CN104115067B - Negative light-sensitive resin combination, cured film and touch panel component - Google Patents
Negative light-sensitive resin combination, cured film and touch panel component Download PDFInfo
- Publication number
- CN104115067B CN104115067B CN201380010587.8A CN201380010587A CN104115067B CN 104115067 B CN104115067 B CN 104115067B CN 201380010587 A CN201380010587 A CN 201380010587A CN 104115067 B CN104115067 B CN 104115067B
- Authority
- CN
- China
- Prior art keywords
- resin combination
- sensitive resin
- methyl
- negative light
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0751—Silicon-containing compounds used as adhesion-promoting additives or as means to improve adhesion
-
- 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
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Human Computer Interaction (AREA)
- Materials For Photolithography (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Position Input By Displaying (AREA)
Abstract
It is an object of the invention to provide development nargin is wide, and the excellent composition of improved in adhesion of the substrate surface with being made up of metal or inorganic matter.The present invention is negative light-sensitive resin combination, it is characterised in that at least containing the silane coupler shown in specific formula, alkali soluble resin, multifunctional acrylic monomer, optical free radical polymerization initiator.
Description
Technical field
The present invention relates to used for forming the thin film transistor (TFT)s such as liquid crystal display cells or organic EL display element (TFT) substrate
The diaphragm or dielectric film of planarization film, touch panel sensor element etc., the resin group of the interlayer dielectric of semiconductor element
The closely sealed modifying agent that compound is applicable.In addition, further relate to the negative photosensitive composition using it, the cured film formed by it,
With the touch panel component with the cured film.
Background technology
Now, the purposes of hard coat material is varied.For example, container, piece available for automobile component, cosmetics etc.
The case hardness of material, film, CD, thin display etc. is improved.As the characteristic required by hard coat material, except hardness, anti-scratch
Outside wound property, heat resistance, against weather, cementability etc. can be also enumerated.As the typical example of hard coat material, there is radical polymerization
The UV curing types hard coat material (non-patent literature 1) of type.The composition of hard coat material is：Contain the oligomeric of polymerizable group
Thing, monomer, Photoepolymerizationinitiater initiater and other additives.
Oligomer and monomer is occurred radical polymerization by UV irradiations, be thus crosslinked and obtained the film of high rigidity.
Time needed for hard coat material solidification is short, thus is improved using productivity ratio at that time.And then, due to can be used based on common
The negative photosensitive material of radical polymerization mechanism, thus have the advantages that manufacturing cost is cheap.
When negative photosensitive material is used for into various display elements and capacitive touch panel, substrate has mostly
By the pattern of the metal film production such as ITO (Indium Tin Oxide, tin indium oxide) films or Mo (Molybdenum, molybdenum).Therefore,
Negative photosensitive resin has the good bonding to ITO and Mo, is for various display elements and electrostatic capacitive
Desired characteristic in touch panel purposes.In the capacitive touch panel particularly attracted attention in recent years, ito film or
Shared area is big in the substrate for metal film, solves the hard coat material of the problem by demand.
As the method for cementability is improved, the method for addition silane coupler is widely known by the people (patent document 1).Particularly ammonia
It is high and useful that the cementability of base alkyl silane improves effect.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2000-187321 publications
Non-patent literature
Non-patent literature 1：Great Yuan Noboru ら write, " the design of material coating technique of the hard coating film based on plastic basis material and
Raising (the プ ラ ス チ ッ Network base material The center と ハ ー ド コ ー ト film To お け Ru Cai Liao Let Meter Tu Gong Ji Intraoperative of hardness
と hardness is upward) ", technical information association, on April 28th, 2005, p.301.
The content of the invention
The invention technical problem to be solved
As described above, to improve effect high and useful for the cementability of Aminoalkylsilanes, if but being improved to improve cementability
Effect and increase addition, then can be placed due to the long-time after prebake conditions and insoluble in alkaline developer.This quilt in mass production
It is considered as problem.
The problem of the present invention is that the improved in adhesion for providing the substrate surface with being made up of metal or inorganic matter is excellent, i.e.,
Make to place for a long time after prebake conditions also will not be insoluble in alkaline developer composition.
Method for solving technical problem
The present inventor is conceived to silane coupler to solve above-mentioned problem, finds silane coupled with specific structure
Agent is to solving the problems, such as to contribute.The present invention includes following composition.
That is, negative light-sensitive resin combination, it is characterised in that contain（A）Formula（1）Or formula（2）Shown silane
Coupling agent,（B）Alkali soluble resin,（C）Multifunctional acrylic monomer,（D）Optical free radical polymerization initiator,
The formula（1）For：
（N represents 0~2 integer；R1Represent the organic group or fluorine-based of 1 valency of carbon number 1~30；R1Can have and take
Dai Ji；R2Represent the organic group of the divalent of carbon number 1~6；R3Can be each identical or different, represent carbon number 1~6
Alkyl, the alkoxy of carbon number 1~6, phenyl, hydroxyl and phenoxy group；R3At least one be selected from carbon number 1~6 alcoxyl
Base, hydroxyl）；
The formula（2）For：
（ R4Represent the aryl of 1 valency of carbon number 1~12；R4There can be substituent；R5Represent the 2 of carbon number 1~6
The organic group of valency；R6Can be each identical or different, represent alkyl, the alcoxyl of carbon number 1~6 of carbon number 1~6
Base, phenyl, hydroxyl and phenoxy group；R6At least one be selected from carbon number 1~6 alkoxy, hydroxyl）.
Invention effect
The improved in adhesion of substrate surface of the negative photosensitive composition of the present invention with being made up of metal or inorganic matter is excellent
Different, alkaline developer will not dissolved in by being placed for a long time after prebake conditions yet.And then, the present invention in silane coupler due to
It can be used in combination with Cardo resins, thus also there are following effects：It can provide containing the substrate with being made up of metal or inorganic matter
The composition for being bonded excellent Cardo resins on surface.
Embodiment
The negative light-sensitive resin combination of the present invention, it is characterised in that at least containing (A) formula (1) or formula (2) institute
Silane coupler, (B) alkali soluble resin, (C) multifunctional acrylic monomer, (D) the optical free radical polymerization initiator shown.
Hereinafter, each constituent of the negative light-sensitive resin combination of the present invention is illustrated.
The negative photosensitive composition of the present invention has following formulas (A) formula (1) or silane coupled shown in formula (2)
Agent.
N represents 0~2 integer；R1Represent the organic group or fluorine-based of 1 valency of carbon number 1~30；R2Represent carbon atom
The organic group of the divalent of number 1~6；R3Can be each identical or different, represent the alkyl of carbon number 1~6, carbon number 1~
6 alkoxy, phenyl, hydroxyl and phenoxy group；R3At least one be selected from carbon number 1~6 alkoxy, hydroxyl；
R4Represent the aryl of 1 valency of carbon number 1~12；R4There can be substituent；R5Represent the divalent of carbon number 1~6
Organic group；R6Can be each identical or different, represent the alkyl of carbon number 1~6, the alkoxy of carbon number 1~6,
Phenyl, hydroxyl and phenoxy group；R6At least one be selected from carbon number 1~6 alkoxy, hydroxyl.
R1、R4There can also be the substituents such as alkoxy, aryl, phenoxy group, halogen group.Here, as R3、R6, preferably
Methoxyl group, ethyoxyl, butoxy, particularly obtain aspect, preferably methoxyl group, ethyoxyl from raw material.
