WO2020179744A1 - Composition de résine photosensible négative, procédé de production de film durci l'utilisant, et panneau tactile - Google Patents

Composition de résine photosensible négative, procédé de production de film durci l'utilisant, et panneau tactile Download PDF

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Publication number
WO2020179744A1
WO2020179744A1 PCT/JP2020/008738 JP2020008738W WO2020179744A1 WO 2020179744 A1 WO2020179744 A1 WO 2020179744A1 JP 2020008738 W JP2020008738 W JP 2020008738W WO 2020179744 A1 WO2020179744 A1 WO 2020179744A1
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WIPO (PCT)
Prior art keywords
resin composition
photosensitive resin
negative photosensitive
group
cured film
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PCT/JP2020/008738
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English (en)
Japanese (ja)
Inventor
福崎雄介
妹尾将秀
Original Assignee
東レ株式会社
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Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to JP2020515784A priority Critical patent/JP7405075B2/ja
Priority to KR1020217023351A priority patent/KR20210135217A/ko
Priority to CN202080016528.1A priority patent/CN113474730A/zh
Publication of WO2020179744A1 publication Critical patent/WO2020179744A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/068—Polysiloxanes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

Definitions

  • the present invention relates to a negative photosensitive resin composition containing a siloxane resin having a radically polymerizable group, a monoma having a radically polymerizable group, and a photoradical polymerization initiator, a method for producing a cured film using the same, and a touch panel. ..
  • the touch panel is composed of a display unit such as a liquid crystal panel and a touch panel sensor or the like that detects information input at a specific position.
  • the touch panel method is roughly classified into a resistive film method, a capacitance method, an optical method, an electromagnetic induction method, an ultrasonic method, and the like, depending on the input position detection method.
  • a capacitance type touch panel is widely used because of its optical brightness, excellent design, simple structure, and excellent functionality.
  • a transparent electrode substrate having a transparent electrode formed on the substrate is used for the display unit of the touch panel, and as the transparent electrode, indium oxide (ITO) doped with tin has been conventionally used.
  • a photosensitive resin composition which is excellent in pattern processability and gives sufficient chemical resistance and substrate adhesion even at low temperature curing of 150° C. or lower
  • a photoreactive resin containing an ethylenically unsaturated group and a carboxyl group is used as a photosensitive resin composition which is excellent in pattern processability and gives sufficient chemical resistance and substrate adhesion even at low temperature curing of 150° C. or lower.
  • a photosensitive resin composition containing a specific epoxy compound, a specific polyfunctional epoxy compound and a photopolymerization initiator see, for example, Patent Document 1 has been proposed.
  • an adhesion promoter containing a siloxane oligomer having a crosslinkable functional group, a photopolymerization initiator, and a coordination compound of aluminum and/or zirconium is used as a raw material composition of an insulating coating having excellent adhesion and chemical resistance.
  • a composition for an insulating material to be contained (for example, see Patent Document 2) has been proposed.
  • benzoin-based, benzophenone-based, thioxanthone-based, acetophenone-based, and acylphosphine-based agents are known as photoradical polymerization initiators.
  • oxime ester-based products have also been introduced (see Patent Document 3 and Patent Document 4).
  • the present invention was devised in view of the problems of the prior art, and has a high resolution and a high pencil hardness even when cured at a low temperature of 150° C. or lower, excellent in chemical resistance, weather resistance, electrode and wiring processing. It is an object of the present invention to provide a negative type photosensitive resin composition capable of forming a cured film capable of suppressing the generation of outgas at the time.
  • the object of the present invention is achieved by the following means.
  • the following negative photosensitive resin composition (A) A siloxane resin having a radically polymerizable group, (B) a monoma having a radically polymerizable group, and (C) having a light absorption peak in the wavelength region of 350 to 370 nm, and the absorbance at a wavelength of 400 nm is that of the absorbance at a wavelength of 365 nm.
  • a negative photosensitive resin composition containing 10% or less of a photo radical polymerization initiator.
  • Method for producing a cured film which comprises a step of applying the negative photosensitive resin composition of the present invention onto a substrate, a step of exposing the composition, and a step of curing the exposed composition at a temperature of 150° C. or lower. ..
  • a touch panel having a substrate, electrodes and/or wirings containing copper, and a cured film obtained by curing the negative photosensitive resin composition of the present invention.
  • the negative photosensitive resin composition of the present invention has a high resolution. According to the negative photosensitive resin composition of the present invention, even when cured at a low temperature of 150° C. or less, the pencil hardness is high, the chemical resistance and the weather resistance are high. It is possible to obtain a cured film having excellent properties and capable of suppressing the generation of outgas during processing of electrodes and wiring.
  • the negative photosensitive resin composition of the present invention contains at least (A) a siloxane resin having a radical polymerizable group (hereinafter sometimes simply referred to as “(A) siloxane resin”) and (B) a radical polymerizable group.
  • the radical polymerization of the monoma having the (A) siloxane resin radical-polymerizable group and (B) radical-polymerizable group proceeds in the light irradiation section. It is possible to process a negative type pattern in which the light irradiation portion is insolubilized.
  • the siloxane resin has a siloxane skeleton having high heat resistance and weather resistance in the main chain, has a radically polymerizable group, and the silanol condensation reaction proceeds even at 150 ° C. or lower.
  • the crosslink density of the cured film can be increased, chemical resistance and weather resistance can be improved, and the pencil hardness can be increased.
  • the present invention in the exposure using a general ultra-high pressure mercury lamp or LED as a light source having a strong emission line emission spectrum for i-line (wavelength 365 nm), the present invention causes an absorption peak in a wavelength region of 350 to 370 nm.
  • the photoradical polymerization initiator By using the photoradical polymerization initiator to have, the concentration of radicals generated in the light irradiation section is increased, and the reaction of the radically polymerizable group is promoted.
  • the crosslink density of the film due to photocuring can be increased, and the pencil hardness and chemical resistance can be improved.
  • the weather resistance can be improved and the outgas during electrode and wiring processing can be reduced.
  • the photoradical polymerization initiator of the present invention having an absorbance at a wavelength of 400 nm of 10% or less of the absorbance at a wavelength of 365 nm can improve the resolution because it suppresses the absorption of long-wavelength light which causes a decrease in the resolution. it can.
