CN104040432B - Negative light-sensitive resin combination - Google Patents
Negative light-sensitive resin combination Download PDFInfo
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- CN104040432B CN104040432B CN201380004941.6A CN201380004941A CN104040432B CN 104040432 B CN104040432 B CN 104040432B CN 201380004941 A CN201380004941 A CN 201380004941A CN 104040432 B CN104040432 B CN 104040432B
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- resin combination
- sensitive resin
- negative light
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/38—Amides
Abstract
The subject of the invention is to provide a kind of negative light-sensitive resin combinations, the resin combination being capable of thick-film, do not have viscosity before exposure yet, pattern can be formed with high-resolution by alkali development, it is high and small in rear baking after-contraction to be formed by the film transparency.Solution is the negative light-sensitive resin combination containing following (A) ingredients, (B) ingredient and (C) solvent.(A) ingredient：Copolymer made of being copolymerized by monomer mixture, the monomer mixture, which at least contains (i) N alkoxy methyls (methyl) acrylamide and (ii), has the monomer of alkali solubility group；(B) ingredient：Photoacid generator；(C) solvent.
Description
Technical field
The cured film obtained the present invention relates to negative light-sensitive resin combination and by it.More specifically, the present invention relates to
And with suitable photosensitive polymer combination and its cured film on the way and use the various materials of the cured film in display material
Material.
Background technology
Known containing the polymerization of the epoxy-cationic of epoxide and photoacid generator is UV solidified resins, and the transparency is high and energy
Enough thick-films (for example, patent document 1).However, since film has viscosity after coating and before exposure, so operational
Difference.In addition, since the development using aqueous alkali cannot be carried out, so the development using organic solvent must be carried out.It is aobvious with regard to alkali
For shadow, although it is believed that carboxyl can be introduced in the polymer, but with epoxy group monomer with the monomer of carboxyl
Combined polymerization in the case of, be easy to happen and react with carboxyl in polymerization epoxy group, it is difficult to control the synthesis of polymer.In addition,
Allow to control reaction synthetic polymer, storage stability is also low.
As the substance for capableing of alkali development, it is known that contain polymer, multifunctional acrylic monomer with acryloyl group
With the minus material (for example, patent document 2) of the radical polymerization collaboration of optical free radical initiator.In the invention, although passing through
In the polymer introduce carboxyl can alkali development, but in order to carry out thick-film must high viscosity, so operability it is poor.Separately
Outside, due to being polymerized to free radical system, so being easy the oxygen inhibition by surface in photocuring, there are the films on surface to reduce change
Big problem.
On the other hand, although eurymeric material high resolution, it can be difficult to thick-film and the transparency it is also low (for example, patent is literary
It offers 3).
From the aspects of, it is expected that the transparency it is high and can alkali development, the operability also high material in thick-film.
Existing technical literature
Patent document
Patent document 1：International application published WO2008/007764 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2004-302389 bulletins
Patent document 3：Japanese Unexamined Patent Publication 8-339082 bulletins
Invention content
Problems to be solved by the invention
In view of the foregoing, the present invention provides a kind of negative light-sensitive resin combination, can thick-film, before exposure
Do not have viscosity, pattern can be formed with high-resolution by alkali development, film transparency height is formed by, after rear baking yet
It shrinks also small.
The means solved the problems, such as
It is that present inventor is careful studied to solve the above-mentioned problems as a result, final be made that the present invention.
That is, it is related to following aspect,
As the 1st aspect, a kind of negative light-sensitive resin combination, containing following (A) ingredients, (B) ingredient and (C) it is molten
Agent,
(A) ingredient：Copolymer made of being copolymerized by monomer mixture, the monomer mixture at least contain (i) N- alcoxyls
Ylmethyl (methyl) acrylamide and (ii) have the monomer of alkali solubility group,
(B) ingredient：Photoacid generator,
(C) ingredient：Solvent；
As the 2nd aspect, according to the negative light-sensitive resin combination described in the 1st aspect, (ii) for (A) ingredient has
It is maleimide to have the monomer of alkali solubility group；
100 matter are based on according to the negative light-sensitive resin combination described in the 1st aspect or the 2nd aspect as the 3rd aspect
Part photosensitive polymer combination is measured, the sensitizer for also containing 0.1~10 mass parts is used as (D) ingredient；
Tool is also contained according to the negative light-sensitive resin combination described in the 1st aspect or the 2nd aspect as the 4th aspect
There is the polymer of hydroxyl to be used as (E) ingredient；
As the 5th aspect, according to the negative light-sensitive resin combination described in the 1st aspect to the 3rd aspect, (A) ingredient is
Copolymer made of being copolymerized by monomer mixture, the monomer mixture also contain the monomer with hydroxyl；
As the 6th aspect, according to the negative light-sensitive resin combination described in the 1st aspect to the 5th aspect, also contains and hand over
Join agent and is used as (F) ingredient；
As the 7th aspect, a kind of cured film is for the use of the 1st to the negative photosensitive described in any one of for the use of the 6th
Property resin combination and obtain；
As the 8th aspect, a kind of liquid crystal display interlayer dielectric, it includes the cured films described in the 7th aspect；
As the 9th aspect, a kind of optical light filter, it includes the cured films described in the 7th aspect.
The effect of invention
The present invention photosensitive polymer combination, due to before exposure do not have viscosity, can alkali development, even if in thick film
In the case of, the painting film figure of the transparency, high resolution can be also formed, so being most suitable for forming the construction as optical component
Body.
Specific implementation mode
The negative light-sensitive resin combination of the present invention is to contain the photosensitive of following (A) ingredients, (B) ingredient and (C) solvent
Property resin combination.
(A) ingredient：Copolymer made of being copolymerized by monomer mixture, the monomer mixture at least contain (i) N- alcoxyls
Ylmethyl (methyl) acrylamide and (ii) have the monomer of alkali solubility group,
(B) ingredient：Photoacid generator,
(C) solvent.