As the silane coupler shown in formula (1), it can enumerate for example：Ethyl sulfonic acid 3- (trimethoxysilyl) third
Alkane -1- amine, 10- camphorsulfonic acids 3- (trimethoxysilyl) propane -1- amine, 10- camphorsulfonic acids 3- (triethoxy first
Silylation) propane -1- amine, trifluoromethanesulfonic acid 3- (trimethoxysilyl) propane -1- amine etc..
As the silane coupler shown in formula (2), it can enumerate for example：Benzene sulfonic acid 3- (trimethoxysilyl) third
Alkane -1- amine, 4- toluene sulfonic acides 3- (trimethoxysilyl) propane -1- amine, 4- toluene sulfonic acide 3- (triethoxies
Silicyl) propane -1- amine etc..
When these silane couplers are added in negative photosensitive resin, it can be used alone, can also be mixed.
As the manufacture method of these silane couplers, from ease of manufacturing, preferably by by aminoalkyl silicon
Alkane is mixed and is reacted the method to manufacture at room temperature in organic solvent with alkyl (aryl) sulfonic acid.Although it is believed that
Also a small amount of unreacted reactant can be remained in the synthetic method, but not big influence, Ke Yi are caused to adaptation improved effect
Used in the case of not being isolated especially, purify.Wherein, in order to reduce the residual quantity of amino silane, preferably by alkyl (virtue
Base) mol ratio of sulfonic acid is set to larger.
It is relative to the resin component of negative light-sensitive resin combination, i.e., relative as the addition of (A) silane coupler
In the total amount of (B) alkali soluble resin He (C) multifunctional acrylic monomer, preferably 0.5~10 mass %, more preferably 1~5
Quality %.If less than 0.5 mass %, cementability improved effect is insufficient, if more than 15 mass %, it is sometimes micro- in alkali development
Thin pattern becomes to be difficult to dissolve, resolution ratio reduction.
As (B) alkali soluble resin, it can enumerate：Polysiloxanes, acrylic resin, vinyl ether resin, poly- hydroxyl
Styrene, novolac resin, polyimides, polyamide, Cardo resins etc..(B) in alkali soluble resin, at least a portion
It is preferred that ethylenical unsaturated double bonds group, which is imported with, for improving the hardness of cured film.In these polymer, from olefinic
The easiness of the importing of unsaturated double-bond group is set out, more preferably polysiloxanes, acrylic resin, Cardo resins.In addition,
These polymer of more than two kinds can also be contained.In order to improve chemical-resistant or refractive index, further preferably Cardo resins.
Here, the inventors discovered that, using Cardo resins situation in, if addition Aminoalkylsilanes, Cardo
Resin is insoluble and produces precipitation, thus is difficult to be used in combination sometimes, but by silane coupler of the present invention, realizes and eliminate above-mentioned ask
The new effects of topic.
As (B) alkali soluble resin, preferred embodiment is enumerated below, but be not limited to this.
As polysiloxanes, particularly preferably 3 functionality alkoxysilane compound containing trialkylsilyl group in molecular structure are hydrolyzed, obtained by condensation reaction
Reaction product.As 3 functionality alkoxysilane compound containing trialkylsilyl group in molecular structure, following compound can be enumerated.
For example, MTMS, MTES, ethyl trimethoxy silane, ethyl triethoxy
Silane, hexyl trimethoxy silane, octadecyl trimethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane,
Naphthyl trimethoxy silane, anthryl trimethoxy silane, APTES, N- (2- amino-ethyls) -3- ammonia
Base propyl trimethoxy silicane, 3- (N, N- diglycidyl) TSL 8330,3- glycidoxypropyls third
Base trimethoxy silane, glycidoxypropyl MTMS, glycidoxypropyl MTES, α-contracting
Water glycerine epoxide ethyl trimethoxy silane, α-glycidoxypropyl ethyl triethoxysilane, β-glycidoxypropyl ethyl
Trimethoxy silane, β-glycidoxypropyl ethyl triethoxysilane, α-glycidoxypropyltrimewasxysilane, α-
Glycidoxypropyl triethoxysilane, β-glycidoxypropyltrimewasxysilane, β-glycidoxypropyl third
Ethyl triethoxy silicane alkane, γ-glycidoxypropyltrimewasxysilane, γ-glycidoxypropyl triethoxysilicane
Alkane, γ-glycidoxypropyl tripropoxy silane, the isopropoxy silane of γ-glycidoxypropyl three, γ-shrink
The butoxy silane of glycerine epoxide propyl group three, α-glycidoxypropyl butyl trimethoxy silane, α-glycidoxypropyl butyl three
Ethoxysilane, β-glycidoxypropyl butyl trimethoxy silane, β-glycidoxypropyl butyl triethoxysilane, γ-
Glycidoxypropyl butyl trimethoxy silane, γ-glycidoxypropyl butyl triethoxysilane, δ-glycidoxypropyl fourth
Base trimethoxy silane, δ-glycidoxypropyl butyl triethoxysilane, (3,4- epoxycyclohexyls) methyl trimethoxy epoxide silicon
Alkane, (3,4- epoxycyclohexyls) MTES, (3,4- epoxycyclohexyls) MTMS, (3,4- rings
Oxygen cyclohexyl) MTES, 2- (3,4- epoxycyclohexyls) ethyl tripropoxies silane, 2- (3,4- epoxy hexamethylenes
Base) three butoxy silane of ethyl, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 2- (3,4- epoxycyclohexyls) ethyl
Triethoxysilane, 3- (3,4- epoxycyclohexyls) propyl trimethoxy silicane, the ethoxy of 3- (3,4- epoxycyclohexyls) propyl group three
Base silane, 4- (3,4- epoxycyclohexyls) butyl trimethoxy silane, 4- (3,4- epoxycyclohexyls) butyl triethoxysilane,
Trifluoromethyl trimethoxy silane, trifluoromethyl triethoxysilane, trifluoro propyl trimethoxy silane, the ethoxy of trifluoro propyl three
Base silane etc..
And then, can be easily to poly- silicon by using the 3 functionality alkoxy silanes containing ethylenical unsaturated double bonds group
Oxygen alkane imports ethylenical unsaturated double bonds group, can improve the hardness of cured film, thus more preferably.
Specially：Vinyltrimethoxy silane, VTES, γ-methacryloxypropyl three
Methoxy silane, γ-methacryloxypropyl, γ-acryloxypropyl trimethoxy silane,
γ-acryloxypropyl triethoxysilane etc..
As acrylic resin, (methyl) acrylic acid, (methyl) acrylate are preferably subjected to radical polymerization and
Those obtained.As (methyl) acrylate, it can be used：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) third
Olefin(e) acid propyl ester, (methyl) acrylic acid ring propyl ester, (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) propylene
Sour cyclohexene ester, (methyl) acrylic acid 4- methoxycyclohexyls ester, (methyl) acrylic acid 2- cyclopropyl Epoxide carbonyls ethyl ester, (methyl)
Acrylic acid 2- cyclopentyloxy carbonyls ethyl ester, (methyl) acrylic acid 2- cyclohexyl Epoxide carbonyls ethyl ester, (methyl) acrylic acid 2- rings
Hexenyl Epoxide carbonyl ethyl ester, (methyl) acrylic acid 2- (4- methoxycyclohexyls) Epoxide carbonyl ethyl ester, (methyl) acrylic acid drop
Borneol base ester, (methyl) isobornyl acrylate, (methyl) acrylic acid tricyclodecyl ester, the cyclodecyl of (methyl) acrylic acid four
Ester, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid adamantane esters, (methyl) acrylic acid adamantyl methyl esters, (first
Base) acrylic acid 1- methyl adamantane base esters etc..Can also be by styrene, p-methylstyrene, o-methyl styrene, a methylbenzene
The aromatic ethenyl compounds such as ethene, α-methylstyrene and above-mentioned (methyl) acrylic acid or (methyl) acrylate are common
It is poly-.