  • the absorbance at each wavelength, and h-line (405 nm) or g having an emission spectrum having a wavelength longer than that of i-line was selected as an index of the absorbance in a wavelength region such as a line (436 nm).
  • the fact that the absorbance at a wavelength of 400 nm is 10% or less of the absorbance at a wavelength of 365 nm means that light in the wavelength region of the i-line is selectively absorbed.
  • the negative photosensitive resin composition of the present invention contains (A) a siloxane resin.
  • the siloxane resin refers to a polymer having a repeating unit having a siloxane skeleton.
  • the siloxane resin (A) in the present invention has a radically polymerizable group, and a hydrolyzed condensate of an organosilane compound having a radically polymerizable group is preferable.
  • a hydrolyzable group is directly linked to the silicon atom of this organosilane compound. Examples of the hydrolyzable group include an alkoxy group and a carboxyl group.
  • the weight average molecular weight (Mw) of the (A) siloxane resin is preferably 500 or more, more preferably 1,000 or more, from the viewpoint of further improving chemical resistance.
  • the Mw of the siloxane resin (A) is preferably 10,000 or less, more preferably 5,000 or less, from the viewpoint of improving the solubility in the developing solution when forming a pattern.
  • (A) Mw of the siloxane resin means a polystyrene-equivalent value measured by gel permeation chromatography (GPC).
  • Examples of the radically polymerizable group include a vinyl group, an ⁇ -methylvinyl group, an allyl group, a styryl group, a (meth) acryloyl group and the like.
  • a (meth) acryloyl group is preferable from the viewpoint of further improving the pencil hardness of the cured film and the sensitivity during pattern processing.
  • the double bond equivalent of the siloxane resin (A) is preferably 150 g / mol or more, and more preferably 200 g / mol or more, from the viewpoint of improving the adhesion to the underlying substrate.
  • the double bond equivalent of the (A) siloxane resin is preferably 2,000 g/mol or less from the viewpoint of further increasing the crosslink density of the cured film, further improving the chemical resistance, and further increasing the pencil hardness. , 500 g / mol or less is more preferable.
  • the double bond equivalent of the acryloyl group and the meta-acryloyl group combined further increases the crosslink density of the cured film and is resistant to chemicals. From the viewpoint of further improving the properties and increasing the pencil hardness, 2,000 g / mol or less is preferable, and 1,500 g / mol or less is more preferable.
  • the double bond equivalent of the siloxane resin can be calculated by measuring the iodine value. ..
  • organosilane compound having a radically polymerizable group examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldi (methoxyethoxy) silane, and allyl.
  • 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane from the viewpoint of further improving the pencil hardness of the cured film and the sensitivity during pattern processing.
  • -Methoxyloxypropyltriethoxysilane is preferred.
  • the siloxane resin (A) may be a hydrolyzed condensate of the above-mentioned organosilane compound having a radically polymerizable group and another organosilane compound. Also in the latter organosilane compound, it is preferable that a hydrolyzable group is directly bonded to a silicon atom. Examples of the hydrolyzable group include an alkoxy group and a carboxyl group.
  • organosilane compounds examples include methyltrimethoxysilane, methyltriethoxysilane, methyltri (methoxyethoxy) silane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, and ethyltri.
  • methyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like are preferable.
  • the siloxane resin (A) of the present invention can be obtained by hydrolyzing and condensing the above-mentioned organosilane compound.
  • it can be obtained by hydrolyzing an organosilane compound having a hydrolyzable group and then subjecting the obtained silanol compound to a condensation reaction in the presence of an organic solvent or in the absence of a solvent.
  • the (A) siloxane resin is not completely condensed, and a hydrolyzable group or a silanol group remains. preferable. When these functional groups disappear, the molecular weight is increased and further cross-linking causes difficulty in dissolving or dispersing in a solvent or mixing with other additives.
  • Various conditions of the hydrolysis reaction can be appropriately set in consideration of the reaction scale, the size and shape of the reaction vessel, and the like. For example, it is preferable to add an acid catalyst and water to the organosilane compound in a solvent over 1 to 180 minutes, and then react at room temperature to 110 ° C. for 1 to 180 minutes. By carrying out the hydrolysis reaction under such conditions, a rapid reaction can be suppressed.
  • the reaction temperature is more preferably 30 to 105 ° C.
  • the hydrolysis reaction is preferably carried out in the presence of an acid catalyst.
  • an acid catalyst an acidic aqueous solution containing formic acid, acetic acid, phosphoric acid and nitric acid is preferable.
  • the amount of the acid catalyst added is preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the total organosilane compound used in the hydrolysis reaction. By setting the amount of the acid catalyst within the above range, the hydrolysis reaction can proceed more efficiently.
  • a condensation reaction by heating the reaction solution as it is at 50 ° C. or higher and below the boiling point of the solvent for 1 to 100 hours after generating a silanol group by a hydrolysis reaction of the organosilane compound to obtain a silanol compound. Further, in order to increase the degree of polymerization of polysiloxane, reheating or addition of a base catalyst may be performed.
  • organic solvent used for the hydrolysis reaction of the organosilane compound and the condensation reaction of the silanol compound examples include, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentene.
  • Alcohols such as tanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, 1-t-butoxy-2-propanol, diacetone alcohol; glycols such as ethylene glycol and propylene glycol; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethyl ether, etc.
  • glycols such as ethylene glycol and propylene glycol
  • Ethylene glycol monomethyl ether ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propy
  • Ethers methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, 2-heptanone, and other ketones; dimethylformamide, dimethylacetamide, and other amides; ethyl acetate, propyl acetate , Butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate and other acetates; toluene , Aromatic or aliphatic hydrocarbons such as xylene, hexane and cyclohexane, ⁇ -butyrolactone, N
  • diacetone alcohol propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol mono t-butyl ether, propylene glycol monopropyl ether, propylene glycol Monobutyl ether, ⁇ -butyrolactone and the like are preferably used.
  • a solvent When a solvent is generated by the hydrolysis reaction, it is also possible to hydrolyze without a solvent. It is also preferable to adjust the concentration to an appropriate level as the resin composition by further adding a solvent after the reaction is completed. Further, depending on the purpose, after hydrolysis, an appropriate amount of the produced alcohol or the like may be distilled off and removed under heating and / or reduced pressure, and then a suitable solvent may be added.
  • the amount of the solvent used in the hydrolysis reaction is preferably 80 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the total organosilane compound. By setting the amount of the solvent within the above range, the hydrolysis reaction can proceed more efficiently.