＜ (A) ingredients ＞
(A) ingredient is copolymer made of being copolymerized by monomer mixture, and the monomer mixture at least contains (i) N- alcoxyls
Ylmethyl (methyl) acrylamide and (ii) have the monomer of alkali solubility group.
In the present invention, copolymer refers to using acrylate, methacrylate, acrylamide, methacryl
The monomer with unsaturated double-bond such as amine, styrene is copolymerized and the polymer that obtains.
(A) copolymer of ingredient, as long as the copolymer having a structure in which, constitutes the high molecular of copolymer
The skeleton of main chain and the type of side chain etc. are not particularly limited.
However, the copolymer of (A) ingredient, if number-average molecular weight is excessive more than 100000, the development in unexposed portion
Property reduce, on the other hand, if number-average molecular weight is too small less than 2000, the solidification of exposure portion is insufficient, when to develop
The case where existence component dissolves out.Therefore, number-average molecular weight is in the range of 2000~100000.
The representation of (i) N- alkoxy methyl (methyl) acrylamides formula (1) for (A) ingredient：
[changing 1]
(R in formula1Indicate the alkyl of hydrogen atom, halogen atom or carbon atom number 1~6.R in formula2Indicate that hydrogen atom or carbon are former
The alkyl of subnumber 1~10.)
As the concrete example of these monomers, N- (methoxy) acrylamide, N- (methoxy) first can be enumerated
Base acrylamide, N- (n-butoxy methyl) acrylamide, N- (n-butoxy methyl) Methacrylamide, N- (isobutoxies
Methyl) acrylamide, N- (isobutoxymethyl) Methacrylamide etc..
As for (A) ingredient (ii) have alkali solubility group monomer, can enumerate, have carboxyl, phenolic hydroxyl group,
The monomer of anhydride group, dimaleoyl imino.
It as the monomer with carboxyl, can enumerate, for example, acrylic acid, methacrylic acid, crotonic acid, mono- (2- (propylene
Acyloxy) ethyl) phthalic acid ester, mono- (2- (methacryloxy) ethyl) phthalic acid ester, N- (carboxyl phenyl)
Maleimide, N- (carboxyl phenyl) Methacrylamide, N- (carboxyl phenyl) acrylamide, 4 vinyl benzoic acids etc..
As the monomer with phenolic hydroxyl group, can enumerate, for example, hydroxy styrenes, N- (hydroxy phenyl) acrylamide,
N- (hydroxy phenyl) Methacrylamide, N- (hydroxy phenyl) maleimide etc..
It as the monomer with anhydride group, can enumerate, for example, maleic anhydride, itaconic anhydride etc..
It as the monomer with dimaleoyl imino, can enumerate, for example, maleimide.
In addition, in the present invention, when obtaining the copolymer with particular functional group, can be used together with particular functional group
Monomer and copolymerizable monomer.
It as the concrete example of this monomer, can enumerate, acrylate compounds, methacrylate compound, N- take
For maleimide compound, acrylonitrile, acrylamide compound, methacrylamide compounds, distyryl compound and second
Alkenyl compound etc..
In the following, although the concrete example of above-mentioned monomer has been enumerated, but be not restricted to that these monomers.
It as foregoing acrylates compound, can enumerate, for example, methyl acrylate, ethyl acrylate, acrylic acid isopropyl
Ester, benzyl acrylate, acrylic acid naphthalene ester, acrylic acid anthracene ester, acrylic acid anthrylmethyl, phenyl acrylate, acrylic acid 2,2,2-
Trifluoro ethyl ester, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, acrylic acid 2- methoxy acrylates, methoxyl group three
Ethylene glycol acrylate, acrylic acid 2- ethoxy ethyl esters, tetrahydrofurfuryl acrylate, acrylic acid 3- methoxybutyls, 2- methyl -2-
Adamantyl acrylate, 2- propyl -2- adamantyl acrylates, 8- methyl -8- tricyclodecyls acrylate, acrylic acid 2-
Hydroxy methacrylate, acrylic acid 2- hydroxy propyl esters, acrylic acid 4- hydroxybutyls, acrylic acid 2,3- dihydroxy propyl ester, diethylene glycol list third
Olefin(e) acid ester, caprolactone 2- (acryloxy) ethyl ester, poly(ethylene glycol) ethyl ether acrylate, 5- acryloxy -6- hydroxyls
Base norbornene -2- carboxyl -6- lactones, acryloyl ethyl isocyanates and 8- ethyl -8- tricyclodecyls acrylate, third
Olefin(e) acid ethylene oxidic ester etc..
It as aforementioned methacrylate compound, can enumerate, for example, methyl methacrylate, methacrylic acid second
Ester, isopropyl methacrylate, benzyl methacrylate, methacrylic acid naphthalene ester, methacrylic acid anthracene ester, methacrylic acid
Anthrylmethyl, phenyl methacrylate, methacrylic acid 2,2,2- trifluoro ethyl esters, Tert-butyl Methacrylate, methacrylic acid
Cyclohexyl, isobornyl methacrylate, methacrylic acid 2- methoxy acrylates, methoxy triethylene methacrylate,
Methacrylic acid 2- ethoxy ethyl esters, tetrahydrofurfuryl methacrylate, methacrylic acid 3- methoxybutyls, 2- methyl -2- gold
Rigid alkylmethacrylate, gamma-butyrolacton methacrylate, 2- propyl -2- adamantyl methacrylates, 8- first
Base -8- tricyclodecyls methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid 2- hydroxy propyl esters, metering system
Sour 4- hydroxybutyls, methacrylic acid 2,3- dihydroxy propyl ester, diethylene glycol monomethyl acrylate, caprolactone 2- (methyl-props
Alkene acyloxy) ethyl ester, poly(ethylene glycol) ethyl ether methacrylate, 5- methacryloxy -6- hydroxy norbomenes -
2- carboxyl -6- lactones, methylacryloyl ethyl isocyanate and 8- ethyl -8- tricyclodecyls methacrylate, methyl
Glycidyl acrylate etc..