In addition, anti-by making the epoxide with ethylenical unsaturated double bonds group and (methyl) acrylic acid carry out addition
Should, ethylenical unsaturated double bonds group can be imported.As the epoxide with ethylenical unsaturated double bonds group, it can enumerate following
Compound.
Specially：(methyl) glycidyl acrylate, (methyl) acrylic acid α-ethyl glycidyl ester, (methyl) propylene
Sour α-n-propyl ethylene oxidic ester, (methyl) acrylic acid α-n-butyl glycidyl ester, (methyl) acrylic acid 3,4- epoxies butyl ester,
(methyl) acrylic acid 3,4- epoxies heptyl ester, (methyl) acrylic acid α-ethyl -6,7- epoxies heptyl ester, allyl glycidyl ether,
Vinyl glycidyl ether, adjacent vinylbenzyl glycidyl base ether, a vinylbenzyl glycidyl base ether, to vinyl
Benzyl glycidyl ether, Alpha-Methyl-neighbour's vinylbenzyl glycidyl base ether, an Alpha-Methyl-vinylbenzyl glycidyl
Base ether, Alpha-Methyl-vinylbenzyl glycidyl base ether, 2,3- diglycidyl epoxides methyl styrene, 2,4- bis- are contracted
Water glyceryl epoxide methyl styrene, 2,5- diglycidyl epoxides methyl styrene, 2,6- diglycidyl epoxide first
Base styrene, 2,3,4- triglycidyl group epoxides methyl styrene, 2,3,5- triglycidyl group epoxides methyl styrene, 2,
3,6- triglycidyl group epoxides methyl styrene, 3,4,5- triglycidyl group epoxides methyl styrene, 2,4,6- tri- shrink
Glyceryl epoxide methyl styrene etc..
As Cardo resins, preferably using commercially available product, it can enumerate：OGSOL (オ グ ゾ ー Le) (registration mark) CR-
TR1, OGSOL (registration mark) CR-TR2, OGSOL (registration mark) CR-TR3, OGSOL (registration mark) CR-TR4, OGSOL
(registration mark) CR-TR5, OGSOL (registration mark) CR-TR6 (more than, it is Osaka ガ ス ケ ミ カ Le systems) etc..
In the negative light-sensitive resin combination of the present invention, the content of (B) alkali soluble resin is not particularly limited, can root
Arbitrarily selected according to desired thickness or purposes.(B) alkali soluble resin is preferably with respect to negative light-sensitive resin combination
Solid constituent adds 10~70 mass %.
The negative photosensitive composition of the present invention contains (C) polyfunctional monomer.Polyfunctional monomer refers to have in the molecule
The compound of at least two above ethylenical unsaturated double bonds.If considering free-radical polymerised easiness, preferably there is acryloyl
The polyfunctional monomer of base (ア Network リ Le base).
As concrete example, it can enumerate：Bisphenol-A diglycidyl ether (methyl) acrylate, poly- (methyl) acrylate
Carbamate, modified bisphenol A epoxy (methyl) acrylate, adipic acid 1,6-HD (methyl) acrylate, adjacent benzene two
Formic anhydride expoxy propane (methyl) acrylate, trimellitic acid diethylene glycol (DEG) (methyl) acrylate, (first of rosin modified epoxy two
Base) acrylate, the oligomer of alkyd modified (methyl) acrylate etc or tripropylene glycol two (methyl) acrylate, 1,
6- hexylene glycols two (methyl) acrylate, bisphenol-A diglycidyl ether two (methyl) acrylate, trimethylolpropane tris
(methyl) acrylate, pentaerythrite three (methyl) acrylate, triacryl dimethoxym ethane (triacrylformal), season penta
Tetrol four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, three
Pentaerythrite seven (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, [double [4- (the 2- acryloxy second of 9,9-
Epoxide) phenyl] fluorenes etc..
The negative light-sensitive resin combination of the present invention contains (D) optical free radical polymerization initiator.(D) optical free radical polymerize
As long as initiator is decomposed by light (including ultraviolet, electron ray) and/or reacted and produce free radical, can be then
Arbitrary substance.In order to further improve the hardness of cured film, preferably use：Alpha-aminoalkyl benzophenone (Off ェ ノ Application) compound,
Acylphosphine oxide compound, oxime ester compound, the benzophenone cpd with amino or the esterification of the benzoic acid with amino
Compound.Furthermore, it is possible to contain these compounds of more than two kinds.
As the concrete example of alpha-aminoalkyl benzophenone compound, it can enumerate：2- methyl-[4- (methylsulfany) phenyl] -2-
Morpholino propane -1- ketone, 2- dimethylaminos -2- (4- methyl-benzyls) -1- (4- morpholines -4- bases-phenyl)-butyl- 1- ketone, 2- benzyls
Base -2- dimethylaminos -1- (4- morphlinophenyls)-butanone -1 etc..
As the concrete example of acylphosphine oxide compound, it can enumerate：2,4,6- trimethylbenzoyl phenyls phosphine is aoxidized
Thing, double (2,4,6- trimethylbenzoyls)-phenylphosphine oxides, double (2,6- Dimethoxybenzoyls)-(2,4,4- front threes
Base amyl group)-phosphine oxide etc..
As the concrete example of oxime ester compound, it can enumerate：1- phenyl -1,2- propanedione -2- (adjacent ethoxy carbonyl) oxime, 1,
2- octanediones, 1- [4- (phenylsulfartyl) -2- (O- benzoyl oximes)], 1- phenyl -1,2- diacetyl -2- (O-methoxy carbonyls
Base) oxime, 1,3- diphenyl propane triketones -2- (adjacent ethoxy carbonyl) oxime, ethyl ketone (エ タ ノ Application), 1- [9- ethyls -6- (2- first
Base benzoyl) -9H- carbazole -3- bases] -, 1- (0- acetyl group oxime) etc..
As the concrete example of the benzophenone cpd with amino, it can enumerate：Double (dimethylamino) the hexichol first of 4,4-
Double (diethylamino) benzophenone of ketone, 4,4- etc..
As the concrete example of the benzoic acid ester compounds with amino, it can enumerate：ESCAROL 507 ethyl ester, 2-
Ethylhexyl-ESCAROL 507 ester, to diethylamino ethyl benzoate etc..
(D) content of optical free radical polymerization initiator is preferably in the solid constituent of negative light-sensitive resin combination
More than 0.01 mass %, more preferably more than 0.1 mass %.Furthermore it is preferred that for below 20 mass %, more preferably 10 mass % with
Under.By for above range, can fully carry out radically curing, and the radical polymerization initiator of residual can be prevented
Dissolution etc., so that it is guaranteed that solvent resistance.
The negative light-sensitive resin combination of the present invention can contain polymerization inhibitor.By containing polymerization inhibitor, the guarantor of composition
Deposit stability raising, and the resolution ratio in the purposes for needing pattern to process after raising development., can as the concrete example of polymerization inhibitor
Enumerate：Phenol, catechol, resorcinol, hydroquinones, 4- tert-butyl catechols, 2,6- bis- (tert-butyl group)-paracresol, fen thiophene
Piperazine, 4- metoxyphenols etc..
The content of polymerization inhibitor is preferably more than 0.01 mass %, more in the solid constituent of negative light-sensitive resin combination
Preferably more than 0.1 mass %.On the other hand, from height keep cured film hardness from the viewpoint of, preferably 5 mass % with
Under, more preferably below 1 mass %.