  • the water used for the hydrolysis reaction is preferably ion-exchanged water.
  • the amount of water is preferably 1.0 to 4.0 mol per 1 mol of silicon atom.
  • the content of the siloxane resin having a radically polymerizable group (A) in the negative photosensitive resin composition of the present invention increases the crosslink density of the cured film by the silanol condensation reaction to increase the pencil hardness of the cured film, and the electrode. From the viewpoint of further suppressing the generation of outgas during wiring processing, 30% by mass or more is preferable, 40% by mass or more is more preferable, and 50% by mass or more is further preferable. On the other hand, from the viewpoint of further improving the chemical resistance of the cured film, the content of the (A) siloxane resin is preferably 70% by mass or less, more preferably 60% by mass or less in the solid content.
  • the negative photosensitive resin composition of the present invention contains (B) a monomer having a radically polymerizable group.
  • the radically polymerizable group the group exemplified as the radically polymerizable group of the (A) siloxane resin is preferable, and the (meth) acryloryl group is more preferable.
  • (B) monomers having radically polymerizable groups are (B1) polyfunctional monomers and (B2) aromatic rings and / or It is preferable to contain a monomer having an alicyclic carbon ring.
  • the (B1) polyfunctional monomer refers to a compound having two or more radically polymerizable groups, and preferably has two or more (meth) acryloyl groups.
  • Examples of the compound having two (meth) acryloyl groups include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylpropantri (meth) acrylate, glycerin di (meth) acrylate, and tripropylene glycol di.
  • Compounds having three or more (meth) acryloyl groups include, for example, glycerintri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and penta.
  • a compound having two or more radically polymerizable groups shall be classified as (B1) polyfunctional monoma even if it contains an aromatic ring or an alicyclic carbon ring.
  • Examples of the monomer having an aromatic ring and / or an alicyclic carbon ring include 2,2- [9H-fluorene-9,9-diylbis (1,4-phenylene) bisoxy] diethanoldi (meth).
  • Examples thereof include acrylates, acrylates such as dimethyloltricyclodecanedi (meth) acrylates and ethoxylated bisphenol A di (meth) acrylates. You may contain 2 or more types of these.
  • the content of the (B2) monoma having an aromatic ring and / or an alicyclic carbon ring in the negative photosensitive resin composition of the present invention is from the viewpoint of increasing the hydrophobicity of the cured film and further improving the chemical resistance. , 10% by mass or more, more preferably 15% by mass or more, based on the solid content.
  • the content of the monoma having an aromatic ring and / or an alicyclic carbon ring is in the solid content. It is preferably 35% by mass or less, and more preferably 25% by mass or less.
  • the total content of the monomer having a radically polymerizable group is preferably 20% by mass or more, preferably 30% by mass or more, from the viewpoint of increasing the crosslink density and hydrophobicity of the cured film to further improve the chemical resistance. The above is more preferable.
  • the negative photosensitive resin composition of the present invention contains (C) a photoradical polymerization initiator having an absorption peak in the wavelength region of 350 to 370 nm and having an absorbance at a wavelength of 400 nm of 10% or less of the absorbance at a wavelength of 365 nm.
  • C photoradical polymerization initiators
  • examples of such (C) photoradical polymerization initiators include TR-PBG-326, TR-PBG-331, TR-PBG-345 (trade name, all manufactured by TRONLY), and "Irgacure” (registered trademark).
  • OXE03 trade name, manufactured by BASF
  • NCI-738 trade name, manufactured by ADEKA Corporation
  • those containing two or more ketoxime ester groups in one molecule represented by the following general formula (1), such as TR-PBG-345, are particularly preferable.
  • the radical concentration can be further increased because the radicals are cleaved by light irradiation and the radicals are generated at two or more places.
  • the reaction of radically polymerizable groups is promoted, so that the crosslink density of the film due to photocuring can be increased, and the pencil hardness and chemical resistance can be further improved.
  • the weather resistance can be further improved and the outgas during electrode and wiring processing can be reduced.
  • the oxime ester group is a ketooxime ester group, high transparency can be maintained even after light irradiation.
  • n is an integer of 2 or more. n is preferably 6 or less, more preferably 4 or less, and further preferably 3 or less.
  • R 1 represents a hydrogen atom, an alkyl group or a phenyl group, and from the viewpoint of reactivity, a methyl group that produces a highly reactive methyl radical with little steric hindrance is most preferred.
  • R 2 represents an alkyl group, a cycloalkyl group or a cycloalkylalkyl group, and the number of carbon atoms is preferably 1 to 7 from the viewpoint of solubility in a solvent. In the general formula (1), there are a plurality of R 1 and R 2 respectively.
  • R 1 may be the same or different.
  • R 2 may be the same or different.
  • Ar represents an aromatic group.
  • Ar may contain nitrogen, oxygen, sulfur, and a carbonyl group, as disclosed in Patent Documents 3 and 4. And Ar includes the following structures, bonds between these structures, and those to which other functional groups are bonded.
  • the absorption peak wavelength and absorbance of the photoradical polymerization initiator can be determined by the following methods. First, the photoradical polymerization initiator is diluted with propylene glycol methyl ether acetate to a concentration of 0.001% by weight. The absorbance of the obtained diluent is measured at a wavelength of 300 to 400 nm using an ultraviolet-visible spectrophotometer UV-2600 (manufactured by Shimadzu Corporation). From the obtained absorbance spectrum, the absorption peak wavelength, the absorbance at a wavelength of 365 nm, and the absorbance at a wavelength of 400 nm can be obtained, respectively.
  • UV-2600 ultraviolet-visible spectrophotometer
  • the content of the (C) photoradical polymerization initiator in the negative photosensitive resin composition of the present invention sufficiently promotes radical curing, further improves chemical resistance, increases pencil hardness, and processes electrodes and wiring. From the viewpoint of further suppressing the generation of outgas at the time, 0.1% by weight or more is preferable, 1% by weight or more is more preferable, and 4% by weight or more is further preferable. On the other hand, from the viewpoint of (C) suppressing the residue of the photoradical polymerization initiator to further improve the chemical resistance and suppressing excessive radical generation to further improve the resolution, the (C) photoradical polymerization initiator is contained. The amount is preferably 20% by weight or less, more preferably 10% by weight or less, still more preferably 6% by weight or less in the solid content.