It as aforementioned N- substituted maleimides amine compounds, can enumerate, for example, N- methylmaleimidos, N- phenyl
Maleimide and N- N-cyclohexylmaleimides etc..
It as aforementioned distyryl compound, can enumerate, for example, styrene, methyl styrene, chlorostyrene, bromobenzene second
Alkene etc..
It as aforementioned vinyl compound, can enumerate, for example, methyl vinyl ether, benzyl vinyl ethers, vinyl
Naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2- hydroxyethyl vinyl ethers, Vinyl phenyl ether and propyl ethylene
Base ether etc..
It obtains and is not particularly limited for the method for the copolymer with particular functional group of the present invention, for example, can be with
By in the monomer for making that there is particular functional group, copolymerizable with non-reaction other than the monomer with particular functional group
In the monomer of property functional group and the solvent coexisted according to desired polymerization initiator etc., carried out at a temperature of 50~110 DEG C
Polymerisation and obtain.At this point, used solvent, is total to as long as can dissolve and constitute the acrylic acid series with particular functional group
The solvent of the monomer of polymers and acrylic acid series copolymer with particular functional group, is just not particularly limited.As concrete example,
Solvent recorded in aftermentioned (C) solvent can be enumerated.
The acrylic acid series copolymer with particular functional group obtained in this way usually dissolves in a solvent molten
Liquid status.
In addition, the solution of the copolymer obtained in the above described manner, which is put under stiring in ether, water etc., makes it sink again
It forms sediment, by the sediment filtration washing of generation, room temperature or heat drying is then carried out under normal or reduced pressure, so as to be formed
The powder of copolymer.Operation in this way can remove the polymerization initiator coexisted with copolymer, unreacted monomer, as a result,
The copolymerization powder refined can be obtained.In the case where once-through operation cannot be refined fully, the powder of acquisition is redissolved
In solvent, repeat aforesaid operations.
In the present invention, the polymeric solution of above-mentioned acrylic acid series copolymer can also be directly used, or can also should
Powder is re-dissolved in for example aftermentioned (C) solvent and forms solution state and use.
In addition, in the present invention, the copolymer of (A) ingredient may be the mixture of a variety of specific copolymers.
As the copolymerization ratios of monomer, preferably N- alkoxy methyls (methyl) acrylamide/alkaline soluble monomers/other=
10~60/10~40/0~80 parts by weight.In the case where alkaline soluble monomers are very few, unexposed portion is easy insoluble in developer solution
The reason of as residual film, residue.In the case of excessive, the curability of exposure portion is insufficient, there is the possibility that cannot form pattern
Property.In the case where N- alkoxy methyls (methyl) acrylamide is very few, photo-curable is insufficient, and it is molten in development that there are exposure portions
The possibility of solution.In the case of excessive, and possibility as residual film, residue the reason of insufficient there are the dissolubility in unexposed portion
Property.
＜ (B) ingredients ＞
(B) ingredient is photoacid generator.There is no special for the type of the acid of compositions of thermosetting resin for use in the present invention
It limits.As the concrete example of such photoacid generator, following substance can be enumerated.
[changing 2]
[changing 3]
[changing 4]
[changing 5]
[changing 6]
[changing 7]
[changing 8]
[changing 9]
[changing 10]
In addition, the photoacid generator as (B) ingredient, can enumerate, chlorinated diphenyl base iodine, diphenyl iodineFluoroform
Sulfonate, diphenyl iodineMesylate, diphenyl iodineToluene fulfonate, brominated diphenyl base iodine, diphenyl iodineFour
Borofluoride, diphenyl iodineHexafluoro antimonate, diphenyl iodineHexafluoro arsenate, two (to tert-butyl-phenyl) iodineHexafluoro
Phosphate, two (to tert-butyl-phenyl) iodineMesylate, two (to tert-butyl-phenyl) iodineToluene fulfonate, two are (to tertiary fourth
Base phenyl) iodineFluoroform sulphonate, two (to tert-butyl-phenyl) iodineTetrafluoroborate, chlorination two (to tert-butyl-phenyl)
Iodine, chlorination two (rubigan) iodine, two (rubigan) iodineTetrafluoroborate, chlorinated triphenyl base sulfonium, bromination triphen
Base sulfonium, triphenylsulfonium triflate sulfonate, three (p-methoxyphenyl) sulfonium tetrafluoroborates, three (p-methoxyphenyl) sulfonium hexafluoros
Phosphonate, three (to ethoxyl phenenyl) sulfonium tetrafluoroborates, chlorinated triphenyl base sulfonium, triphenylsulphonium bromide, three are (to methoxybenzene
Base) sulfonium tetrafluoroborate, three (p-methoxyphenyl) sulfonium hexafluorophosphonates, three (to ethoxyl phenenyl) sulfonium tetrafluoroborates etc..
The content of (B) ingredient in the negative light-sensitive resin combination of the present invention, relative to 100 mass parts (A) ingredient,
Preferably 0.5~20 mass parts, more preferably 1~15 mass parts, further preferably 2~10 mass parts.It is less than in the ratio
In the case of 0.5 mass parts, there are photoreactivity drop the case where susceptibility reduction.In addition, if it exceeds 20 mass parts, then deposit
The case where the storage stability of the decrease in transmission, solution that are formed by film reduces.
＜ (C) solvents ＞
It is dissolving for the present invention (A) ingredient and (B) ingredient, and dissolve according to it is expected addition aftermentioned (D) at
Point, the solvent of (E) ingredient, (F) ingredient etc., as long as the solvent with this solvability, type and structure etc. are not
It is particularly limited to.