The negative light-sensitive resin combination of the present invention can also contain solvent.From each composition of uniform dissolution and institute can be made
From the viewpoint of the transparency raising for obtaining film, preferably using the compound with alcohol hydroxyl group or the ring-type with carbonyl
Compound.They can contain two or more.In addition, the boiling point more preferably under atmospheric pressure is 110~250 DEG C of compound.
By making boiling point be more than 110 DEG C, suitably it is dried in film, the good of no crawling can be obtained
Film.On the other hand, can be less, Ke Yijin by the residual solvent amount control in film when it is less than 250 DEG C to make boiling point
Film when one step reduces heat cure shrinks, thus available better flatness.
As with concrete example of the boiling point under alcohol hydroxyl group, atmospheric pressure for 110~250 DEG C of compound, it can enumerate：Third
Keto-alcohol, 3- hydroxy-3-methyl -2- butanone, 4- hydroxy-3-methyl -2- butanone, 5- hydroxyls -2 pentanone, 4- hydroxy-4-methyls -2-
Pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl, propane diols list n-propyl
Ether, propane diols list n-butyl ether, propane diols list tertbutyl ether, 3- methoxyl groups-n-butyl alcohol, 3- methyl -3- methoxyl groups-n-butyl alcohol
Deng.Wherein, from the viewpoint of storage stability, preferred diacetone alcohol is coated to from the viewpoint of property from difference of height, and preferably the third two
Alcohol list tertbutyl ether.
As with concrete example of the boiling point under carbonyl, atmospheric pressure for 110~250 DEG C of cyclic compound, it can enumerate：
Gamma-butyrolacton, gamma-valerolactone, δ-valerolactone, propylene carbonate, 1-METHYLPYRROLIDONE, cyclohexanone, cycloheptanone etc..Wherein,
It is preferred that gamma-butyrolacton.
In addition, the negative light-sensitive resin combination of the present invention can also contain acetate esters other than the above, ketone, ethers
Etc. various solvents.
The content of solvent is not particularly limited, and can correspond to coating method etc. and uses arbitrary amount.For example, passing through rotation
When coating carries out film forming, it is 50~95 overall mass % of negative light-sensitive resin combination that can generally make quantity of solvent.
The negative light-sensitive resin combination of the present invention, which can contain, to be promoted the solidification of resin combination or holds solidification
Easy various curing agent.It is not particularly limited as curing agent, known curing agent can be used.As concrete example, including containing
Nitrogen organic, organic siliconresin curing agent, various metal alkoxides, various metal chelate compounds, isocyanate compound and its
Polymer, methylolation melamine derivative, methylolation urea derivative etc..They can contain two or more.Wherein, from solidification
Stability, processability of gained film of agent etc. are set out, and are preferably derived using metal chelate compound, methylolation melamine
Thing, methylolation urea derivative.
In the negative light-sensitive resin combination of the present invention, in order to improve mobility during coating, fluorine system can also be contained
The various surfactants such as surfactant, silicone based surfactants.The species of surfactant is not particularly limited, can
With using for example：Fluorine system surfactant, silicone based surfactants, polyalkylene oxide system surfactant, poly- (methyl) third
Olefin(e) acid ester system surfactant etc..They two or more can be used.
As the commercially available product of fluorine system surfactant, preferably use：" MEGAFAC (メ ガ Off ァ ッ Network) " (registrar
Mark) F142D, MEGAFAC " (registration mark) F172, MEGAFAC " (registration mark) F173, MEGAFAC " (registration mark)
F183, MEGAFAC " (registration mark) F445, MEGAFAC " (registration mark) F470, MEGAFAC " (registration mark) F475,
MEGAFAC " (registration mark) F477 (more than, be that big Japan イ Application キ chemical industry (strain) is made), NBX-15, FTX-218
((strain) ネ オ ス systems).As the commercially available product of silicone based surfactants, preferably use：BYK-333、BYK-301、BYK-
331st, BYK-345, BYK-307 (PVC ッ Network ケ ミ ー ジ ャ パ Application (strain) system).
Representative manufacture method for the negative light-sensitive resin combination of the present invention is illustrated.For example, by (A) formula
Or the silane coupler shown in formula (2), (B) alkali soluble resin, (C) multifunctional acrylic monomer, (D) light are free (1)
Base polymerization initiator and other additives as needed are added in arbitrary solvent, and stirring is allowed to after dissolving, to resulting solution
Filtered, obtain negative light-sensitive resin combination.
For the forming method of the cured film of the negative light-sensitive resin combination using the present invention, citing is illustrated.
The negative light-sensitive resin combination of the present invention is passed through into micro gravure coating method, spin-coating method, dip coating, curtain stream rubbing method, roller
Method known to coating, spraying process, slot coated method etc. is coated on basal substrate, is carried out with heaters such as hot plate, baking ovens
Prebake conditions.Preferably, prebake conditions are carried out 30 seconds~30 minutes in 50~150 DEG C of scope, thickness after prebake conditions for 0.1~
15μm。
After prebake conditions, stepping exposure machine, mirror projection mask aligner (MPA), directional light mask aligner (PLA) are used
It is exposed Deng exposure machine.It is 10~4000J/m in exposure intensity2Under conditions of left and right (conversion of wavelength 365nm light exposures), every
Or do not irradiate the light across desired mask.Exposure light source is not limited, and can use the purples such as i rays, g rays, h rays
Outside line or KrF (wavelength 248nm) laser, ArF (wavelength 193nm) laser etc..
Then, exposure portion is dissolved by development, the pattern of minus can be obtained.As developing method, preferably to spray,
The methods such as dipping, stirring (パ De Le) impregnate 5 seconds~10 minutes in developer solution.As developer solution, known alkali can be used
Developer solution.As concrete example, it can enumerate containing one kind or two or more aqueous solution in following etc.：The hydroxide of alkali metal,
The amines such as the inorganic bases such as carbonate, phosphate, silicate, borate, 2- DEAE diethylaminoethanols, MEA, diethanol amine,
The quaternary ammonium salts such as TMAH, choline.After development, preferably rinsed with water, then can also be in 50~140 DEG C of scope
Baking is dried.
Then, the scope by heaters such as film hot plate, the baking ovens at 140~320 DEG C heats 15 minutes~1 hour left side
It is right.
By the present invention negative light-sensitive resin combination solidification obtained by cured film may be used as touch panel diaphragm,
Touch panel dielectric film, various hard coat materials, antireflection film, filter.Further, since with negative-type photosensitive, thus can
It is suitably used for liquid crystal or TFT planarization films, dielectric film, antireflection film, colour filter coating, the post material of organic el display
Material etc..Wherein, it can be used as requiring after the substrate and heat treatment without Si such as ITO or molybdenum and after chemical treatments particularly suitablely
The touch panel diaphragm or touch panel dielectric film of cementability.As the mode of touch panel, resistance membrane type, optics can be enumerated
Formula, induction, electrostatic capacitive etc..Capacitive touch panel specially requires chemicals-resistant treatability, thus can fit
Preferably using the cured film of the present invention.
Using the present invention cured film as touch panel diaphragm when, preferably 1.5 μm of thickness when hardness be 4H
Above, transmissivity is that more than 95%, resolution ratio is less than 20 μm.Hardness or transmissivity can be by selecting light exposure, heat curing temperature
To adjust.