  • the negative photosensitive resin composition of the present invention may further contain a photoradical polymerization initiator other than the photoradical polymerization initiator represented by the general formula (1).
  • a photoradical polymerization initiator other than the photoradical polymerization initiator represented by the general formula (1).
  • an alkylphenone-based photoradical polymerization initiator. Acylphosphine oxide-based photoradical polymerization initiator, one oxime ester-based photoradical polymerization initiator in one molecule, benzophenone-based photoradical polymerization initiator, oxantone-based photoradical polymerization initiator, imidazole-based photoradical polymerization initiator, Benzothiazole-based photoradical polymerization initiator, benzoxazole-based photoradical polymerization initiator, carbazole-based photoradical polymerization initiator, triazine-based photoradical polymerization initiator, benzoic acid ester-based photoradical polymerization initiator
  • the negative photosensitive resin composition of the present invention may contain an adhesion improver such as a silane coupling agent.
  • a silane coupling agent include a silane coupling agent having a functional group such as a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group and an amino group.
  • the negative photosensitive resin composition of the present invention may contain various curing agents, and can accelerate or facilitate the curing of the negative photosensitive resin composition.
  • the curing agent include nitrogen-containing organic substances, silicone resin curing agents, metal alkoxides, metal chelates, isocyanate compounds and polymers thereof, epoxy compounds and polymers thereof, methylolated melamine derivatives, methylolated urea derivatives and the like. You may contain 2 or more types of these. Among them, a metal chelate compound, a methylolated melamine derivative, and a methylolated urea derivative are preferably used because of the stability of the curing agent and the processability of the obtained coating film.
  • thermoacid generator examples include various onium salt-based compounds such as aromatic diazonium salt, sulfonium salt, diaryliodonium salt, triarylsulfonium salt and triarylselenium salt, sulfonic acid ester and halogen compound.
  • the negative photosensitive resin composition of the present invention may contain a polymerization inhibitor.
  • a polymerization inhibitor By containing the polymerization inhibitor, the storage stability and resolution of the negative photosensitive resin composition can be further improved.
  • the polymerization inhibitor include phenol, catechol, resorcinol, hydroquinone, 4-t-butylcatechol, 2,6-di (t-butyl) -p-cresol, phenothiazine, 4-methoxyphenol and the like.
  • the content of the polymerization inhibitor in the negative photosensitive resin composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more in the solid content.
  • the content of the polymerization inhibitor is preferably 5% by mass or less, and more preferably 1% by mass or less in the solid content.
  • the negative photosensitive resin composition of the present invention may contain an ultraviolet absorber as long as it does not interfere with the effects of the present invention. By containing the ultraviolet absorber, the resolution of the negative photosensitive resin composition and the weather resistance of the cured film can be further improved.
  • an ultraviolet absorber a benzotriazole-based compound, a benzophenone-based compound, and a triazine-based compound are preferably used from the viewpoint of transparency and non-coloring property.
  • benzotriazole-based compound examples include 2- (2H benzotriazole-2-yl) phenol, 2- (2H-benzotriazole-2-yl) -4,6-t-pentylphenol, and 2- (2H benzotriazole).
  • 2--yl) -4- (1,1,3,3-tetramethylbutyl) phenol examples include 2- (2H-benzotriazole-2-yl) -6-dodecyl-4-methylphenol, 2- (2'- Hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole, RUVA-93 (trade name, manufactured by Otsuka Chemical Co., Ltd.) and the like can be mentioned.
  • benzophenone compound examples include 2-hydroxy-4-methoxybenzophenone.
  • triazine compound examples include 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-[(hexyl) oxy] -phenol, Tinuvin477 (trade name, manufactured by BASF) and the like. Can be mentioned.
  • the content of the ultraviolet absorber in the negative photosensitive resin composition of the present invention is preferably 10% by weight or less in the solid content, from the viewpoint of improving the adhesion to a substrate such as glass as the base of the cured film. 5, 5% by weight or less is more preferable.
  • the negative photosensitive resin composition of the present invention may contain a solvent.
  • a solvent By containing a solvent, each component can be uniformly dissolved.
  • the solvent include aliphatic hydrocarbons, carboxylic acid esters, ketones, ethers, alcohols and the like. You may contain 2 or more types of these. From the viewpoint of uniformly dissolving each component and improving the transparency of the obtained coating film, a compound having an alcoholic hydroxyl group and a cyclic compound having a carbonyl group are preferable.
  • Examples of the compound having an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, and 4-hydroxy-4.
  • -Methyl-2-pentanone diacetone alcohol
  • ethyl lactate butyl lactate
  • propylene glycol monomethyl ether propylene glycol monoethyl ether
  • propylene glycol mono n-propyl ether propylene glycol mono n-butyl ether
  • propylene glycol mono t-butyl ether propylene glycol mono t-butyl ether
  • 3-methoxy-1-butanol 3-methyl-3-methoxy-1-butanol and the like.
  • cyclic compound having a carbonyl group examples include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, cycloheptanone and the like. Of these, ⁇ -butyrolactone is particularly preferably used.
  • Examples of the aliphatic hydrocarbon include xylene, ethylbenzene, solvent naphtha and the like.
  • carboxylic acid ester examples include benzyl acetate, ethyl benzoate, ⁇ -butyrolactone, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butoxyethyl acetate, 3-methoxy-3-methyl-butyl acetate, diethyl oxalate.
  • Ethyl Acetate Cyclohexyl Acetate, 3-methoxy-Butyl Acetate, Methyl Acetate Acetate, Ethyl-3-ethoxypropionate, 2-Ethyl Butyl Acetate, Isopentyl Propionate, Propropylene Glycol Monomethyl Ether Propionate, Propylene Glycol Examples thereof include monoethyl ether acetate, ethyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, and propylene glycol monomethyl ether acetate.
  • ketones examples include cyclopentanone and cyclohexanone.
  • ether examples include aliphatic ethers such as propylene glycol derivatives such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tertiary butyl ether, and dipropylene glycol monomethyl ether.
  • propylene glycol derivatives such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tertiary butyl ether, and dipropylene glycol monomethyl ether.
  • the negative photosensitive resin composition of the present invention may contain a surfactant.
  • a surfactant By containing a surfactant, the flowability at the time of coating can be improved.