It as such (C) solvent, can enumerate, for example, glycol monoethyl ether, ethylene glycol monoethyl ether, methyl cellosolve
Acetic acid esters, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, third
Glycol monomethylether acetate, propylene glycol propyl ether acetic acid esters, toluene, dimethylbenzene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2- butanone,
3- methyl -2 pentanone, 2 pentanone, 2-HEPTANONE, gamma-butyrolacton, 2 hydroxy propanoic acid ethyl ester, 2- hydroxy-2-methyls ethyl propionate, second
Oxygroup ethyl acetate, hydroxacetic acid ethyl ester, 2- hydroxy-3-methyls methyl butyrate, 3- methoxy methyl propionates, 3- methoxypropionic acids
Ethyl ester, 3- ethoxyl ethyl propionates, 3- ethoxypropanoates, methyl pyruvate, ethyl pyruvate, ethyl acetate, acetic acid fourth
Ester, ethyl lactate, butyl lactate, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and N-Methyl pyrrolidone etc..
These solvents can be used alone, or can be applied in combination two or more.
In these (C) solvents, from applying, film property is good, from the point of view of safe, preferably propylene glycol monomethyl ether, diethyl two
Alcohol monomethyl ether, propylene glycol methyl ether acetate, ethyl lactate, butyl lactate etc..These solvents are usually as photoresist material
The solvent of material uses.
＜ (D) ingredients ＞
(D) ingredient is sensitizer.(B) ingredient photoacid generator to make by the present invention negative light-sensitive resin combination
In the case that the reactivity of the wavelength of the film exposure of formation is small, reactivity can be improved by adding sensitizer.As this
The concrete example of the sensitizer of sample can be enumerated, 9,10- dibutoxy anthracenes, 9- hydroxymethyls anthracene, thioxanthones, 2- isopropylthioxanthones
Ketone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4- diethyl thioxanthones, anthraquinone, 1,2- dihydroxy anthraquinones, 2- ethyl hydrazine,
1,4- diethoxy naphthalenes etc..
As (D) ingredient, a kind in aforementioned sensitizer can be used, or two or more can be applied in combination.
The additive amount of these sensitizers, relative to 100 mass parts (A) ingredient, it is often preferred that 0.1~10 mass parts, more
Preferably 0.1~8 mass parts.If the amount of sensitizer is excessive compared with aforementioned range, reduced there are the transparency of film
Situation.
＜ (E) ingredients ＞
(E) ingredient is the polymer with hydroxyl.It as the polymer with hydroxyl, can enumerate, for example, by with hydroxyl
Polymer made of the monomer polymerization of base；Cellulose, hydroxypropyl cellulose；Bis-epoxy and dicarboxylic acids are copolymerized and what is obtained polymerize
Object；Bis-epoxy is copolymerized with diphenol and the polymer of acquisition；Polyester polyol, polyether polyol, polycaprolactone polyol etc., still
Preferably polymer or hydroxypropyl cellulose made of the monomer polymerization with hydroxyl.
It as the above-mentioned polymer made of the monomer polymerization with hydroxyl, can enumerate, be enumerated in above-mentioned (A) ingredient
Copolymerizable monomer in monomer homopolymerization with hydroxyl or with polymer made of copolymerizable monomer copolymerization.
As the monomer with hydroxyl in the copolymerizable monomer enumerated in (A) ingredient, can enumerate, acrylic acid 2- hydroxyls
Base ethyl ester, acrylic acid 2- hydroxy propyl esters, acrylic acid 4- hydroxybutyls, acrylic acid 2,3- dihydroxy propyl ester and 5- acryloxies-
6- hydroxy norbomene -2- carboxyl -6- lactones；2-hydroxyethyl methacrylate, methacrylic acid 2- hydroxy propyl esters, methyl-prop
Olefin(e) acid 4- hydroxybutyls, methacrylic acid 2,3- dihydroxy propyl ester and 5- methacryloxy -6- hydroxy norbomene -2- carboxylics
Base -6- lactones etc..
It as copolymerizable monomer, can enumerate, for example, the copolymerizable monomer enumerated in (A) ingredient.
These polymer with hydroxyl can be used alone, or two or more can be applied in combination.
The content of the polymer with hydroxyl of (E) ingredient in the negative light-sensitive resin combination of the present invention, is based on
The copolymer of 100 mass parts (A) ingredient, preferably 5~150 mass parts, more preferably 10~120 mass parts.The ratio with
Aforementioned range is compared in the case of too small, the case where reduction there are the susceptibility of negative light-sensitive resin combination, another aspect,
In the case of excessive compared with aforementioned range, there are the developability in unexposed portion reduce and as residual film, residue the reason of
Situation.
＜ (F) ingredients ＞
As the present invention (F) ingredient crosslinking agent, as long as can by the acid generated by (B) ingredient with (A) at
Divide the crosslinking agent of reaction.As such crosslinking agent, the compounds such as epoxide, methylol compound can be enumerated,
It is preferred that being methylol compound.
It as the concrete example of above-mentioned methylol compound, can enumerate, aikoxymethytated glycolurils, aikoxymethytated benzene
The compounds such as guanamines and aikoxymethytated melamine.
It as the concrete example of aikoxymethytated glycolurils, can enumerate, for example, 1,3,4,6- tetra- (methoxy) is sweet
Urea, 1,3,4,6- tetra- (butoxymethyl) glycoluril, 1,3,4,6- tetra- (hydroxymethyl) glycoluril, 1,3- bis- (hydroxymethyl) urea, 1,
1,3,3- tetra- (butoxymethyl) urea, 1,1,3,3- tetra- (methoxy) urea, (the hydroxymethyl) -4,5- of 1,3- bis- dihydroxy -
2- imidazolones and 1,3- bis- (methoxy) -4,5- dimethoxy -2- imidazolones etc..As commercially available product, can enumerate,
Glycoluril compounds (the trade name of three well サ イ テ ッ Network (strain) production：サ イ メ Le (registered trademark) 1170, パ ウ ダ ー リ Application Network
(registered trademark) 1174) etc. compounds, methylate carbamide resin (trade name：UFR (registered trademark) 65), butylation carbamide resin (quotient
The name of an article：UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), big Japan's イ Application キ chemical industry (strain)
Urea/diaion (high condensed type, the trade name of production：ベ ッ カ ミ Application (registered trademark) J-300S, ベ ッ カ ミ Application P-955, ベ
ッ カ ミ Application N) etc..