Embodiment
Hereinafter, enumerate embodiment and further illustrate the present invention.The present invention is not limited by these embodiments.Synthesis example and
It is as follows using the compound of abbreviation in embodiment in compound used,
PGMEA：Propylene glycol monomethyl ether
DAA：Diacetone alcohol
MB：3- methoxyl groups-n-butyl alcohol.
The synthesis of the silane coupler solution of synthesis example 1 (a-1)
Trifluoromethanesulfonic acid 1.501g (10mmol) and 3- TSL 8330s are added into MB 62.586g
1.793g (10mmol), is stirred at room temperature 15 minutes, obtains trifluoromethanesulfonic acid 3- (trimethoxysilyl) propane -1- amine
5%MB solution (a-1).
The synthesis of the silane coupler solution of synthesis example 2 (a-2)
P-methyl benzenesulfonic acid monohydrate 1.902g (10mmol) and 3- aminopropyl trimethoxies are added into MB 64.983g
Base silane 1.793g (10mmol), is stirred at room temperature 15 minutes, obtains 4- toluene sulfonic acides 3- (trimethoxysilyl) third
The 5%MB solution (a-2) of alkane -1- amine.
The synthesis of the silane coupler solution of synthesis example 3 (a-3)
10- camphorsulfonic acids 2.323g (10mmol) and 3- TSL 8330s are added into MB 77.944g
1.793g (10mmol), is stirred at room temperature 15 minutes, obtains 10- camphorsulfonic acids 3- (trimethoxysilyl) propane -1- amine
5%MB solution (a-3).
The preparation of the silane coupler solution of synthesis example 4 (a-4)
3- TSL 8330s 1.793g (10mmol) is added into MB 34.067g, 15 points are stirred at room temperature
Clock, obtains the 5%MB solution (a-4) of 3- TSL 8330s.
The synthesis of the silane coupler solution of synthesis example 5 (a-5)
Concentrated sulfuric acid 0.981g (10mmol) and 3- TSL 8330s 1.793g is added into MB 52.706g
(10mmol), is stirred at room temperature 15 minutes, obtains the 5%MB solution of hydrogen sulfate 3- (trimethoxysilyl) propane -1- amine
(a-5)。
The synthesis of the silane coupler solution of synthesis example 6 (a-6)
Methanesulfonic acid 0.961g (10mmol) and 3- TSL 8330s 1.793g is added into MB 52.326g
(10mmol), is stirred at room temperature 15 minutes, obtains the 5%MB solution of methanesulfonic acid 3- (trimethoxysilyl) propane -1- amine
(a-6)。
The synthesis of the siloxane resin solution of synthesis example 7 (b-1)
By MTMS 13.62g (0.1 mole), phenyltrimethoxysila,e 118.98g (0.6 mole), 3-
Trimethoxy-silylpropyl butanedioic acid 39.39g (0.15 mole), γ-methacryloxypropyl trimethoxy silane
35.16g, DAA 140.87g are added in 500mL three-necked flask.Then, in room temperature while mixed liquor is stirred, while through 30 points
Clock addition dissolving phosphoric acid 0.106g (being 0.05 mass % relative to addition monomer) in water 59.4g phosphate aqueous solution.So
Afterwards, flask is impregnated in 40 DEG C of oil bath, after stirring 30 minutes, oil bath is warming up to 115 DEG C through 30 minutes.Heating starts 1
After hour, the internal temperature of solution reaches 100 DEG C, and then heating stirring 45 minutes (internal temperature is 100~110 DEG C).Reaction
In distillate methanol as accessory substance, water and amount to 89g.With the DAA solution relative to gained polysiloxanes, polymer concentration reaches
40 mass % mode adds DAA, obtains siloxane resin solution (b-1).The weight average molecular weight of resulting polymers is 7500.
The synthesis of the acrylic resin solution (b-2) of synthesis example 8
Double (isobutyronitrile) 3g, the PGMEA (methyl proxitol acetate) of 2,2 '-azo are added in 500mL flask
50g.Then, methacrylic acid 30g, styrene 22.48g, cyclohexyl methacrylate 25.13g are added.Then, it will mix
Liquid is stirred at room temperature a little while, to carrying out nitrogen displacement in flask, then in 70 DEG C of heating stirrings 5 hours.Then, in resulting solution
Middle addition GMA 15g, dimethyl benzyl amine 1g, p methoxy phenol 0.2g, PGMEA 100g, 90
DEG C heating stirring 4 hours.Added in the way of the solid component concentration of gained acrylic resin solution reaches 40 mass %
PGMEA, obtains acrylic resin solution (b-2).The weight average molecular weight of acrylic resin is 13500, and acid number is
100mgKOH/g。
The preparation of the Cardo resin solutions (b-3) of synthesis example 9
It is used as OGSOL (registration mark) CR-TR5 (Osaka ガ ス ケ ミ カ Le Co., Ltd. of Cardo resin PGMEA solution
System) it is that solid constituent is the product that 52.7%, solid constituent acid number is 135.Weigh CR-TR5 100g, addition PGMEA 31.75g
And be stirred.So obtain the Cardo resin solutions (b-3) that solid component concentration is 40 mass %.
(1) evaluation of MAM cementabilities
On alkali-free glass substrate (glass thickness 0.7mm), by MAM with 2500 angstroms of thickness, 0.3 Ω of resistance value/ mode
Form substrate.For the cured film of 1.5 μm of the thickness made on the substrate (following, to be designated as MAM substrates), according to JIS
" K5400 " 8.5.2 (nineteen ninety) checker-wise adhesive tape method, is evaluated the cementability of MAM substrates and cured film.In glass base
Cured film surface on plate, is drawn with cutter orthogonal each in length and breadth in the way of the raw material for reaching glass plate with 1mm intervals
11 parallel lines, make 1mm × 1mm grid 100.Cut cured film surface mount glassine paper adhesive tape (it is wide=
18mm, adhesion=3.7N/10mm), scraped with rubber (JIS S6050 certified products) and be allowed to closely sealed.Then, by visual observation to by
Firmly one end of the adhesive tape and residual number of grid when keeping right angle and moment stripping with plate is evaluated.Pass through the release surface of grid
Product proceeds as described below judgement,
5：Peels off area 0%
4：0~＜ of peels off area 5%
3：5~＜ of peels off area 15%
2：15~＜ of peels off area 35%
1：35~＜ of peels off area 65%
0：Peels off area 65~100%.
(2) chemical-resistant (TOK106 patience)
On alkali-free glass substrate (glass thickness 0.7mm), by ITO in the way of 200 angstroms of thickness, 100 Ω of resistance value/ shape
Into substrate.The cured film of 1.5 μm of thickness is made on the substrate (following, to be designated as ito substrate).It is allowed to soak according to following condition
Stain is in the TOK-106 as anticorrosive additive stripping liquid controlling, then according to JIS " K5400 " 8.5.2 (nineteen ninety) checker-wise adhesive tape
Method, is evaluated the cementability of ito substrate and cured film.When the peels off area of grid is less than 5%, it is judged as that there is this
Chemical-resistant under part；
Condition 1：60 DEG C, 80 seconds
Condition 2：60 DEG C, 5 minutes
Condition 3：85 DEG C, 5 minutes；
The condition being had no problem based on chemical-resistant, chemical-resistant is evaluated with 4 stages as described below；
3：Chemical-resistant is respectively provided with condition 1,2,3
2：There is chemical-resistant in condition 1,2
1：There is chemical-resistant only in condition 1
0：Without chemical-resistant in each condition.