  • the surfactant include a fluorine-based surfactant; a silicone-based surfactant; a fluorothermally decomposable surfactant; a polyether-modified siloxane-based surfactant; a polyalkylene oxide-based surfactant; a poly (meth).
  • Acrylic surfactants such as ammonium lauryl sulfate, polyoxyethylene alkyl ether sulfate triethanolamine; cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride; lauryldimethylamine oxide, laurylcarboxymethyl Amphoteric surfactants such as hydroxyethyl imidazolium betaine; nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate and the like. You may contain 2 or more types of these.
  • fluorine-based surfactants include, for example, "Mega Fvck” (registered trademark) F142D, F172, F173, F183, F445, F470, F475, and F477 (above, DIC Corporation). ), NBX-15, FTX-218 (manufactured by Neos Co., Ltd.) and the like.
  • silicone-based surfactants include "BYK” (registered trademark) -333, BYK-301, BYK-331, BYK-345, and BYK-307 (manufactured by Big Chemie Japan Co., Ltd.). Be done.
  • Examples of commercially available products of the fluorine-containing pyrolytic surfactant include “Mega Fvck” (registered trademark) DS-21 (manufactured by DIC Corporation).
  • Commercially available products of the polyether-modified siloxane-based surfactant include, for example, “BYK” (registered trademark) -345, BYK-346, BYK-347, BYK-348, BYK-349 (above, Big Chemie Japan Co., Ltd.).
  • “Silface” registered trademark
  • SAG002, SAG005, SAG0503A, SAG008 all manufactured by Nisshin Chemical Industry Co., Ltd.
  • the negative photosensitive resin composition of the present invention may contain a dispersant.
  • the dispersant include polyacrylic acid-based dispersants, polycarboxylic acid-based dispersants, phosphoric acid-based dispersants, and silicone-based dispersants.
  • the negative photosensitive resin composition of the present invention may contain a resin other than the (A) siloxane resin, and may contain, for example, a siloxane resin having no radically polymerizable group.
  • a cured film can be obtained by curing the negative photosensitive resin composition of the present invention.
  • a method for producing the cured film a method having a step of applying the negative photosensitive resin composition of the present invention on a substrate, a step of exposing the film, and a step of curing at a temperature of 180 ° C. or lower is preferable.
  • a negative type photosensitive resin composition is applied onto a substrate to obtain a coating film.
  • the substrate include a glass base material and a resin film. Electrodes and wirings containing metals such as ITO, copper, and copper alloys may be formed on the surface of these base materials.
  • the coating method include rotary coating using a spinner, spray coating, inkjet coating, die coating, roll coating and the like.
  • the film thickness of the coating film can be appropriately selected depending on the coating method and the like. Generally, the film thickness after drying is 0.1 to 10 ⁇ m.
  • the obtained coating film is dried to obtain a dry film.
  • the drying method include heat drying, air drying, reduced pressure drying, and infrared irradiation.
  • the heating / drying device include an oven and a hot plate.
  • the drying temperature is preferably 50 to 150 ° C., and the drying time is preferably 1 minute to several hours.
  • the obtained dry film is irradiated (exposed) with chemical rays through a mask having a desired pattern to obtain an exposed film.
  • the chemical beam to be irradiated include ultraviolet rays, visible rays, electron beams, X-rays and the like.
  • the negative photosensitive resin composition of the present invention is preferably irradiated with the i-line (365 nm) of a mercury lamp or with light containing the i-line.
  • the unexposed portion is removed by developing the obtained exposed film with an alkaline developer or the like to obtain a pattern.
  • alkaline compound used in the alkaline developing solution include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; ethylamine, n-propylamine, etc.
  • TMAH tetramethylammonium hydroxide
  • alcohol amines such as triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, diethylaminoethanol
  • pyrrole piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene
  • organic alkalis such as cyclic amines such as 1,5-diazabicyclo [4,3,0] -5-nonane and morpholin.
  • the concentration of the alkaline compound in the alkaline developer is generally 0.01 to 50% by weight, preferably 0.02 to 1% by weight.
  • a surfactant such as a nonionic surfactant may be added in an amount of 0.1 to 5% by weight.
  • a water-soluble organic solvent such as ethanol, ⁇ -butyrolactone, dimethylformamide, or N-methyl-2-pyrrolidone may be added to the developer.
  • Development methods include, for example, dipping method, spraying method, paddle method and the like.
  • the obtained pattern may be rinsed with pure water or the like.
  • the pattern By heat-treating (post-baking) the obtained pattern, the pattern can be cured to obtain a patterned cured film.
  • the heat treatment may be performed in air, in a nitrogen atmosphere, or in a vacuum state.
  • the heating temperature is preferably 80 to 180 ° C., and the heating time is preferably 0.25 to 5 hours.
  • the heating temperature may be changed continuously or stepwise.
  • the touch panel of the present invention has a base material, copper-containing electrodes and / or wiring, and a cured film obtained by curing the negative photosensitive resin composition of the present invention.
  • a base material copper-containing electrodes and / or wiring
  • a cured film obtained by curing the negative photosensitive resin composition of the present invention.
  • Examples of the base material include a glass base material and a resin film.
  • Examples of electrodes and wiring include thin films and laminated films of metals such as copper, copper alloys, gold, silver, aluminum, molybdenum, and molybdenum-niobium alloys.
  • the negative photosensitive resin composition of the present invention can be cured at a low temperature of 150° C. or lower. Therefore, it can be suitably used in combination with a copper-containing electrode and / or wiring.
  • the electrodes and wiring preferably have a so-called metal mesh pattern in which conductor wires are arranged in a mesh pattern.
  • an electrode thin film containing copper is formed on the base material.
  • the method for forming the electrode thin film include physical methods such as vacuum deposition, sputtering, ion plating, and ion beam deposition; chemical vapor deposition, and the like.
  • a resist material is applied onto the electrode thin film, pattern processing is performed by photolithography technology, the electrode thin film is chemically etched with an etching solution, and the resist is peeled with a stripping solution to conduct X-axis electrode conduction. Form the wiring.
  • a transparent insulating film is formed by forming a cured film by the above-mentioned method at the intersection of the X-axis electrode conductive wiring and the Y-axis electrode conductive wiring to be formed later.
  • the connection wiring with the IC driver and the Y-axis electrode conduction wiring are formed in the same manner as the X-axis electrode conduction wiring.