It as the concrete example of aikoxymethytated benzoguanamine, can enumerate, tetramethoxymethyl benzoguanamine etc..As commercially available
Product can be enumerated, (the trade name of three well サ イ テ ッ Network (strain) production：サ イ メ Le (registered trademark) 1123), (strain) three and ケ
(the trade name of ミ カ Le production：ニ カ ラ ッ Network (registered trademark) BX-4000, ニ カ ラ ッ Network BX-37, ニ カ ラ ッ Network BL-60,
ニ カ ラ ッ Network BX-55H) etc..
It as the concrete example of aikoxymethytated melamine, can enumerate, for example, hexamethoxy methyl cyanuramide etc..As city
Product are sold, can be enumerated, the methoxy methyl fundamental mode melamine compound (trade name of three well サ イ テ ッ Network (strain) production：サイメル
(registered trademark) 300, サ イ メ Le 301, サ イ メ Le 303, サ イ メ Le 350), butoxymethyl type melamine compound (quotient
The name of an article：マ イ コ ー ト (registered trademark) 506, マ イ コ ー ト 508)；The methoxy methyl fundamental mode melamine of three and ケ ミ カ Le production
Close object (trade name：ニ カ ラ ッ Network (registered trademark) MW-30, ニ カ ラ ッ Network MW-22, ニ カ ラ ッ Network MW-11, ニ カ ラ ッ Network
MS-001, ニ カ ラ ッ Network MX-002, ニ カ ラ ッ Network MX-730, ニ カ ラ ッ Network MX-750, ニ カ ラ ッ Network MX-035), fourth oxygen
Ylmethyl type melamine compound (trade name：ニ カ ラ ッ Network (registered trademark) MX-45, ニ カ ラ ッ Network MX-410, ニ カ ラ ッ Network
MX-302) etc..
Furthermore it is possible to be can make the hydrogen atom of this amino by methylol or alkoxy methyl instead of melamine chemical combination
Object, carbamide compound, glycoluril compounds and benzoguanamine compound condensation and the compound obtained.For example, can enumerate, United States Patent (USP)
The compound of the high molecular weight manufactured by melamine compound and benzoguanamine compound recorded in No. 6323310.As aforementioned
The commercially available product of melamine compound can be enumerated, trade name：(three well サ イ テ ッ Network (strain) are raw for サ イ メ Le (registered trademark) 303
Production) etc., as the commercially available product of aforementioned benzoguanamine compound, can enumerate, trade name：サ イ メ Le (registered trademark) 1123 (three
Well サ イ テ ッ Network (strain) produces) etc..
These crosslinking agents can be used alone, or two or more can be applied in combination.
The content of the crosslinking agent of (F) ingredient in the negative light-sensitive resin combination of the present invention is based on 100 mass parts
(A) copolymer of ingredient, preferably 5~100 mass parts, more preferably 10~80 mass parts.In the ratio and aforementioned range phase
In the case of too small, the case where reduction there are the photo-curable of negative light-sensitive resin combination, on the other hand, with it is aforementioned
Range compared in the case of excessive, there are the developability in unexposed portion reduce and the case where as the reason of residual film, residue.
The other additive ＞ of ＜
In addition, the negative light-sensitive resin combination of the present invention, under the premise of not damaging the effect of the present invention, Ke Yigen
According to need containing quencher, surfactant, rheology control agent, pigment, dyestuff, preserving stabilizer, antifoaming agent or polyphenol,
Dissolution accelerators such as polybasic carboxylic acid etc..
＜ negative light-sensitive resin combinations ＞
The negative light-sensitive resin combination of the present invention be in (C) solvent the polymer of dissolving (A) ingredient and (B) at
Point photoacid generator composition, and sensitizer, (E) ingredient that can also contain (D) ingredient according to expectation respectively have
One or more of the polymer of hydroxyl, the crosslinking agent of (F) ingredient and other additives.
Wherein, the preferred example of negative light-sensitive resin combination of the invention is as described below.
[1]：A kind of negative light-sensitive resin combination contains 0.5~20 mass parts based on 100 mass parts (A) ingredient
(B) ingredient, and these ingredients are dissolved in (C) solvent.
[2]：A kind of negative light-sensitive resin combination, in the composition of above-mentioned [1], based on 100 mass parts (A) at
Point, also contain 0.1~10 mass parts (D) ingredient.
[3]：A kind of negative light-sensitive resin combination is based on 100 mass parts in the composition of above-mentioned [1] or [2]
(A) ingredient also contains 5~150 mass parts (E) ingredient.
[4]：A kind of negative light-sensitive resin combination is based on 100 mass parts in the composition of above-mentioned [1]~[3]
(A) ingredient also contains 5~100 mass parts (F) ingredient.
The present invention negative light-sensitive resin combination in solid constituent ratio, as long as each ingredient be equably dissolved in it is molten
It is just not particularly limited in agent, for example, 1~80 mass %, is either such as 5~60 mass % or be 10~50 matter
Measure %.Here, solid constituent refers to the ingredient after removing (C) solvent in the whole components of negative light-sensitive resin combination.
The modulator approach of the negative light-sensitive resin combination of the present invention, is not particularly limited, can as its modulation method
To enumerate, for example, (A) ingredient (copolymer) is dissolved in (C) solvent, (B) ingredient (light is mixed with regulated proportion in the solution
Acid agent), the method for forming uniform solution, alternatively, the stage appropriate in the modulator approach further add as needed
Add (D) ingredient (sensitizer), (E) ingredient (polymer with hydroxyl), (F) ingredient (crosslinking agent) and other additives and mixes
Method.
In the negative light-sensitive resin combination of the modulation present invention, it can be directly used in (C) solvent and pass through polymerization
React the solution of the specific copolymer obtained, in this case, by with it is aforementioned it is same in a manner of (B) ingredient etc. is added to
It, can also further additional input (C) for the purpose that concentration is adjusted when forming uniform solution in the solution of (A) ingredient
Solvent.At this point, (C) solvent used in the forming process of specific copolymer and in modulation negative light-sensitive resin combination
When for concentration adjust (C) solvent both can be the same or different.
