive-type liquid repellent resist composition
JP6398774B2 (en) 2014-02-18 2018-10-03 Ａｇｃ株式会社 Negative photosensitive resin composition, cured resin film, partition and optical element
WO2017126610A1 (en) * 2016-01-20 2017-07-27 日産化学工業株式会社 Positive photosensitive resin composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09208704A (en) * 1996-01-31 1997-08-12 Toshiba Corp Production of organosilicon polymeric material and colored member
JP2008107529A (en) * 2006-10-25 2008-05-08 Toray Ind Inc Photosensitive siloxane composition, cured film formed from the same and element with cured film
JP2012118354A (en) * 2010-12-01 2012-06-21 Jsr Corp Radiation-sensitive resin composition, interlayer insulating film, and method for forming interlayer insulting film
WO2013161829A1 (en) * 2012-04-27 2013-10-31 旭硝子株式会社 Partial hydrolysis condensation product, ink-repellent agent, negative-type photosensitive resin composition, cured film, partition wall, and optical element
WO2015163379A1 (en) * 2014-04-25 2015-10-29 旭硝子株式会社 Negative photosensitive resin composition, partition, and optical element

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20220149672A (en) 2020-03-04 2022-11-08 에이지씨 가부시키가이샤 Positive photosensitive resin composition
WO2021182329A1 (en) * 2020-03-13 2021-09-16 東レ・ファインケミカル株式会社 Method for producing silicone polymer
CN115244109A (en) * 2020-03-13 2022-10-25 东丽精细化工株式会社 Method for producing siloxane polymer
CN115244109B (en) * 2020-03-13 2023-07-07 东丽精细化工株式会社 Process for producing siloxane polymer
EP4119596A4 (en) * 2020-03-13 2024-04-17 Toray Fine Chemicals Co., Ltd. Method for producing silicone polymer
WO2022181351A1 (en) * 2021-02-24 2022-09-01 東レ株式会社 Multilayer body, display device and method for producing display device
WO2022224826A1 (en) * 2021-04-23 2022-10-27 Jsr株式会社 Photosensitive composition
WO2023119900A1 (en) * 2021-12-21 2023-06-29 株式会社レゾナック Photosensitive resin composition and color filter

Also Published As

Publication number Publication date
TW201940553A (en) 2019-10-16
JPWO2019156000A1 (en) 2021-02-04
JP7406181B2 (en) 2023-12-27
KR20200118067A (en) 2020-10-14
CN111684358A (en) 2020-09-18

Similar Documents

Publication Publication Date Title
JP7406181B2 (en) Photosensitive resin composition
JP7239895B2 (en) Photosensitive resin composition
WO2017217292A1 (en) Photosensitive resin composition, photosensitive sheet, cured film, element, organic el display device, semiconductor electronic component, semiconductor device, and method for production of organic el display device
JP2024038456A (en) Formation method of bank pattern
JP6826327B2 (en) Positive photosensitive resin composition
KR101334753B1 (en) Method for manufacturing transparent cured film using positive-working photosensitive resin layer for half exposure
CN110537147B (en) Photosensitive resin composition
JP7041402B2 (en) Photosensitive resin composition
JP7324581B2 (en) Bank pattern formation method
WO2021014956A1 (en) Photosensitive resin composition
WO2023095785A1 (en) Photosensitive resin composition, cured article, organic el display device, semiconductor device, and method for producing cured article
WO2015076219A1 (en) Liquid crystal display element and radiation-sensitive resin composition
WO2022168732A1 (en) Positive-acting photosensitive resin composition
WO2024024501A1 (en) Positive photosensitive resin composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19751296

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019570723

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20207023999

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 19751296

Country of ref document: EP

Kind code of ref document: A1