  • a transparent protective film can be formed and a touch panel can be obtained by forming a cured film on a portion other than the connection portion with the IC driver at the end of the base material by the above-mentioned method.
  • the negative photosensitive resin composition of the present invention includes, for example, various protective films such as a protective film for a touch panel and a protective film for metal wiring, an insulating film for a touch panel, a glass reinforced resin layer, an insulating film for a TFT, and an interlayer insulating film. It is suitably used as various insulating films, various hard coating materials, flattening films for TFTs, overcoats for color filters, passivation films, antireflection films, optical filters, photo spacers for color filters, and microlenses. Since it has negative photosensitive properties, it is suitably used for TFT flattening films, insulating films, antireflection films, color filter overcoats, pillar materials, etc. for liquid crystals and organic EL displays.
  • various protective films such as a protective film for a touch panel and a protective film for metal wiring, an insulating film for a touch panel, a glass reinforced resin layer, an insulating film for a TFT, and an interlayer insulating film.
  • a copper-containing electrode and / or wiring is provided because it has high chemical resistance even when cured at a low temperature of 180 ° C. or lower and can suppress the generation of outgas during electrode and wiring processing. It can be suitably used as an insulating film for a touch panel, a protective film, and a glass reinforced resin layer.
  • a substrate was prepared by laminating molybdenum / niobium / copper / molybdenum / niobium on a non-alkali glass substrate (glass thickness 0.55 mm) in this order.
  • metal laminated substrate The film thicknesses of the laminated molybdenum / niobium / copper / molybdenum / niobium were 20 nm, 300 nm, and 20 nm, respectively.
  • the negative photosensitive resin composition obtained in each of Examples and Comparative Examples was spin-coated on a metal laminated substrate using a spin coater (MS-A150 manufactured by Mikasa Co., Ltd.).
  • a metal laminated substrate coated with a negative photosensitive resin composition was prebaked at 90 ° C. for 2 minutes using a hot plate (HHP-230SQ manufactured by AS ONE Corporation) to prepare a prebaked film having a film thickness of 2.3 ⁇ m.
  • the obtained prebake film was exposed to an exposure amount of 100 mJ / cm 2 (i-line conversion) using a mask aligner (LA-610 manufactured by Sanaga Denki Seisakusho Co., Ltd.) using an ultra-high pressure mercury lamp as a light source.
  • the negative photosensitive resin composition obtained in each Example and Comparative Example was spin-coated on a non-alkali glass substrate (glass thickness 0.55 mm) using a spin coater (MS-A150 manufactured by Mikasa Co., Ltd.). did.
  • the non-alkali glass substrate coated with the negative photosensitive resin composition was prebaked at 90° C. for 2 minutes using a hot plate (HHP-230SQ manufactured by As One Co., Ltd.) to prepare a prebaked film having a thickness of 2.3 ⁇ m. ..
  • the obtained prebaked film was used in a mask aligner (LA-610 manufactured by Sanei Denki Seisakusho Co., Ltd.) with an ultra-high pressure mercury lamp as a light source to form a 5, 10, 20, 30, 40, 50 ⁇ m wide 1:1 L&S pattern.
  • a mask gap of 200 ⁇ m was exposed with a mask gap of 200 ⁇ m.
  • an automatic developing device AD-1200 manufactured by Takizawa Sangyo Co., Ltd.
  • shower development was carried out for 60 seconds using a 0.5 wt% potassium hydroxide aqueous solution (manufactured by Mitsubishi Gas Chemical Co., Inc.), and then with water Rinse for 30 seconds.
  • the minimum pattern size after development was measured and used as the resolution.
  • ⁇ b * was calculated from the value of b * before and after the test using an ultraviolet-visible spectrophotometer UV-2600 (manufactured by Shimadzu Corporation) to evaluate the weather resistance.
  • the weather resistance was evaluated from ⁇ b * according to the following criteria. A or higher was accepted. A: ⁇ b * is less than 1. B: ⁇ b * is 1 or more and less than 3. C: ⁇ b * is 3 or more.
  • B and above were accepted.
  • the flask was immersed in an oil bath at 40° C., and while stirring the contents, an aqueous nitric acid solution prepared by dissolving 3.1 g of 1 mol/L nitric acid (0.1 part by weight with respect to the charged monomers) in 55.8 g of water was added dropwise. Add on funnel over 10 minutes. After stirring at 40° C. for 1 hour, the oil bath temperature was set at 70° C. and stirring was performed for 1 hour, and the oil bath was further heated to 115° C. over 30 minutes. The internal temperature of the solution reached 100° C. 1 hour after the start of temperature increase, and from there, the mixture was heated and stirred for 2 hours at an internal temperature of 100 to 120° C.
  • the flask is immersed in an oil bath at 40 ° C., and while stirring the contents, an aqueous nitric acid solution prepared by dissolving 3.0 g of 1 mol / L nitric acid (0.1 part by weight with respect to the charged monoma) in 55.8 g of water is added dropwise. It was added in a funnel over 10 minutes.
  • the oil bath temperature was set at 70° C. and stirring was performed for 1 hour, and the oil bath was further heated to 115° C. over 30 minutes.
  • the internal temperature of the solution reached 100 ° C. 1 hour after the start of temperature rise, and the mixture was heated and stirred at an internal temperature of 100 to 120 ° C. for 2 hours thereafter.
  • the flask was immersed in an oil bath at 40° C., and while stirring the contents, an aqueous nitric acid solution prepared by dissolving 2.9 g of 1 mol/L nitric acid (0.1 part by weight with respect to the charged monomers) in 56.7 g of water was added dropwise. It was added in a funnel over 10 minutes. After stirring at 40° C. for 1 hour, the oil bath temperature was set to 70° C. and stirring was performed for 1 hour, and the oil bath was heated to 115° C. over 30 minutes. The internal temperature of the solution reached 100 ° C. 1 hour after the start of temperature rise, and the mixture was heated and stirred at an internal temperature of 100 to 120 ° C. for 2 hours thereafter.
  • an aqueous nitric acid solution prepared by dissolving 2.9 g of 1 mol/L nitric acid (0.1 part by weight with respect to the charged monomers) in 56.7 g of water was added dropwise. It was added in a funnel over 10 minutes. After stirring at
  • PGMEA was added to the obtained PGMEA solution of cardo resin so that the solid content concentration was 30% by weight to obtain a cardo resin solution (PA-2).