Also, it is preferred that the negative light-sensitive resin combination that will be modulated by 0.2 μm or so of filter etc. using aperture
Solution filtering after reuse.
＜ films and cured film ＞
Rotary coating, ink-jet application etc. are connected half by rotary coating, flow coat, print roll coating, slit coating, slit
Conductor substrate is (for example, silicon/silicon dioxide is substrate coated；Silicon nitride board；It is coated with substrate of the metal such as aluminium, molybdenum, chromium；
Glass substrate；Quartz base plate；Ito substrate etc.) on be coated with the present invention negative light-sensitive resin combination, then, by using
Heating plate or baking oven etc. carry out predrying, can form film.Then, it by heating to the film, can be formed
Negative photosensitive resin film.
As the condition of the heat treatment, for example, may be used be conveniently selected from temperature 70 C~160 DEG C, the time 0.3~
Heating temperature in 60 minutes ranges and heating time.Heating temperature and heating time be preferably 80 DEG C~140 DEG C, 0.5~
10 minutes.
In addition, the film thickness of the negative photosensitive resin film formed by negative light-sensitive resin combination is such as 0.1~30 μ
M, or be such as 0.5~20 μm, it is further such as 1~15 μm.
The negative photosensitive resin film formed by the negative light-sensitive resin combination of the present invention, if using having regulation figure
The mask of case passes through ultraviolet light, ArF, KrF, F2The light exposures such as laser, then by contained in negative photosensitive resin film
(B) effect for the acid that the photoacid generator (PAG) of ingredient generates, the exposure portion in the film become the part insoluble in alkaline-based developer.
Then, (PEB) is heated after being exposed to negative photosensitive resin film.As heating condition in this case,
It may be used and be conveniently selected from temperature 70 C~150 DEG C, the heating temperature in the range of 0.3~60 minute time and heating time.
Then, developed using alkaline-based developer.Accordingly, the part not being exposed in negative photosensitive resin film is removed
It goes, forms the relief of pattern-like.
It as the alkaline-based developer that can be used, can enumerate, for example, the alkali metal hydrogen-oxygen such as potassium hydroxide, sodium hydroxide
The aqueous solution of compound；The aqueous solution of the quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline；Ethanol amine, third
The alkaline aqueous solution of the amine aqueous solutions such as amine, ethylenediamine etc..In addition it is also possible to add surfactant etc. in these developer solutions.
In above-mentioned developer solution, usually using the tetraethyl ammonium hydroxide aqueous solution of 0.1~2.38 mass % as photic
The developer solution of resist will not be caused molten even if in the photosensitive polymer combination of the present invention using the alkaline-based developer
The problems such as swollen, can develop well.
In addition, as developing method, liquid pool method, infusion process, shake infusion process etc. can use.Developing time at this time
Usually 15~180 seconds.
After development, the washing for carrying out such as 20~90 seconds to negative photosensitive resin film by flowing water, then by making
Removed with compressed air or compressed nitrogen or by moisture on rotary wind capable person's substrate, to obtain formed it is figuratum
Film.
Then, the rear baking for heat cure is carried out by forming film to this pattern, specifically, by using heating
Plate, baking oven etc. are heated, can obtain heat resistance, the transparency, planarization property, low water absorbable, chemical-resistant etc. it is excellent and
Film with good embossed pattern.
As rear baking, the following method of generally use, under the heating temperature in 140 DEG C~250 DEG C temperature ranges,
In the case of on hot plate, handle 5~30 minutes, in an oven in the case of, handle 30~90 minutes.
Then, by this rear baking, the cured film with good pattern form of target can be obtained.
As described above, the film with fine pattern can be formed using the negative light-sensitive resin combination of the present invention,
The film does not have viscosity before exposure, can alkali development, there is adequately high sensitivity for 10 μm or so of film thickness
Degree, and in development, the film reduction of exposure portion is very small.In addition, the cured film is transparent, heat resistance and excellent solvent resistance.
Therefore, the various films that can be suitably used in liquid crystal display, organic el display, touch panel element etc., such as interlayer
Insulating film, protective film, insulating film, optical film etc..
Embodiment
The present invention will be described in more detail in a manner of enumerating embodiment below, but the present invention is not by these realities
Apply the restriction of example.
[dummy suffix notation used in embodiment]
The meaning of dummy suffix notation used in following embodiment is as described below.
MAA：Methacrylic acid
MI：Maleimide
MMA：Methyl methacrylate
BMAA：N- (n-butoxy methyl) acrylamide
HEMA：2-hydroxyethyl methacrylate
GMA：Glycidyl methacrylate
ST：Styrene
AIBN：Azodiisobutyronitrile
PAG1：TPS-TF (Japan synthesizes (strain) production) (chemical combination name：Triphenylsulfonium triflate sulfonate)
PAG2：GSID-26-1 (BASF productions) (compound represented by previously described formula (79))
PAG3：IRGACURE369 (BASF productions) (Photoepolymerizationinitiater initiater)
CYM：303 (ProductName) (chemical combination name of サ イ メ Le of サ イ テ ッ Network ジ ャ パ Application production：Hexamethoxy methyl
Melamine)
HMA：9- hydroxymethyl anthracenes
HPC：Hydroxy propyl cellulose
DPHA：Five/six acrylate of dipentaerythritol
BTEAC：Benzyl triethyl ammonium chloride
PGME：Propylene glycol monomethyl ether
PGMEA：Propylene glycol methyl ether acetate
JE：The JER157S70 of ジ ャ パ Application エ Port キ シ レ ジ Application (strain) production
[measurement of number-average molecular weight and weight average molecular weight]
Using the GPC devices (Shodex (registered trademark) column KF803L and KF804L) of Japan's light splitting (strain) production, make
Eluting solvent tetrahydrofuran with 1ml/ minutes flows in column (40 DEG C of column temperature) flow and elute under conditions of to according to
The number-average molecular weight and weight average molecular weight of specific copolymer and specific crosslinked that lower synthesis example obtains are measured.Under in addition,
Number-average molecular weight (the hereinafter referred to as Mn stated.) and weight average molecular weight (hereinafter referred to as Mw.) all indicated with polystyrene scaled value.