(3) the developability change (develop nargin (マ ー ジ Application after prebake conditions) caused by being placed after prebake conditions)
Rotary coating is carried out with arbitrary revolution using spinner (ミ カ サ (strain) 1H-360S processed) on an ito substrate, will
Substrate carries out 2 minutes prebake conditions with hot plate (big Japan ス ク リ ー Application manufactures (strain) SCW-636 processed) at 110 DEG C, makes 4 films
Thickness is 1.5 μm of film.
The time of step of exposure after will transfer to is divided within 30 minutes, after 6 hours, after 12 hours, after 24 hours
4 kinds studied.Using directional light mask aligner (キ ヤ ノ Application (strain) PLA-501F processed), using ultrahigh pressure mercury lamp as light
Source, using the mask with a width of 50 μm of 1 to 1 width, with light exposure 200mJ (i rays), 100 μm of mask gap, to making
Film be exposed.Then, using automatic developing device (AD-2000, Takizawa swamp industry (strain) system), with 0.4 mass % hydroxides four
Methyl aqueous ammonium ELM-D (Mitsubishi ガ ス chemistry (strain) system) carries out spray development in 90 seconds, is then rinsed 30 seconds with water.This
When, placed after prebake conditions, pattern that also can be wide to 50 μm carries out exploring.It is evaluated as with placing abundant after prebake conditions
Degree.
Embodiment 1
Under amber light, by 2- methyl-[4- (methylsulfany) phenyl] -2- morpholino propane -1- ketone (trade name " イ Le
ガ キ ュ ア (registration mark) 907 " チ バ ス ペ シ ャ リ テ ィ ケ ミ カ Le (strain) society system, (following, to be designated as IC907))
Double (diethylamino) benzophenone of 1.557g, 4,4- (following, to be designated as EK) 0.173g is dissolved in DAA 15.000g, MB
In 5.914g, PGMEA 30.000g.Dipentaerythritol acrylate (trade name " カ ヤ ラ ッ De (registration is added to the solution
Trade mark) the new Nippon Kayaku (strain) Club systems of DPHA " (following, to be designated as DPHA) 8.652g, silane coupler solution (a-1) 6.922g,
The mass % solution 8.652g of PGMEA 1, siloxane resin solution (b-1) 21.630g, the silicon-type table of 4- tert-butyl catechols
Face activating agent is BYK-333 (PVC ッ Network ケ ミ ー ジ ャ パ Application (strain) system) the mass % solution 1.500g of PGMEA 1, is stirred
Mix.Then, filtered with 0.45 μm of filter, obtain negative light-sensitive resin combination (N-1).
Using spinner (ミ カ サ (strain) 1H-360S processed), with arbitrary revolution by gained negative light-sensitive resin combination
(N-1) difference rotary coating is in MAM substrates and ito substrate.Then, by these substrates hot plate (big Japan ス ク リ ー Application systems
Make (strain) SCW-636 processed) 2 minutes prebake conditions are carried out at 110 DEG C, make the film of 1.5 μm of thickness.
Using directional light mask aligner (キ ヤ ノ Application (strain) PLA-501F processed), using ultrahigh pressure mercury lamp as light source, to expose
Light quantity 200mJ (i rays) is exposed to the film of making.Then, using automatic developing device (AD-2000, Takizawa swamp industry (strain)
System), 90 seconds sprays are carried out with 0.4 mass % tetramethyl ammonium hydroxide aqueous solution ELM-D (Mitsubishi ガ ス chemistry (strain) is made) aobvious
Shadow, is then rinsed 30 seconds with water.Finally, entered in atmosphere at 220 DEG C using baking oven (エ ス ペ ッ Network (strain) IHPS-222 processed)
Row solidifies for 1 hour, makes cured film.For gained cured film, manner described above is commented MAM cementabilities, TOK106 patience
Valency.In addition, evaluating nargin of developing after prebake conditions by preceding method.
Embodiment 2
Instead of silane coupler solution (a-1) 6.922g use silane coupler solution (a-2) 1.731g, except this with
Outside, carry out same as Example 1ly, obtain negative light-sensitive resin combination (N-2).Negative photosensitive resin group obtained by use
Compound (N-2), is evaluated same as Example 1ly.
Embodiment 3
Instead of silane coupler solution (a-1) 6.922g use silane coupler solution (a-2) 6.922g, except this with
Outside, carry out same as Example 1ly, obtain negative light-sensitive resin combination (N-3).Negative photosensitive resin group obtained by use
Compound (N-3), is evaluated same as Example 1ly.
Embodiment 4
Instead of silane coupler solution (a-1) 6.922g use silane coupler solution (a-2) 20.766g, except this with
Outside, carry out same as Example 1ly, obtain negative light-sensitive resin combination (N-4).Negative photosensitive resin group obtained by use
Compound (N-4), is evaluated same as Example 1ly.
Embodiment 5
Instead of silane coupler solution (a-1) 6.922g use silane coupler solution (a-3) 6.922g, except this with
Outside, carry out same as Example 1ly, obtain negative light-sensitive resin combination (N-5).Negative photosensitive resin group obtained by use
Compound (N-5), is evaluated same as Example 1ly.
Embodiment 6
Under amber light, by 1.557g IC907,0.173g EK be dissolved in DAA 17.597g, MB 5.914g,
In PGMEA 30.000g.10.382g DPHA, silane coupler solution (a-2) 6.922g, 4- tert-butyl group is added to the solution
The mass % solution 8.652g of PGMEA 1 of catechol, acrylic resin solution (b-2) 17.303g, silicon-type surface-active
Agent is BYK-333 (PVC ッ Network ケ ミ ー ジ ャ パ Application (strain) system) the mass % solution 1.500g of PGMEA 1, is stirred.Then,
Filtered with 0.45 μm of filter, obtain negative light-sensitive resin combination (N-6).Negative photosensitive resin obtained by use
Composition (N-6), is evaluated same as Example 1ly.
Embodiment 7
Silane coupler solution (a-2) 6.922g addition is changed into 20.766g, in addition, with the phase of embodiment 6
Carry out together, obtain negative light-sensitive resin combination (N-7).Negative light-sensitive resin combination (N-7) obtained by use, with reality
Example 1 is applied to be evaluated in the same manner.
Embodiment 8
Under amber light, IC907 1.557g IC907,0.173g EK are dissolved in DAA 15.000g, MB
In 5.914g, PGMEA 27.405g.6.922g DPHA, silane coupler solution (a-2) 6.922g, 4- is added to the solution
The mass % solution 8.652g of PGMEA 1, acrylic resin solution (b-2) 17.303g, Cardo resin of tert-butyl catechol are molten
Liquid (b-3) 8.652g, silicone based surfactants are the PGMEA 1 of BYK-333 (PVC ッ Network ケ ミ ー ジ ャ パ Application (strain) system)
Quality % solution 1.500g, are stirred.Then, filtered with 0.45 μm of filter, obtain negative photosensitive resin combination
Thing (N-8).Negative light-sensitive resin combination (N-8), is evaluated same as Example 1ly obtained by use.
Embodiment 9
Under amber light, by 1.557g IC907,0.173g EK be dissolved in DAA 25.000g, MB 5.914g,
In PGMEA 20.000g.8.652g DPHA, silane coupler solution (a-1) 6.922g, 4- tert-butyl group is added to the solution
PGMEA 1 mass % solution 8.652g, Cardo resin solution (b-3) 21.630g, the silicone based surfactants of tea phenol are
BYK-333 (PVC ッ Network ケ ミ ー ジ ャ パ Application (strain) system) the mass % solution 1.500g of PGMEA 1, are stirred.Then, use
0.45 μm of filter is filtered, and obtains negative light-sensitive resin combination (N-9).