  • PA-2 cardo resin solution
  • the acid value of the obtained cardo resin was 100 mgKOH/g.
  • a negative photosensitive resin composition C-1 having a solid content concentration of 15% by weight.
  • a cured film was prepared in the same manner as the evaluation method described in the above "Chemical resistance” or “resolution”, and each item was evaluated by the above-mentioned method. ..
  • Example 2 Example 1 except that pentaerythritol tetraacrylate ("Light acrylate (registered trademark)" PE-4A (trade name) "manufactured by Kyoeisha Chemical Co., Ltd.) was added instead of" Kayarad "DPHA (trade name)”.
  • Negative photosensitive resin composition C-2 was prepared in the same manner as in. Using the obtained negative photosensitive resin composition C-2, evaluation was performed in the same manner as in Example 1.
  • Example 3 Under a yellow light, 0.71 g of "TR-PBG-345 (trade name)" and 0.014 g of TBC were dissolved in 64.79 g of PGMEA, and 0.30 g of a 10 wt% solution of "BYK” -333 (trade name) ". , "" Kayarad "DPHA (trade name)” 2.85 g, dimethylol-tricyclodecanediacrylate ((""lightacrylate” DCP-A (trade name) "manufactured by Kyoeisha Chemical Co., Ltd.) 2.85 g, synthetic example 28.49 g of the siloxane resin solution (PS-1) obtained in 1 was added and stirred. Then, filtration was performed with a 0.20 ⁇ m filter to obtain a negative photosensitive resin composition C-3 having a solid content concentration of 15% by mass. The negative photosensitive resin composition C-3 thus obtained was used and evaluated in the same manner as in Example 1.
  • Example 4 Under yellow light, 0.43 g of “TR-PBG-345 (trade name)” and 0.014 g of TBC are dissolved in 61.69 g of PGMEA, and “0.18 g of “Tinuvin” 477 (trade name)” and “BYK”- 333 (trade name)” PGMEA 10 wt% solution 0.30 g, ""Kayarad” DPHA (trade name) 2.88 g, ""Ogsol "EA-0250P (trade name)” 5.75 g, obtained by Synthesis Example 1 28.76 g of the obtained siloxane resin solution (PS-1) was added and stirred. Then, the mixture was filtered with a 0.20 ⁇ m filter to prepare a negative photosensitive resin composition C-4 having a solid content concentration of 15% by mass. Using the obtained negative photosensitive resin composition C-4, evaluation was carried out in the same manner as in Example 1.
  • Example 5 Under yellow light, 1.10 g of “TR-PBG-345 (trade name)” and 0.014 g of TBC are dissolved in 62.74 g of PGMEA, and “0.18 g of “Tinuvin” 477 (trade name)” and ““BYK”- 333 (trade name)” PGMEA 10 mass% solution 0.30 g, ""Kayarad” DPHA (trade name) 2.74 g, ""Ogsol "EA-0250P (trade name)” 5.49 g, obtained by Synthesis Example 1 27.44 g of the obtained siloxane resin solution (PS-1) was added and stirred. Then, the mixture was filtered with a 0.20 ⁇ m filter to prepare a negative photosensitive resin composition C-5 having a solid content concentration of 15% by weight. Using the obtained negative photosensitive resin composition C-5, evaluation was carried out in the same manner as in Example 1.
  • Example 6 Under yellow light, 0.71 g of "TR-PBG-345 (trade name)" and 0.014 g of TBC are dissolved in 63.39 g of PGMEA, and 0.18 g of ""Tinuvin” 477 (trade name)” and “"BYK”- 333 (trade name)” PGMEA 10% by weight solution 0.30 g, ""Kayarad” DPHA (trade name) 4.09 g, ""Ogsol "EA-0250P (trade name)” 3.10 g, obtained by Synthesis Example 1 28.22 g of the obtained siloxane resin solution (PS-1) was added and stirred. Then, the mixture was filtered with a 0.20 ⁇ m filter to prepare a negative photosensitive resin composition C-6 having a solid content concentration of 15% by weight. Using the obtained negative photosensitive resin composition C-6, evaluation was carried out in the same manner as in Example 1.
  • Example 8 Under yellow light, 0.71 g of "TR-PBG-345 (trade name)" and 0.014 g of TBC are dissolved in 64.71 g of PGMEA, and 0.18 g of ""Tinuvin” 477 (trade name)" and ""BYK”- 0.33 g of a 10% by weight PGMEA solution of "333 (trade name)", 3.53 g of ""Kayarad” DPHA (trade name)", "05” of "OGSOL” EA-0250P (trade name)", obtained by Synthesis Example 1 23.52 g of the obtained siloxane resin solution (PS-1) was added and stirred. Then, the mixture was filtered with a 0.20 ⁇ m filter to prepare a negative photosensitive resin composition C-8 having a solid content concentration of 15% by weight. Using the obtained negative photosensitive resin composition C-8, evaluation was carried out in the same manner as in Example 1.
  • Example 9 Under yellow light, 0.71 g of "TR-PBG-345 (trade name)" and 0.014 g of TBC are dissolved in 59.53 g of PGMEA, and 0.18 g of ""Tinuvin” 477 (trade name)" and ""BYK”- 0.33 g of a 10% by weight PGMEA solution of "333 (trade name)", “Kayalad” DPHA (trade name) 2.11 g, ""Ogsol” EA-0250P (trade name)” 4.23 g, obtained by Synthesis Example 1 32.92 g of the obtained siloxane resin solution (PS-1) was added and stirred. Then, the mixture was filtered with a 0.20 ⁇ m filter to prepare a negative photosensitive resin composition C-9 having a solid content concentration of 15% by weight. The negative photosensitive resin composition C-9 obtained was used for evaluation in the same manner as in Example 1.
  • Example 10 The solid content concentration was 15 weight in the same manner as in Example 1 except that the siloxane resin solution (PS-2) obtained in Synthesis Example 2 was added instead of the siloxane resin solution (PS-1) obtained in Synthesis Example 1. % Negative photosensitive resin composition C-10 was prepared. Using the obtained negative photosensitive resin composition C-10, evaluation was carried out in the same manner as in Example 1.
  • Example 11 Solid content concentration of 15% by weight in the same manner as in Example 3 except that the siloxane resin solution (PS-2) obtained in Synthesis Example 2 was added in place of the siloxane resin solution (PS-1) obtained in Synthesis Example 1. % Negative photosensitive resin composition C-11 was prepared. The negative photosensitive resin composition C-11 obtained was used for evaluation in the same manner as in Example 1.