1 ＞ of ＜ synthesis examples
Using MI (26.0g), BMAA (45.0g), ST (29.0g) as the monomer component for forming copolymer, AIBN is used
(2g) is used as radical polymerization initiator, by making them carry out polymerisation in solvent PGME (238g), obtains
Copolymer solution (the copolymer concentration of Mn4300, Mw9800：30 mass %) (P1).In addition, polymerization temperature is adjusted to 60 DEG C
~90 DEG C of temperature.
2 ＞ of ＜ synthesis examples
Using MAA (20.0g), BMAA (50.0g), ST (30.0g) as the monomer component for forming copolymer, AIBN is used
(2g) is used as radical polymerization initiator, by making them carry out polymerisation in solvent PGME (238g), obtains
Copolymer solution (the copolymer concentration of Mn4000, Mw9200：30 mass %) (P2).In addition, polymerization temperature is adjusted to 60 DEG C
~90 DEG C of temperature.
3 ＞ of ＜ synthesis examples
Using MAA (20.0g), BMAA (50.0g), HEMA (30.0g) as the monomer component for forming copolymer, use
AIBN (2g) is used as radical polymerization initiator, by making them carry out polymerisation in solvent PGME (238g), obtains
Copolymer solution (the copolymer concentration of Mn4800, Mw10500：30 mass %) (P3).In addition, polymerization temperature is adjusted to 60 DEG C
~90 DEG C of temperature.
4 ＞ of ＜ synthesis examples
Using MAA (20.0g), HEMA (40.0g) MMA (40.0g) as the monomer component for forming copolymer, AIBN is used
(2g) is used as radical polymerization initiator, by making them carry out polymerisation in solvent PGME (238g), obtains
Copolymer solution (the copolymer concentration of Mn3900, Mw8500：30 mass %) (P4).In addition, polymerization temperature is adjusted to 60 DEG C
~90 DEG C of temperature.
＜ compares 1 ＞ of synthesis example
Using MAA (50.0g), MMA (50.0g) as the monomer component for forming copolymer, using AIBN (2g) as certainly
By base polymerization initiator copolymer solution is obtained by making them carry out polymerisation in solvent PGMEA (120g) (altogether
Oligomer concentrations：40 mass %).In addition, polymerization temperature to be adjusted to 60 DEG C~90 DEG C of temperature.By in the 200g copolymers
Be added GMA (33.0g), BTEAC (1.1g), PGMEA (49.5g) and reacted, obtain (A) of Mn8700, Mw22000 at
Divide solution (the specific copolymer concentration of (specific copolymer)：40.5 mass %) (P5).In addition, reaction temperature is adjusted to 90~
120℃。
＜ compares 2 ＞ of synthesis example
Using MAA (30.0g), GMA (50.0g), ST (20.0g) as the monomer component for forming copolymer, AIBN is used
(2g) is used as radical polymerization initiator, although them is made to be carried out at a temperature of 60 DEG C~90 DEG C in solvent PGME (238g)
Polymerisation, but the evaluation after gelation occurs in polymerisation and cannot be used for.
1~2 ＞ of ＜ Examples 1 to 7 and comparative example
It is formed according to shown in the following table 1, with defined ratio mixing (B) ingredient, (C) solvent in the solution of (A) ingredient
(D) ingredient and (E) ingredient and (F) ingredient, are stirred at room temperature 3 hours, form uniform solution, each to modulate
The negative light-sensitive resin combination of embodiment and each comparative example.
Table 1
For the Examples 1 to 7 and comparative example 1 that are obtained and 2 each negative light-sensitive resin combination, measure respectively
Film thickness after prebake conditions has inviscid, transmissivity, resolution ratio, susceptibility.
[evaluation of film thickness after prebake conditions]
Negative light-sensitive resin combination is coated on silicon chip using spin coater, is then being added at a temperature of 110 DEG C
120 seconds prebake conditions are carried out on hot plate, to form film.The film thickness of the film is measured using the FILMETRICS F20 produced.
[evaluation of transmissivity]
Negative light-sensitive resin combination is coated on a quartz substrate, then at a temperature of 110 DEG C using spin coater
120 seconds prebake conditions are carried out on hot plate, to form film.The ultraviolet lamp PLA- produced by キ ャ ノ Application
600FA is 5.5mW/cm with the luminous intensity at 365nm2Ultraviolet light to the film irradiate 36 seconds.It should at a temperature of 95 DEG C
Film heats after carrying out exposure in 120 seconds on hot plate, is toasted after then carrying out 15 minutes in an oven at a temperature of 150 DEG C,
To form cured film.Use ultraviolet light visible spectrophotometer (the SIMADSU UV-2550 types of (strain) Shimadzu Seisakusho Ltd. production
Number) to the transmissivity of cured film measurement 400nm wavelength.
[evaluation of resolution ratio]
Negative light-sensitive resin combination is coated on alkali-free glass using spin coater, then at a temperature of 110 DEG C
120 seconds prebake conditions are carried out on hot plate, to form film.The ultraviolet lamp produced using キ ヤ ノ Application (strain)
PLA-600FA is 5.5mW/cm with the luminous intensity at 365nm2Ultraviolet light by the masks of line ＆ intermittent patterns to the film into
Row 190mJ/cm2Irradiation.Then, it is heated after carrying out exposure in 120 seconds on hot plate at a temperature of 110 DEG C.Then by
It impregnates 60 seconds and develops in tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution of 2.38 mass %, then using super
Pure water carries out 20 seconds water displacement wash, to form pattern.The pattern made is calcined 15 minutes in 150 DEG C of baking oven, it is right
Pattern after calcining carries out SEM observations, and the line width of the pattern minimum pattern size consistent with the line width of mask is set as resolution ratio.