Embodiment 10
Instead of silane coupler solution (a-1) 6.922g use silane coupler solution (a-2) 6.922g, except this with
Outside, carry out same as Example 9ly, obtain negative light-sensitive resin combination (N-10).Negative photosensitive resin obtained by use
Composition (N-10), is evaluated same as Example 1ly.
Embodiment 11
Instead of silane coupler solution (a-1) 6.922g use silane coupler solution (a-3) 6.922g, except this with
Outside, carry out same as Example 9ly, obtain negative light-sensitive resin combination (N-11).Negative photosensitive resin obtained by use
Composition (N-11), is evaluated same as Example 1ly.
Embodiment 12
Instead of silane coupler solution (a-1) 6.922g use silane coupler solution (a-2) 20.766g, except this with
Outside, carry out same as Example 9ly, obtain negative light-sensitive resin combination (N-12).Negative photosensitive resin obtained by use
Composition (N-12), is evaluated same as Example 1ly.
Comparative example 1
Without silane coupler solution (a-1) 6.922g, in addition, carry out same as Example 1ly, obtain minus
Photosensitive polymer combination (N-13).Negative light-sensitive resin combination (N-13), is carried out same as Example 1ly obtained by use
Evaluate.
Comparative example 2
Instead of silane coupler solution (a-1) 6.922g use silane coupler solution (a-4) 6.922g, except this with
Outside, carry out same as Example 1ly, obtain negative light-sensitive resin combination (N-14).Negative photosensitive resin obtained by use
Composition (N-14), is evaluated same as Example 1ly.
Comparative example 3
Instead of silane coupler solution (a-1) 6.922g use silane coupler solution (a-4) 20.766g, except this with
Outside, carry out same as Example 1ly, obtain negative light-sensitive resin combination (N-15).Negative photosensitive resin obtained by use
Composition (N-15), is evaluated same as Example 1ly.
Comparative example 4
Instead of silane coupler solution (a-1) 6.922g use silane coupler solution (a-5) 6.922g, except this with
Outside, carry out same as Example 1ly, obtain negative light-sensitive resin combination (N-16).Negative photosensitive resin obtained by use
Composition (N-16), is evaluated same as Example 1ly.
Comparative example 5
Instead of silane coupler solution (a-1) 6.922g use silane coupler solution (a-6) 6.922g, except this with
Outside, carry out same as Example 1ly, obtain negative light-sensitive resin combination (N-17).Negative photosensitive resin obtained by use
Composition (N-17), is evaluated same as Example 1ly.
Comparative example 6
Without silane coupler solution (a-3) 6.922g, in addition, carry out same as Example 6ly, obtain minus
Photosensitive polymer combination (N-18).Negative light-sensitive resin combination (N-18), is carried out same as Example 1ly obtained by use
Evaluate.
Comparative example 7
Instead of silane coupler solution (a-3) 6.922g use silane coupler solution (a-4) 20.766g, except this with
Outside, carry out same as Example 6ly, obtain negative light-sensitive resin combination (N-19).Negative photosensitive resin obtained by use
Composition (N-19), is evaluated same as Example 1ly.
Comparative example 8
Without silane coupler solution (a-1) 6.922g, in addition, carry out same as Example 9ly, obtain minus
Photosensitive polymer combination (N-20).Negative light-sensitive resin combination (N-20), is carried out same as Example 1ly obtained by use
Evaluate.
Comparative example 9
Instead of silane coupler solution (a-1) 6.922g use silane coupler solution (a-4) 6.922g, except this with
Outside, carry out same as Example 9ly, prepare negative light-sensitive resin combination (N-21).However, occur gonorrhoea in solution, nothing
Method is filtered by 0.45 μm of filter.If solution is placed 1 day in room temperature, some sediments of generation can be confirmed.
Therefore, the evaluation for nargin of developing after MAM cementabilities, TOK106 patience, prebake conditions can not be implemented.
Comparative example 10
Instead of silane coupler solution (a-1) 6.922g use silane coupler solution (a-5) 6.922g, except this with
Outside, carry out same as Example 9ly, prepare negative light-sensitive resin combination (N-22).However, occur gonorrhoea in solution, nothing
Method is filtered by 0.45 μm of filter.If solution is placed 1 day in room temperature, some sediments of generation can be confirmed.
Therefore, the evaluation for nargin of developing after MAM cementabilities, TOK106 patience, prebake conditions can not be implemented.
Comparative example 11
Instead of silane coupler solution (a-1) 6.922g use silane coupler solution (a-6) 6.922g, except this with
Outside, carry out same as Example 9ly, prepare negative light-sensitive resin combination (N-23).However, occur gonorrhoea in solution, nothing
Method is filtered by 0.45 μm of filter.If solution is placed 1 day in room temperature, some sediments of generation can be confirmed.
Therefore, the evaluation for nargin of developing after MAM cementabilities, TOK106 patience, prebake conditions can not be implemented.
[table 1]
。
Industrial applicability
The present invention may be suitably used to negative light-sensitive resin combination, the cured film using said composition and with this
The touch-panel device of cured film.
Claims (4)
1. negative light-sensitive resin combination, it is characterised in that at least contain（A）Formula（1）Or formula（2）Shown silane is even
Connection agent,（B）Alkali soluble resin,（C）Multifunctional acrylic monomer,（D）Optical free radical polymerization initiator,
Relative to the total amount of (B) alkali soluble resin He (C) multifunctional acrylic monomer, the content of (A) silane coupler is
0.5~10 mass %,
Relative to the solid constituent of negative light-sensitive resin combination, the content of (B) alkali soluble resin is 10~70 mass %,
(D) content of optical free radical polymerization initiator is 0.01 mass % in the solid constituent of negative light-sensitive resin combination
Above and below 20 mass %,
The formula（1）For：
N represents 0~2 integer；R1Represent methyl, bicyclic [2,2,1] heptane -1- bases or fluorine-based of 7,7- dimethyl -2- oxos；R2
Represent propylidene；R3Can be each identical or different, represent the alkyl of carbon number 1~6, the alkoxy of carbon number 1~6,
Phenyl, hydroxyl and phenoxy group；R3At least one be selected from carbon number 1~6 alkoxy, hydroxyl；
The formula（2）For：
R4Represent p-methylphenyl；R5Represent propylidene；R6Can be each identical or different, represent alkyl, the carbon of carbon number 1~6
Alkoxy, phenyl, hydroxyl and the phenoxy group of atomicity 1~6；R6At least one be selected from carbon number 1~6 alkoxy, hydroxyl
Base.
2. the negative light-sensitive resin combination described in claim 1, wherein,（B）Alkali soluble resin is with olefinic insatiable hunger
With the Cardo resins of group.
3. cured film, it is to solidify the negative light-sensitive resin combination described in claim 1 or 2.