  • Example 12 Negative type having a solid content concentration of 15% by weight in the same manner as in Example 1 except that "TR-PBG-331 (trade name)" (manufactured by TRONLY) was added in place of "TR-PBG-345 (trade name)”.
  • Photosensitive resin composition C-12 was prepared. Using the obtained negative photosensitive resin composition C-12, evaluation was carried out in the same manner as in Example 1.
  • Example 13 Solid content concentration 15% by weight in the same manner as in Example 1 except that "Irgacure” (registered trademark) OXE03 (trademark) "(manufactured by BASF) was added instead of” TR-PBG-345 (trade name) ".
  • Negative-type photosensitive resin composition C-12 was prepared. Using the obtained negative photosensitive resin composition C-12, evaluation was carried out in the same manner as in Example 1.
  • Negative-type photosensitive resin composition was obtained in the same manner as in Example 1 except that ““IRGACURE” (registered trademark) OXE01 (trade name)” (manufactured by BASF) was added instead of “TR-PBG-345 (trade name)”.
  • Product C-14 was prepared. Using the obtained negative photosensitive resin composition C-14, evaluation was carried out in the same manner as in Example 1.
  • a negative photosensitive resin composition C-15 was prepared in the same manner as in Example 1 except that ““IRGACURE OXE02 (trade name)” (manufactured by BASF) was added instead of “TR-PBG-345 (trade name)”. Prepared. Using the obtained negative photosensitive resin composition C-15, evaluation was carried out in the same manner as in Example 1.
  • Example 1 was repeated except that "TR-PBG-345 (trade name)” was replaced with ""Adeka Archurus” (registered trademark) NCI-930 (trade name)” (manufactured by ADEKA Corporation).
  • a negative photosensitive resin composition C-17 having a solid content concentration of 15% by weight was prepared. Using the obtained negative photosensitive resin composition C-17, evaluation was carried out in the same manner as in Example 1.
  • Example 1 was repeated except that "TR-PBG-345 (trade name)” was replaced with "Adeka Archurus” (registered trademark) N-1919 (trade name) (manufactured by ADEKA Corporation). Thus, a negative photosensitive resin composition C-18 having a solid content concentration of 15% by weight was prepared. The obtained negative photosensitive resin composition C-18 was used for evaluation in the same manner as in Example 1.
  • Example 1 was repeated except that "TR-PBG-345 (trade name)” was replaced with "Adeka Archurus” (registered trademark) NCI-831 (trade name) (manufactured by ADEKA Corporation). To prepare a negative photosensitive resin composition C-19. The negative photosensitive resin composition C-19 obtained was used for evaluation in the same manner as in Example 1.
  • Negative-type photosensitive resin composition was obtained in the same manner as in Example 1 except that ““Omnirad” (registered trademark) 819 (trade name)” (manufactured by IGM) was added instead of “TR-PBG-345 (trade name)”.
  • Product C-20 was prepared. Using the obtained negative photosensitive resin composition C-20, evaluation was carried out in the same manner as in Example 1.
  • Negative photosensitive resin was prepared in the same manner as in Example 1 except that the siloxane resin solution (PS-3) obtained in Synthesis Example 3 was added in place of the siloxane resin solution (PS-1) obtained in Synthesis Example 1.
  • the composition C-21 was prepared. Using the obtained negative photosensitive resin composition C-21, evaluation was carried out in the same manner as in Example 1.
  • Negative photosensitive resin in the same manner as in Example 1 except that the acrylic resin solution (PA-1) obtained in Synthesis Example 4 was added instead of the siloxane resin solution (PS-1) obtained in Synthesis Example 1.
  • Composition C-22 was prepared. Using the obtained negative photosensitive resin composition C-22, evaluation was carried out in the same manner as in Example 1.
  • Table 1 shows the composition of the negative photosensitive resin composition (excluding TBC, surfactant, and solvent) in each Example and Comparative Example, and Table 2 shows the evaluation results.
  • the negative photosensitive resin composition produced in the examples has high resolution, high pencil hardness even when cured at 130 ° C., excellent chemical resistance and weather resistance, and generates outgas during electrode and wiring processing. It can be seen that a cured film that can be suppressed can be formed.
  • the photosensitive negative type photosensitive resin composition of the present invention has high resolution, has high pencil hardness even when cured at a low temperature of 150 ° C. or lower, has excellent chemical resistance and weather resistance, and outgas during electrode and wiring processing. Since a cured film capable of suppressing the occurrence of the above can be obtained, it can be suitably used as an insulating film for a touch panel, a protective film, and a glass-reinforced resin layer having electrodes and / or wirings containing copper.

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Abstract

L'invention concerne une composition de résine photosensible négative qui a une résolution élevée, a une dureté au crayon élevée même lorsqu'elle est durcie à une température basse inférieure ou égale à 150 °C, a une excellente résistance chimique et une excellente résistance aux intempéries, et peut former un film durci qui permet de supprimer le dégazage pendant le traitement d'électrode/câblage. Cette composition de résine photosensible négative contient (A) une résine siloxane qui a un groupe polymérisable par voie radicalaire, (B) un monomère qui a un groupe polymérisable par voie radicalaire, et (C) un initiateur de polymérisation radicalaire qui a un pic d'absorption dans la plage de longueur d'onde de 350 à 370 nm et dans lequel l'absorption de lumière à une longueur d'onde de 400 nm est inférieure ou égale à 10 % de l'absorption de lumière à une longueur d'onde de 365 nm.
PCT/JP2020/008738 2019-03-05 2020-03-02 Composition de résine photosensible négative, procédé de production de film durci l'utilisant, et panneau tactile WO2020179744A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2020515784A JP7405075B2 (ja) 2019-03-05 2020-03-02 ネガ型感光性樹脂組成物、それを用いた硬化膜の製造方法およびタッチパネル
KR1020217023351A KR20210135217A (ko) 2019-03-05 2020-03-02 네가티브형 감광성 수지 조성물, 이것을 사용한 경화막의 제조 방법 및 터치패널
CN202080016528.1A CN113474730A (zh) 2019-03-05 2020-03-02 负型感光性树脂组合物、使用它的固化膜的制造方法及触控面板

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