[evaluation of susceptibility]
Negative light-sensitive resin combination is coated on alkali-free glass using spin coater, then at a temperature of 110 DEG C
120 seconds prebake conditions are carried out on hot plate, to form film.The ultraviolet lamp produced using キ ヤ ノ Application (strain)
PLA-600FA is 5.5mW/cm with the luminous intensity at 365nm2Ultraviolet light by the masks of 20 μm of line ＆ intermittent patterns every
50mJ/cm2The film is irradiated.Then, it is heated after carrying out exposure in 120 seconds on hot plate at a temperature of 110 DEG C.So
Developed by being impregnated 60 seconds in the TMAH aqueous solutions in 2.38 mass % afterwards, then ultra-pure water is used to carry out 20 seconds flowing water
Washing, to form pattern.The lowest exposure amount that 20 μm of pattern will be formed is set as susceptibility.
[result of evaluation]
It is as shown in table 2 below to carry out the above result evaluated.
Table 2
As judged by result shown in table 2, the equal energy of negative light-sensitive resin combination of Examples 1 to 7
It is enough to be coated with 10 μm or more of thick film, for thick film with high-transmission rate and can alkali development, and keep high-resolution, quick
Sensitivity.
For comparative example 1, can not thick-film, the residual film ratio after rear baking is also 90% hereinafter, be low.For comparative example
2, there is viscosity after prebake conditions, can not be developed using alkaline developer.
Industrial availability
Negative light-sensitive resin combination according to the present invention is suitable as forming thin film transistor (TFT) (TFT) type liquid crystal
Show the cured films such as protective film, planarization film, the insulating film in the various displays such as element, organic EL element, touch panel element
Material, be particularly suitable as being formed the interlayer dielectric of TFT type liquid crystal cells, the protective film of colour filter, array planarization film,
The interlayer dielectric of capacitive touch panels, the insulating film of organic EL element, as the tectosome of display surface anti-reflecting layer
The material of plate etc..
Claims (8)
1. a kind of negative light-sensitive resin combination, containing following (A) ingredients, (B) ingredient and (C) solvent,
(A) ingredient：Copolymer made of being copolymerized by monomer mixture, the monomer mixture at least contain (i) N- alkoxy first
Base (methyl) acrylamide and (ii) have the monomer of alkali solubility group,
(B) ingredient：Photoacid generator,
(C) solvent,
It is maleimide that (ii) for (A) ingredient, which has the monomer of alkali solubility group,.
2. negative light-sensitive resin combination according to claim 1, the photosensitive resin composition based on 100 mass parts
Object, the sensitizer for also containing 0.1~10 mass parts are used as (D) ingredient.
3. negative light-sensitive resin combination according to claim 1 or 2 also contains the polymer conduct with hydroxyl
(E) ingredient.
4. negative light-sensitive resin combination according to claim 1 or 2, (A) ingredient be by monomer mixture copolymerization and
At copolymer, the monomer mixture also contain with hydroxyl monomer.
5. negative light-sensitive resin combination according to claim 1 or 2 also contains crosslinking agent and is used as (F) ingredient.
6. a kind of cured film is obtained using the negative light-sensitive resin combination described in any one of Claims 1 to 55
's.
7. a kind of liquid crystal display interlayer dielectric, it includes the cured films described in claim 6.
8. a kind of optical light filter, it includes the cured films described in claim 6.
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| JP2012-008689 | 2012-01-19 | ||
| JP2012008689 | 2012-01-19 | ||
| PCT/JP2013/050428 WO2013108716A1 (en) | 2012-01-19 | 2013-01-11 | Negative photosensitive resin composition |
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| CN104040432B true CN104040432B (en) | 2018-09-14 |
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| KR (1) | KR102027756B1 (en) |
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| JP6624379B2 (en) * | 2013-10-21 | 2019-12-25 | 日産化学株式会社 | Negative photosensitive resin composition |
| JP6572769B2 (en) | 2014-01-24 | 2019-09-11 | 東レ株式会社 | Negative photosensitive resin composition, cured film obtained by curing the same, method for producing the same, optical device including the same, and back-illuminated CMOS image sensor |
| JP6807752B2 (en) * | 2014-06-03 | 2021-01-06 | ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー | Protective layer containing photocrosslinked fluoropolymer |
| KR20190116319A (en) * | 2017-02-22 | 2019-10-14 | 닛산 가가쿠 가부시키가이샤 | Cured film formation composition, orientation material, and phase difference material |
| CN110392864B (en) * | 2017-03-29 | 2023-05-23 | 东丽株式会社 | Negative photosensitive resin composition, cured film, element and organic EL display having cured film, and method for producing same |
| CN110412829A (en) * | 2018-04-26 | 2019-11-05 | 东友精细化工有限公司 | Negative light-sensitive resin combination, photocuring pattern and image display device |
| KR102170935B1 (en) * | 2019-08-28 | 2020-10-29 | 주식회사 삼양사 | A curable resin composition and an electronic device comprising a cured layer formed therefrom |
| JP7393229B2 (en) | 2020-01-31 | 2023-12-06 | Ntn株式会社 | Power supply and demand adjustment system and power supply and demand adjustment method |
| CN115160495A (en) * | 2022-08-15 | 2022-10-11 | 四川华造宏材科技有限公司 | Photoresist film-forming resin containing maleimide structure and preparation method thereof |
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- 2013-01-11 CN CN201380004941.6A patent/CN104040432B/en active Active
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| CN1558918A (en) * | 2001-09-25 | 2004-12-29 | 大日本印刷株式会社 | Alkali-soluble maleimide copolymer and liquid crystal display comprising the same |
| CN1532566A (en) * | 2003-03-06 | 2004-09-29 | Jsr株式会社 | Radiation sensitive composition for color filter |
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| JPWO2013108716A1 (en) | 2015-05-11 |
| KR20140117512A (en) | 2014-10-07 |
| TWI569100B (en) | 2017-02-01 |
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| TW201348876A (en) | 2013-12-01 |
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