4. touch panel component, it has the cured film described in claim 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012037533A JP5327345B2 (en) | 2012-02-23 | 2012-02-23 | Negative photosensitive resin composition, cured film, and touch panel member. |
| JP2012-037533 | 2012-02-23 | ||
| PCT/JP2013/054341 WO2013125637A1 (en) | 2012-02-23 | 2013-02-21 | Negative photosensitive resin composition, cured film, and member for touch panel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104115067A CN104115067A (en) | 2014-10-22 |
| CN104115067B true CN104115067B (en) | 2017-09-22 |
Family
ID=49005814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380010587.8A Expired - Fee Related CN104115067B (en) | 2012-02-23 | 2013-02-21 | Negative light-sensitive resin combination, cured film and touch panel component |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5327345B2 (en) |
| KR (1) | KR101827784B1 (en) |
| CN (1) | CN104115067B (en) |
| TW (1) | TWI556061B (en) |
| WO (1) | WO2013125637A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6782532B2 (en) * | 2014-07-23 | 2020-11-11 | 日本乳化剤株式会社 | Ionic-binding salt, ionic-binding salt composition and resin composition containing the same |
| WO2016133023A1 (en) * | 2015-02-19 | 2016-08-25 | 日本ゼオン株式会社 | Resin composition, resin film and electronic component |
| US10040967B2 (en) | 2015-11-06 | 2018-08-07 | Hitachi Chemical Company, Ltd. | Photosensitive film, photosensitive element, cured product and touch panel |
| KR102341566B1 (en) * | 2016-03-15 | 2021-12-21 | 도레이 카부시키가이샤 | A photosensitive resin composition, a cured film, a laminated body, the member for touch panels, and the manufacturing method of a cured film |
| JP6551277B2 (en) * | 2016-03-24 | 2019-07-31 | 日立化成株式会社 | Method for producing cured substrate with touch panel, photosensitive resin composition used therefor, photosensitive element and touch panel |
| KR102373030B1 (en) | 2016-03-28 | 2022-03-11 | 도레이 카부시키가이샤 | photosensitive resin composition |
| JP2017181798A (en) | 2016-03-30 | 2017-10-05 | アーゼッド・エレクトロニック・マテリアルズ（ルクセンブルグ）ソシエテ・ア・レスポンサビリテ・リミテ | Low temperature curable negative type photosensitive composition |
| KR102524863B1 (en) * | 2017-03-29 | 2023-04-24 | 도레이 카부시키가이샤 | Film with conductive layer, touch panel, manufacturing method of film with conductive layer, and manufacturing method of touch panel |
| JP2019194709A (en) * | 2019-06-05 | 2019-11-07 | 日立化成株式会社 | Method for manufacturing base material for touch panel with cured film, photosensitive resin composition, photosensitive element and touch panel |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5066304A (en) * | 1973-10-17 | 1975-06-04 | ||
| US4086093A (en) * | 1974-10-11 | 1978-04-25 | Toray Industries, Inc. | Dry planographic printing plate |
| CN1577088A (en) * | 2003-07-09 | 2005-02-09 | 东丽株式会社 | Photosensitive resin precursor composition |
| CN101213491A (en) * | 2005-06-30 | 2008-07-02 | 东丽株式会社 | Photosensitive resin composition and adhesion enhancer |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000035670A (en) * | 1998-07-21 | 2000-02-02 | Sumitomo Chem Co Ltd | Colored photosensitive resin composition |
| US8053159B2 (en) * | 2003-11-18 | 2011-11-08 | Honeywell International Inc. | Antireflective coatings for via fill and photolithography applications and methods of preparation thereof |
| JP2008032860A (en) * | 2006-07-26 | 2008-02-14 | Fujifilm Corp | Curable composition, color filter and method for manufacturing the same |
| JP4833040B2 (en) * | 2006-11-22 | 2011-12-07 | 東京応化工業株式会社 | Photosensitive resin composition and spacer for liquid crystal panel |
| JP2012073601A (en) * | 2010-08-31 | 2012-04-12 | Fujifilm Corp | Photosensitive composition and photosensitive film, permanent pattern, method for forming permanent pattern, and printed substrate |
| JP2012185408A (en) * | 2011-03-08 | 2012-09-27 | Toyo Ink Sc Holdings Co Ltd | Photosensitive resin composition and insulating film for touch panel |
| CN103765254B (en) * | 2011-08-29 | 2016-04-06 | 东丽株式会社 | Colored resin composition and resin black matrix substrate |
-
2012
- 2012-02-23 JP JP2012037533A patent/JP5327345B2/en active Active
-
2013
- 2013-02-21 WO PCT/JP2013/054341 patent/WO2013125637A1/en active Application Filing
- 2013-02-21 KR KR1020147013368A patent/KR101827784B1/en active IP Right Grant
- 2013-02-21 CN CN201380010587.8A patent/CN104115067B/en not_active Expired - Fee Related
- 2013-02-22 TW TW102106113A patent/TWI556061B/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5066304A (en) * | 1973-10-17 | 1975-06-04 | ||
| US4086093A (en) * | 1974-10-11 | 1978-04-25 | Toray Industries, Inc. | Dry planographic printing plate |
| CN1577088A (en) * | 2003-07-09 | 2005-02-09 | 东丽株式会社 | Photosensitive resin precursor composition |
| CN101213491A (en) * | 2005-06-30 | 2008-07-02 | 东丽株式会社 | Photosensitive resin composition and adhesion enhancer |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101827784B1 (en) | 2018-03-22 |
| CN104115067A (en) | 2014-10-22 |
| JP2013174643A (en) | 2013-09-05 |
| KR20140130099A (en) | 2014-11-07 |
| TWI556061B (en) | 2016-11-01 |
| JP5327345B2 (en) | 2013-10-30 |
| TW201344363A (en) | 2013-11-01 |
| WO2013125637A1 (en) | 2013-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104115067B (en) | Negative light-sensitive resin combination, cured film and touch panel component | |
| CN102803274B (en) | Silane coupling agent, negative light-sensitive resin combination, cured film and touch panel component | |
| CN104345567B (en) | photosensitive polysiloxane composition and application thereof | |
| JP5589387B2 (en) | Siloxane resin composition and protective film for touch panel using the same | |
| CN101322074B (en) | Silicon-containing resist underlying layer film forming composition for formation of photocrosslinking cured resist underlying layer film | |
| TWI597265B (en) | A photosensitive resin composition, a protective film or an insulating film, a touch panel, and a method of manufacturing the same | |
| JP5003081B2 (en) | Photosensitive siloxane composition, cured film formed therefrom, and device having cured film | |
| TWI612384B (en) | Photosensitive resin composition, conductive wiring protective film, and touch panel member | |
| TWI491675B (en) | Polyoxometallic compositions containing freejunction groups | |
| KR20130070563A (en) | Negative photosensitive resin composition, and protective film and touch panel member using the same | |
| JPWO2011078106A1 (en) | Positive photosensitive resin composition, cured film formed therefrom, and element having cured film | |
| JP7462724B2 (en) | Photosensitive resin composition, dry film resist and their cured products | |
| JP2008208342A (en) | Resin composition, cured film and color filter with cured film | |
| KR101799361B1 (en) | Photosensitive resin composition | |
| CN104122753A (en) | Photosensitive polysiloxane composition, protective film and element with protective film | |
| CN104849962A (en) | Photosensitive polysiloxane composition, protective film and element with protective film | |
| US20230037301A1 (en) | Negative photosensitive resin composition, pattern structure and method for producing patterned cured film | |
| CN107434941A (en) | Resin combination and cured film | |
| CN109062007A (en) | positive photosensitive polysiloxane composition and application thereof | |
| CN110419000A (en) | Photosensitive siloxane resin composition, cured film and touch panel component | |
| JPWO2021187324A5 (en) | ||
| CN107614554A (en) | Organic mineral complex | |
| KR102167370B1 (en) | Silicone Resin and Method of Preparing the Same | |
| TW202231737A (en) | Resin composition, cured film, method for manufacturing cured film, substrate having multilayer film, method for manufacturing patterned substrate, photosensitive resin composition, method for manufacturing pattern cured film, method for manufacturing polymer, and method for manufacturing resin composition | |
| TW202116880A (en) | Coating film-forming composition, laminate obtained by coating said coating film-forming composition, touch panel obtained by using said laminate, and method for forming cured coating film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170922 Termination date: 20210221 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |